US 20090264669A1 (19) United States (12) Patent Application Publication (10) Pub. No.: US 2009/0264669 A1 Upshaw (43) Pub. Date: Oct. 22, 2009

(54) METHODS AND SYSTEMIS FOR MAKING Publication Classification THOL COMPOUNDS FROM TERMINAL (51) Int. Cl. OLEFINIC COMPOUNDS C07C327/00 (2006.01) (75) Inventor: Thomas A. Upshaw, Bartlesville, OK (US) (52) U.S. Cl...... 558/250 Correspondence Address: (57) ABSTRACT CHEVRON PHILLIPS CHEMICAL COMPANY LP The application discloses thiol ester molecules and C-hy LAW DEPARTMENT - IP, PO BOX 4910 droxy thiol ester molecules having a thiol group located on THE WOODLANDS, TX 77387-4910 (US) one of the final two carbon atoms in a carbon chain or a terminal or C-hydroxyl groups, respectively. The disclosed (73) Assignee: Chevron Phillips Chemical thiolester molecules and or C-hydroxylthiol ester molecules Company LP. The Woodlands, TX es may be made from unsaturated ester molecules having one (US) or more terminal alkene groups. The disclosed techniques also provide methods for making unsaturated ester molecules (21) Appl. No.: 12/427,467 having one or more terminal alkene groups by the metathesis of unsaturated esters having one or more internal carbon (22) Filed: Apr. 21, 2009 carbon double bonds (e.g. natural source oils). The thiolester molecules or C-hydroxy thiol ester molecule may be used in Related U.S. Application Data reactions with isocyanate monomers, epoxide monomer, or (60) Provisional application No. 61/046,701, filed on Apr. material having multiple alkene groups to make sealants, 21, 2008. coatings, adhesives, and other products. US 2009/0264669 A1 Oct. 22, 2009

METHODS AND SYSTEMIS FOR MAKING of 9 to 16 weight %. In an embodiment, the thiol ester mol THOL COMPOUNDS FROM TERMINAL ecules of the thiol ester composition has an average ratio of OLEFINIC COMPOUNDS thiol groups located on a terminal carbonatom to thiol groups located on the carbon atom adjacent to the terminal carbon CROSS REFERENCE TO RELATED atom is greater than 5:1. In an embodiment, the average ratio APPLICATIONS of carboxylic acid residues having a thiol group located on a 0001. This Application claims the benefit of the provi terminal carbon atom or a carbon atom adjacent to the termi sional patent application having U.S. Ser. No. 60/046.701 nal carbon atom to hydroxyl groups of the polyol of the filed on Apr. 21, 2008, which hereby is incorporated by ref residue of the polyol is greater than 0.70:1. In a particular erence in its entirety. embodiment, the thiol ester molecules of the thiol ester com position comprise have ester linkages comprising a) a polyol BACKGROUND residue derived from cyclohexane diol, trimethylol propane, glycerol, pentaerythritol, or combinations thereof, and b) car 0002. This section is intended to introduce the reader to boxylic acid residues having a thiol group located on a ter aspects of art that may be related to aspects of the present minal carbon atom or a carbon atom adjacent to the terminal techniques, which are described herein. This discussion is carbonatom having from 10 to 11 carbonatoms wherein thiol believed to be helpful in providing the reader with back ester molecules have an average ratio of thiol groups located ground information to facilitate a better understanding of the on a terminal carbon atom to thiol groups located on the various aspects of the present techniques. Accordingly, it carbon atom adjacent to the terminal carbon atom is greater should be understood that these statements are to be read in than 5:1, and wherein the thiol ester molecules have an aver this light, and not as admissions of prior art. age thiol sulfur content of 9 to 16 weight%. 0003. As chemical and petrochemical technologies have 0006. The thiol ester compositions comprising the thiol advanced, the products of these technologies have become ester molecules having thiol groups located on a terminal increasingly prevalent in Society. In particular, as techniques carbon atom or on a carbon atom adjacent to the terminal for bonding simple molecular building blocks into longer carbon atom may be produced by a) contacting ethylene and chains, termed polymers, have advanced, the polymer prod natural source oil with a metathesis catalyst composition, b) ucts, typically in the form of various plastics, have been forming unsaturated ester molecules having terminal carbon increasingly incorporated into various everyday items. For carbon double bonds at metathesis conditions capable of example, polyurethane polymers and copolymers, made from forming the unsaturated ester molecules having terminal car the reactions of compounds containing hydroxyl groups with bon-carbon double bonds, c) contacting the unsaturated ester compounds containing isocyanate groups, may be used in molecules having terminal carbon-carbon double bonds and retail and pharmaceutical packaging, furniture, household hydrogen Sulfide, and d) forming the thiol ester composition items, automobile components, adhesives, coatings, and vari comprising thiol ester molecules having the thiol group ous other consumer and industrial products. located on the terminal carbon atom at conditions capable of 0004. The chemical industry strives to make these prod forming thiol ester molecules having the thiol group located ucts with low-cost feedstocks that are in abundant Supply. on the terminal carbon. In an embodiment, wherein the met Currently, the main feedstocks for polyurethanes, and other athesis catalyst composition comprises ruthenium carbene plastics, are petrochemicals isolated from petroleum. How metathesis catalyst or a molybdenum carbene metathesis ever, as fossil fuels deplete over time, alternative sources are catalyst. In some embodiments, metathesis catalyst com being sought as replacements for feedstocks. Further, the prises dichloro(phenylmethylene)bis(tricyclohexylphos chemical industry continuously strives to produce products phine) ruthenium or 1,3-bis-(2,4,6-trimethylphenyl)-2-(imi and use feedstocks that are environmentally friendly. dazolidinylidene)(phenylmethylene) dichloro (tricyclohexylphosphine)ruthenium. In an embodiment, the SUMMARY OF THE INVENTION metathesis conditions include a ethylene partial pressure 0005 Disclosed herein are thiol ester composition com ranging from 50 to 3000 psig and a temperature ranging from prising thiol ester molecules having ester linkages compris 5° C. to 100° C. In an embodiment, the natural source oil ing a) a residue of a polyol and a carboxylic acid residues comprises a tallow oil, an olive oil, a peanut oil, a castor bean having i) at least 4 carbon atoms and ii) a thiol group located oil, a Sunflower oil, a sesame oil, a poppy seed oil, a palm oil, on a terminal carbon atom or a carbon atom adjacent to the an almond seed oil, a hazelnut oil, a rapeseed oil, a canola oil, terminal carbon atom. In an embodiment, the polyol of the a Soybean oil, a corn oil, a safflower oil, a cottonseed oil, a residue of polyol was a diol, triol, or a tetraol. In some camelina oil, a flaxseed oil, or a walnut oil, or any combina embodiments, the polyol of the residue of polyol was cyclo tion thereof. In some embodiments, the natural Source oil is hexane diol, trimethylol propane, glycerol, pentaerythritol, or Soybean oil, corn oil, canola oil, or castor bean oil. In other combinations thereof. In other embodiments, the polyol of embodiments, the natural Source oil is soybean oil. the residue of polyol was glycerol. In an embodiment, the 0007 Disclosed herein are thiol ester composition com carboxylic acid residues having a thiol group located on a prising thiol ester molecules having ester linkages compris terminal carbon atom or a carbon atom adjacent to the termi ing a) a residue of a polyol and a carboxylic acid residues nal carbon atom have from 10 to 11 carbon atoms. In some having i) at least 4 carbon atoms and ii) a terminal C-hydroxy embodiments, the carboxylic acid residues having the thiol thiol group. In an embodiment, the polyol of the residue of group located on the terminal carbonatom or the carbonatom polyol was a diol, triol, or a tetraol. In some embodiments, the adjacent to the terminal carbon atom have only 10 carbon polyol of the residue of polyol was cyclohexane diol, trim atoms. In other embodiments, the carboxylic acid residues are ethylol propane, glycerol, pentaerythritol, or combinations Substantially devoid of hydroxyl groups. In an embodiment, thereof. In other embodiments, the polyol of the residue of the the thiol ester molecules have an average thiol sulfur content polyol is derived from glycerol. In an embodiment, the car US 2009/0264669 A1 Oct. 22, 2009

boxylic acid residues having a terminal C-hydroxy thiol 0011. The terms “a,” “an, and “the are intended, unless group have from 10 to 111 carbon atoms. In an embodiment, specifically indicated otherwise, to include plural alterna the carboxylic acid residues having a terminal C-hydroxy tives, e.g., at least one. For instance, the disclosure of "a thiol thiol group has only 10 carbonatoms. In an embodiment, the compound is meant to encompass one, or mixtures or com thiolester molecules have an average thiol sulfur content of 9 binations of more than one, thiol compound, unless otherwise to 16 weight %. In an embodiment, the average ratio of specified. carboxylic acid residues having a terminal C-hydroxy thiol 0012. As used in this disclosure, the term “composition' group to hydroxyl groups of the polyol of the residue of the indicates a system that includes molecules having the indi polyol is greater than 0.70:1. In a particular embodiment, the cated features. The molecules may have a variety of struc thiolester molecules of the thiol ester composition have ester tures, which have the indicated described herein. Further, a linkages comprising a) a polyol residue derived from cyclo composition may have a variety of other components present, hexane diol, trimethylol propane, glycerol, pentaerythritol, or both intentional and unintentional, which do not have the combinations thereof, and b) a carboxylic acid residues hav indicated features and may or may not participate in the ing a terminal C-hydroxy thiol group having from 10 to 11 reactions described herein. carbon atoms, and wherein the thiol ester molecules have an 0013 The term “hydrocarbyl group' is used herein in average thiol sulfur content of 9 to 16 weight%. accordance with the definition specified by IUPAC: a univa 0008. The thiol ester compositions comprising the thiol lent group formed by removing a hydrogen atom from a ester molecules having a terminal C-hydroxy thiol group may hydrocarbon (i.e., a group containing only carbon and hydro be produced by a) contacting ethylene and natural source oil gen). Similarly, a “hydrocarbylene group' refers to a group with a metathesis catalyst composition, b) forming unsatur formed by removing two hydrogenatoms from a hydrocarbon ated ester molecules having terminal carbon-carbon double (either two hydrogen atoms from one carbon atom or one bonds at metathesis conditions capable of forming the unsat hydrogen atom from two different carbon atoms). A “hydro urated ester molecules having terminal carbon-carbon double carbon group' refers to a generalized group formed by bonds, c) contacting the unsaturated ester molecules having removing one or more hydrogen atoms (as necessary for the terminal carbon-carbon double bonds and an oxygen contain particular group) from a hydrocarbon. A “hydrocarbyl ing compound, d) forming an epoxide ester molecules having group.” “hydrocarbylene group, and "hydrocarbon group' terminal epoxide groups at conditions capable of forming can be acyclic or cyclic groups, and/or may be linear or epoxide ester molecules having terminal epoxide groups, e) branched. A “hydrocarbyl group,” “hydrocarbylene group.” contacting the epoxide ester molecules and hydrogen sulfide, and "hydrocarbon group can include rings, ring Systems, and f) forming the thiol ester composition comprising thiol aromatic rings, and aromatic ring systems, which contain ester molecules having a terminal C-hydroxy thiol groups at only carbon and hydrogen. “Hydrocarbyl groups.” “hydro conditions capable of forming thiol ester molecules. In an carbylene groups, and “hydrocarbon groups' include, by embodiment, the metathesis catalyst composition comprises way of example, aryl, arylene, alkyl, alkylene, cycloalkyl, ruthenium carbene metathesis catalyst or a molybdenum car cycloalkylene, aralkyl, aralkylene, and combinations of these bene metathesis catalyst. In some embodiments, the metathe groups, among others. Finally, it should be noted that the sis catalyst comprises dichloro(phenylmethylene)bis(tricy “hydrocarbyl group,” “hydrocarbylene group, or “hydrocar clohexylphosphine) ruthenium O 1,3-bis-(2,4,6- bon group' definitions include “alkyl group,” “alkylene trimethylphenyl)-2-(imidazolidinylidene) group, and “alkyl groups.” respectively, as members. (phenylmethylene)dichloro (tricyclohexylphosphine) 0014. The term “alkyl group' is used herein in accordance ruthenium. In an embodiment, the metathesis conditions with the definition specified by IUPAC: a univalent group include a ethylene partial pressure ranging from 50 to 3000 formed by removing a hydrogen atom from an alkane. Simi psig and a temperature ranging from 5°C. to 100° C. In an larly, an “alkylene group' refers to a group formed by remov embodiment, the natural source oil comprises a tallow oil, an ing two hydrogenatoms from an alkane (either two hydrogen olive oil, a peanut oil, a castor bean oil, a Sunflower oil, a atoms from one carbonatom or one hydrogen atom from two sesame oil, a poppy seed oil, a palm oil, an almond seed oil, a different carbon atoms). An "alkane group' refers to a gen hazelnut oil, a rapeseed oil, a canola oil, a soybean oil, a corn eralized group formed by removing one or more hydrogen oil, a safflower oil, a cottonseed oil, a camelina oil, a flaxseed atoms (as necessary for the particular group) from a alkane. oil, or a walnut oil, or any combination thereof. In some An “alkyl group.” “alkylene group, and "alkane group' can embodiments, the natural source oil is soybean oil, corn oil, be acyclic or cyclic groups, and/or may be linear or branched canola oil, or castor bean oil. In other embodiments, the unless otherwise specified. natural source oil is soybean oil. 0015 The term “organyl group” in used herein in accor dance with the definition specified by IUPAC: an organic DEFINITIONS Substituent group, regardless of functional type, having one free Valence at a carbon atom. Similarly, an “organylene 0009. To define more clearly the terms used herein, the group' refers to an organic group, regardless of functional following definitions are provided. To the extent that any type, formed by removing two hydrogen atoms from an definition or usage provided by any document incorporated organic compound (either two hydrogenatoms from one car herein by reference conflicts with the definition or usage bon atom or one hydrogen atom from two different carbon provided herein, the definition or usage provided herein con atoms) and an “organic group' refers to a generalized organic trols. group formed by removing one or more hydrogenatoms from 0010 While compositions and methods are described in an organic compound. Thus, an “organyl group, an “orga terms of "comprising various components or steps, the com nylene group, and an “organic group' can contain organic positions and methods can also “consist essentially of or functional group(s) and/or atom(s) other than carbon and “consist of the various components or steps. hydrogen (i.e., an organic group that can comprise functional US 2009/0264669 A1 Oct. 22, 2009 groups and/or atoms in addition to carbon and hydrogen). For not mean that the step of forming the particular ester occurs instance, non-limiting examples of atoms other than carbon via a reaction between the polyol and carboxylic acid, unless and hydrogen include halogens, oxygen, nitrogen, phospho specifically recited as Such. The description is only a method rus, and the like. Non-limiting examples of functional groups for describing the particular ester. include ethers, aldehydes, ketones, esters, sulfides, amines, (0022. The term “polyol of the residue of the polyol” refers and phosphines, and so forth. An "organyl group.” “orga to the parent polyol that formed the residue of the polyol. nylene group.” or “organic group' may be aliphatic, inclusive 0023 For any particular compound disclosed herein, any of being cyclic or acyclic, or aromatic. “Organyl groups.” structure presented also encompasses all conformational iso "organylene groups, and "organic groups' also encompass mers, regioisomers, and stereoisomers that may arise from a heteroatom-containing rings, heteroatom-containing ring particular set of substituents, unless otherwise specified. The systems, heteroaromatic rings, and heteroaromatic ring sys structure also encompasses all enantiomers, diastereomers, tems. “Organyl groups.” “organylene groups.” and "organic and other optical isomers whether in enantiomeric or racemic groups' may be linear or branched unless otherwise specified. forms, as well as mixtures of stereoisomers, as would be Finally, it should be noted that the “organyl group,” “orga recognized by a skilled artisan, unless otherwise specified. nylenegroup. or “organic group' definitions include “hydro 0024 All publications and patents mentioned herein are carbyl group.” “hydrocarbylene group.” “hydrocarbon incorporated herein by reference for the purpose of describ group respectively, and “alkyl group,” “alkylene group.” ing and disclosing the constructs and methodologies and “alkyl group.’ respectively, as members. described in the publications, which might be used in con 0016. The term “natural refers to materials obtained, by nection with the presently described invention. The publica any method, from naturally occurring fruits, nuts, vegetables, tions discussed throughout the text are provided solely for plants and animals. As an example, “natural source oil” refers their disclosure prior to the filing date of the present applica to source oils extracted, and optionally purified, from natu tion. Nothing herein is to be construed as an admission that rally occurring fruits, nuts, vegetables, plants and animals. the inventors are not entitled to antedate such disclosure by Additionally, “unsaturated natural source oil” refers to unsat virtue of prior invention. urated source oils extracted, and optionally purified, from naturally occurring fruits, nuts, vegetables, plants, and ani DETAILED DESCRIPTION mals. It should be noted that “natural source oil and “unsat urated natural source oil also includes the respective oils 0025. The present techniques generally relate to thiolester extracted, and optionally purified, from genetically modified compositions comprising thiol ester molecules having a thiol nuts, vegetables, plant, and animal sources. group located on a terminal carbon atom or a thiol group 0017. The term “natural source raw material” refers to located on a carbonatom adjacent to a terminal carbon atom. materials obtained by extraction, chemical breakdown, or The present techniques, also relate to C-hydroxy thiol ester chemical processing of “natural materials. A non-limiting compositions comprising, or consisting essentially of thiol example includes natural Source oils that can be extracted ester molecules having a terminal C-hydroxy thiol group. from naturally occurring fruits, nuts, vegetables, plants and 0026 Generally, the techniques for forming thiol ester animals. As another non-limiting example, glycerol and car compositions comprising thiol ester molecules having a thiol boxylic acids or carboxylic acid esters, Saturated or unsatur group located on a terminal carbon atom or a thiol group ated, can be produced and isolated by the chemical processing located on a carbon atom adjacent to a terminal carbon atom of triglycerides extracted from naturally occurring fruits, include forming unsaturated ester compositions comprising, nuts, vegetables, plants, and animals. or consisting essentially of unsaturated ester molecules hav 0018. The term “thiol ester composition” refers to a com ing terminal carbon-carbon double bonds and reacting the position that includes “thiol ester molecules. The thiol ester unsaturated ester compositions comprising, or consisting molecule has at least one thiol group and at least one ester essentially of unsaturated ester molecules having terminal group within the thiol ester molecule. carbon-carbon double bonds to form the thiolester composi 0019. The term “hydroxy thiol ester composition” refers tions comprising thiol ester molecules having a thiol group to a composition that includes “hydroxy thiol ester mol located on a terminal carbonatom or a thiol group located on ecules.” The hydroxy thiol ester molecule has at least one a carbon atom adjacent to a terminal carbon atom. The tech thiol group, at least one ester group, and at least one hydroxy niques for forming the C-hydroxy thiol ester compositions or alcohol group within the hydroxy thiolester molecule. The comprising, or consisting essentially of thiolester molecules term "O-hydroxy thiol ester” refers to a composition that having a terminal C-hydroxy thiol group generally include includes “C.-hydroxy thiol ester molecules. The C-hydroxy forming unsaturated ester compositions comprising, or con thiol ester molecule has at least one thiol group, and one sisting essentially of unsaturated ester molecules having ter “O-hydroxy thiol group. The “O-hydroxy thiol group” has a minal carbon-carbon double bonds and reacting the unsatur hydroxy group and a thiol group on adjacent carbon atoms. ated ester compositions comprising, or consisting essentially 0020. The term “unsaturated ester composition” refers to a of unsaturated ester molecules having terminal carbon-car composition that includes “unsaturated ester molecules. The bon double bonds with an oxygen containing compound to unsaturated ester molecules have at least one ester group and form an epoxide ester composition comprising, or consisting at least one carbon-carbon double bond within the unsatur essentially of epoxide ester molecules having terminal ated ester molecule. epoxide groups, and Subsequently reacting the epoxide ester 0021. An ester molecule having an ester linkage compris composition comprising, or consisting essentially of epoxide ing a residue of a polyol and a carboxylic acid residue ester molecules having terminal epoxide groups, with hydro describes esters formed via the combination of the hydroxy gen sulfide to form an O-hydroxy thiol ester compositions group(s) of the polyol and the carboxylic acid group of the comprising, or consisting essentially of thiolester molecules carboxylic acid. It should be noted that this description does having a terminal C-hydroxy thiol group. US 2009/0264669 A1 Oct. 22, 2009

0027. The thiolester compositions comprising, or consist carbon atom adjacent to a terminal carbon atom of the thiol ing essentially of thiol ester molecules having a thiol group ester molecule may not have the same number of functional located on a terminal carbon atom or a thiol group located on groups, the same ratios of functional groups, and/or the same a carbon atom adjacent to a terminal carbon atom and the additional features. Thus, the number of functional group, C-hydroxy thiolester compositions comprising, or consisting ratios of functional groups, and/or additional features of the essentially of thiol ester molecules having a terminal C-hy thiol ester molecules having thiol groups located on terminal droxy thiol group may have advantages over previous mate carbon atoms and/or thiol groups located on a carbon atom rials. For example, the close proximity of the thiol groups to adjacent to a terminal carbonatom of the thiolester molecule a terminal carbonatom may provide advantages in producing may be referred to as an average per thiol ester molecule thiourethanes, polythiourethanes, epoxy compositions, and within the thiol ester composition. materials produced utilizing the thiol-ene reaction. 0032. In an embodiment, the thiol ester molecules having 0028. One or more specific embodiments of the composi thiol groups located on terminal carbon atoms and/or thiol tions and techniques to produce the compositions are groups located on a carbonatom adjacent to a terminal carbon described herein. In an effort to provide a concise description atom have at least 2 ester groups; alternatively at least 3 ester of these embodiments, not all features of an actual implemen groups; or alternatively, at least 4 ester groups. In other tation are described. It should be appreciated that in the devel embodiments, the thiol ester molecules having thiol groups opment of any such actual implementation, as in any engi located on terminal carbonatoms and/or thiol groups located neering or design project, numerous implementation-specific on a carbon atom adjacent to a terminal carbon atom have decisions must be made to achieve the developer's specific from 2 to 8 ester; alternatively, 3 to 6 ester groups; alterna goals, such as compliance with system-related and business tively, 3 to 4 ester groups; alternatively, only 3 ester groups; or related constraints, which may vary from one implementation alternatively, only 4 ester groups. In further embodiments, the to another. Moreover, it should be appreciated that such a thiol ester molecules having thiol groups located on terminal development effort might be complex and time consuming, carbon atoms and/or thiol groups located on a carbon atom but would nevertheless be a routine undertaking of design, adjacent to a terminal carbonatom have an average of at least fabrication, and manufacture for those of ordinary skill hav 2 ester groups per thiolester molecule; alternatively, an aver ing the benefit of this disclosure. age of at least 2.5 ester groups per thiol ester molecule; or alternatively, an average of at least 3 ester groups per thiol Thiol Ester Compositions ester molecule. In yet further embodiments, the thiol esters 0029. In an aspect, the present invention relates to thiol have an average of from 2 to 8 ester groups per thiol ester ester compositions comprising, or consisting essentially of molecule; alternatively, an average of from 2 to 7 ester groups thiol ester molecules having a thiol groups located on termi per thiolester molecule; alternatively, an average of from 2.5 nal carbonatoms and/or thiol groups located on a carbonatom to 5 ester groups per thiol ester molecule; or alternatively, an adjacent to a terminal carbon atom. In an aspect, thiol ester average of from 3 to 4 ester groups perthiolester molecule. In molecules may be described as comprising, consisting essen yet other embodiments, the thiolester molecules having thiol tially of one or more functional groups present in the thiol groups located on terminal carbon atoms and/or thiol groups ester molecules of the thiol ester composition. Each of the located on a carbon atom adjacent to a terminal carbon atom functional groups that may be present in the thiol ester mol have an average of about 3 ester groups per thiol ester mol ecules are independently described herein and may be uti ecule; or alternatively, an average of about 4 ester groups per lized in any combination to describe the thiolester molecules. thiol ester molecule. 0030 The independent functional groups that can be uti 0033. In an embodiment, the thiol ester molecules having lized to describe the thiol ester molecules having a thiol thiol groups located on terminal carbon atoms and/or thiol groups located on terminal carbon atoms and/or thiol groups groups located on a carbonatom adjacent to a terminal carbon located on a carbon atom adjacent to a terminal carbon atom atom of the thiol ester composition have at least 2 thiol include: the location of the thiol group, the number of (or groups; alternatively, at least 3 thiol groups; or alternatively, average number of) ester groups per thiol ester molecule, the at least 4thiol groups. In other embodiments, the thiol ester number of (or average number of) thiol groups per thiol ester molecules having thiol groups located on terminal carbon molecule, the ratio of (or average ratio of) thiol groups to ester atoms and/or thiol groups located on a carbon atom adjacent groups, the number of (or average number of) carbon-carbon to a terminal carbon atom have from 2 to 8 thiol groups; double bonds per thiolester molecule, the average thiol sulfur alternatively, 3 to 6 thiol groups; alternatively, 3 to 4 thiol content of the thiol ester molecules. In some embodiments, groups; alternatively, only 3 thiol groups; or alternatively, the thiolester molecules have thiol groups located on terminal only 4 thiol groups. In further embodiments, the thiol ester carbon atoms and/or thiol groups located on a carbon atom molecules having thiol groups located on terminal carbon adjacent to a terminal carbon atom may be substantially atoms and/or thiol groups located on a carbon atom adjacent devoid of hydroxyl groups. to a terminal carbon atom have an average of at least 1.5 thiol 0031. The thiol ester molecules of the thiol ester compo groups per thiolester molecule; alternatively, an average of at sitions may be produced from any unsaturated ester having least 2.5 thiol groups per thiolester molecule; or alternatively, terminal double bonds, as described herein. It should be noted an average of at least 3 thiol groups per thiol ester molecule. that the feedstock unsaturated esters having terminal double In yet further embodiments, the thiolester molecules have an bonds may have multiple terminal double bonds and may average of from 1.5 to 8thiol groups per thiolester molecule: contain many different unsaturated ester molecules having alternatively, an average of from 2 to 7 thiol groups per thiol terminal double bonds. This fact, combined with carbon ester molecule; alternatively, an average of from 2.5 to 5thiol carbon double bond reactivity and statistical probability, dic groups per thiolester molecule; or alternatively, an average of tate that each thiol ester molecule having thiol groups located from 3 to 4thiol groups per thiol ester molecule. In yet other on terminal carbon atoms and/or thiol groups located on a embodiments, the thiol ester molecules having thiol groups US 2009/0264669 A1 Oct. 22, 2009

located on terminal carbonatoms and/or thiol groups located residue of a polyol and a carboxylic acid residue having a on a carbon atom adjacent to a terminal carbon atom have an thiol group may be described as an average per thiol ester average of about 3 thiol groups per thiol ester molecule; or molecule. alternatively, an average of about 4thiol groups per thiolester 0039. In an embodiment, the thiol ester molecule having molecule. ester linkages comprises a residue of a polyol and a carboxy 0034. In an embodiment, the thiol group, of thiol ester lic acid residues having a thiol group. The residue of the molecules, may be located on a terminal thiol atom, located polyol and the carboxylic acid residue having a thiol group on a carbon adjacent to a terminal carbon atom, or a mixture are independent elements of thiol ester molecules having thereof. In some embodiments, the thiol group of the thiol ester linkage. Consequently, the features of the residue of the ester molecule may be located on a terminal carbon atom polyol and the carboxylic acid having a thiol group are inde group; alternatively, the thiol group of the thiolester molecule pendently described herein and may be used in any combina may be located on the carbon atom adjacent to a terminal tion to describe the thiolester molecules having esterlinkages carbon atom. may comprise residue of a polyol and at least two carboxylic 0035 Generally, the location of the thiol group within the acid residues having a thiol group. thiol ester molecule may depend upon the particular method 0040. The carboxylic acid residue having a thiol group utilized to produce it. For example, when reacting unsaturated may be further described by its structural features. These esters having a terminal carbon-carbon double bond located structural features are independently described herein and at a terminal position, it may be possible to choose reaction may be utilized in any combination to describe the carboxylic conditions to produce a thiol ester molecules having a thiol acid residue of the thiolester molecules having ester linkages group located on a terminal carbon atom (forming a primary comprising a residue of a polyol and carboxylic acid residues thiol group) or a thiol group located on the carbon atom having a thiol group. adjacent to the terminal carbon atom (forming a secondary or 0041. In an embodiment, the carboxylic acid residuehav tertiary thiol group). It should be noted that in further reac ing the thiol group is linear. In another embodiment, the tions, primary, secondary, and tertiary thiol groups may have carboxylic acid residue having the thiol group is branched. different reactivities. Consequently, it may be desirable to 0042. In an embodiment, the thiol group of the carboxylic control the ratio of (or average ratio of) thiol groups located acid residue may be located on a terminal carbon atom (a on a terminal carbonatom to thiol group located on the carbon carboxylic acid residue having a thiol group located on a atom adjacent to the terminal carbon atom. In some embodi terminal carbon atom), located on a carbon adjacent to a ments, the average ratio of thiol groups located on a terminal terminal carbonatom (a carboxylic acid residuehaving a thiol carbon atom to thiol groups located on the carbon atom adja group located on a carbonatom adjacent to a terminal carbon cent to the terminal carbon atom is greater than 5:1, alterna atom), or a mixture thereof. In some embodiments, the thiol tively, greater than 8:1; or alternatively, greater than 10:1. In group of the carboxylic acid residue may be located on a other embodiments the average ratio of thiol groups located terminal carbon atom group; alternatively, the thiol group of on a terminal carbon atom to thiol groups located on the the carboxylic acid residue may be located on the carbonatom carbon atom adjacent to the terminal carbon atom is greater adjacent to a terminal carbon atom. In an embodiment, the than 1:5; alternatively, greater than 1:8; or alternatively, average ratio of carboxylic acid residues having thiol groups greater than 1:10. located on a terminal carbonatom to carboxylic acid residues 0036. In an embodiment, the thiol ester molecules may having thiol groups located on the carbonatom adjacent to the contain carbon-carbon double bonds. These carbon-carbon terminal carbonatom is greater than 5:1, alternatively, greater double bonds may result from incomplete conversion of the than 8:1; or alternatively, greater than 10:1. In other embodi feedstock during the reaction with hydrogen sulfide described ments the average ratio of carboxylic acid residues having herein. In some embodiments, the average ratio of carbon thiol groups located on a terminal carbon atom to carboxylic carbon double bonds to thiol groups is less than 1:5; alterna acid residues having thiol groups located on the carbon atom tively, less than 1:7; or alternatively, less than 1:10. adjacent to the terminal carbon atom is greater than 1:5; 0037. In another aspect, the thiol ester molecules within alternatively, greater than 1:8; or alternatively, greater than the thiolester compositions may be described as having ester 1:10. linkages comprising a residue of a polyol and a carboxylic 0043. In an embodiment, the carboxylic acid residuehav acid residue having a thiol group. Additional features of the ing a thiol group located on a terminal carbon atom and/or residue of the polyol and carboxylic acid residue having a thiol group located on a carbon atom adjacent to a terminal thiol group are independently described herein and may be carbon atom may have at least 4 carbon atoms; alternatively, utilized in any combination to further describe the thiol ester at least 6 carbon atoms; or alternatively, at least 8 carbon molecules. atoms. In some embodiments, the carboxylic acid residue 0038. The thiol ester molecules described as having ester having a thiol group located on a located on a terminal carbon linkages comprising a residue of a polyol and a carboxylic atom and/or thiol group located on a carbon atom adjacent to acid residue having a thiol group may be produced from any a terminal carbon atom may have from 4 to 20 carbonatoms; unsaturated ester, as described herein. It should be noted that alternatively, from 6 to 18 carbonatoms; alternatively, from 8 the feedstock unsaturated esters may have multiple double to 14 carbonatoms; alternatively, from 10 to 11 carbonatoms: bonds and may contain many different unsaturated ester mol alternatively, only 10 carbon atoms; or alternatively, only 11 ecules. This fact, combined with carbon-carbon double bond carbonatoms. In an embodiment, the carboxylic acid residue reactivity and statistical probability, dictate that each thiol having a thiol group located on a located on a terminal carbon ester molecule having ester linkages comprising a residue of atom and/or thiol group located on a carbon atom adjacent to a polyol and a carboxylic acid residue having a thiol group a terminal carbon atom may have an average of at least 4 may not have the same structure. Thus, particular features of carbon atoms; alternatively, at least 6 carbon atoms; or alter the thiol ester molecules having ester linkages comprising a natively, at least 8 carbon atoms. In some embodiments, the US 2009/0264669 A1 Oct. 22, 2009

carboxylic acid residue having a thiol group located on a 8-thiol octanoic acid residue, a 9-thiol nonanoic acid residue, located on a terminal carbon atom and/or thiol group located a 10-thiol decanoic acid residue, a 11-thiol undecanoic acid ona carbonatom adjacent to a terminal carbonatom may have residue, a 12-thiol dodecanoic acid residue, a 13-thiol tride an average of 4 to 20 carbon atoms; alternatively, of 6 to 18 canoic acid residue, a 14-thiol tetradecanoic acid residue, a carbon atoms; alternatively, of 8 to 14 carbonatoms; alterna 15-thiolpentadecanoic acid residue, a 16-thiolhexadecanoic tively, of 10 to 11 carbon atoms; alternatively, of about 10 acid residue, a 17-thiol heptadecanoic acid residue, a 18-thiol carbon atoms; or alternatively, of about 11 carbon atoms. octadecanoic acid residue, a 19-thiol nonadecanoic acid resi 0044. In an embodiment, the carboxylic acid residuehav due, a 20-thiol eicosene, or any combination thereof. In some ing a thiol group is substantially devoid of hydroxyl group. In embodiments, the carboxylic acid residues having a thiol further embodiments, the carboxylic acid residue having a group located on the terminal carbon atom include a 6-thiol thiol group is devoid of hydroxyl groups. In yet other embodi hexanoic acid residue, a 7-thiol heptanoic acid residue, a ments, the carboxylic acid residue having a thiol group is 8-thiol octanoic acid residue, a 9-thiol nonanoic acid residue, substantially devoid of other functional groups. In further a 10-thiol decanoic acid residue, a 11-thiol undecanoic acid embodiments, the carboxylic acid residue having a thiol residue, a 12-thiol dodecanoic acid residue, a 13-thiol tride group is devoid of other functional groups (i.e. outside of the canoic acid residue, a 14-thiol tetradecanoic acid residue, a thiol group located on a terminal carbon atom or the thiol 15-thiolpentadecanoic acid residue, a 16-thiolhexadecanoic group located on a carbonatom adjacent to a terminal carbon acid residue, a 17-thiol heptadecanoic acid residue, a 18-thiol atom and the carbonyl group forming the ester linkage, the octadecanoic acid residue, or any combination thereof, alter carboxylic acid contains only carbon and hydrogen). natively, a 8-thiol octanoic acid residue, a 9-thiol nonanoic 0045. In an embodiment, the carboxylic acid residues hav acid residue, a 10-thiol decanoic acid residue, a 11-thiol ing a thiol group located on a terminal carbonatom may have undecanoic acid residue, a 12-thiol dodecanoic acid residue, Structure CRT 1 a 13-thiol tridecanoic acid residue, a 14-thiol tetradecanoic acid residue, or any combination thereof, or alternatively, a 10-thiol decanoic acid residue, a 11-undecanoic acid residue, CRT1 or any combination thereof. In other embodiment, the car boxylic acid residues having a thiol group located on the terminal carbon atom may be a 6-thiolhexanoic acid residue; ---p alternatively, a 7-thiol heptanoic acid residue; alternatively, a 8-thiol octanoic acid residue, alternatively, a 9-thiol nonanoic wherein p may be positive integer ranging from 1 to 17; acid residue, alternatively, a 10-thiol decanoic acid residue: alternatively from 3 to 15; alternatively, from 5 to 11; or alternatively, a 11-thiol undecanoic acid residue; alterna alternatively 7 to 8. In some embodiments, p may be 7 or tively, a 12-thiol dodecanoic acid residue; alternatively, a alternatively 8. In other embodiments, p may represent an 13-thiol tridecanoic acid residue; alternatively, a 14-thiol tet average number (whole or fractional) of carbonatom ranging radecanoic acid residue, alternatively, a 15-thiol pentade from 1 to 17; alternatively from 3 to 15; alternatively, from 5 canoic acid residue; alternatively, a 16-thiolhexadecanoic to 11; alternatively 7 to 8; alternatively about 7; or alterna acid residue; alternatively, a 17-thiol heptadecanoic acid resi tively, about 8. Within the carboxylic acid residue structure due; or alternatively, a 18-thiol octadecanoic acid residue. CRT 1 the dashed line is the bond to the oxygen atom of the 0048 Suitable carboxylic acid residues having a thiol ester linkage. group adjacent to the terminal carbon atom include a 3-thiol 0046. In an embodiment, the carboxylic acid residues hav butanoic acid residue, a 4-thiolpentanoic acid residue, a 5-thi ing a thiol group located on a carbon atom adjacent to a olhexanoic acid residue, a 6-thiol heptanoic acid residue, a terminal carbon atom may have Structure CRT 2 7-thiol octanoic acid residue, a 8-thiol nonanoic acid residue, a 9-thiol decanoic acid residue, a 10-thiol undecanoic acid residue, a 11-thiol dodecanoic acid residue, a 12-thiol tride CRT 2 canoic acid residue, a 13-thiol tetradecanoic acid residue, a 14-thiolpentadecanoic acid residue, a 15-thiolhexadecanoic acid residue, a 16-thiol heptadecanoic acid residue, a 17-thiol octadecanoic acid residue, a 18-thiol nonadecanoic acid resi --> due, a 19-thiol eicosene, or any combination thereof. In some embodiments, the carboxylic acid residues having a thiol wherein p may be positive integer ranging from 1 to 17; group located on the terminal carbon atom include a 5-thiol alternatively from 3 to 15; alternatively, from 5 to 11; or hexanoic acid residue, a 6-thiol heptanoic acid residue, a alternatively 7 to 8. In some embodiments, p may be 7 or 7-thiol octanoic acid residue, a 8-thiol nonanoic acid residue, alternatively 8. In other embodiments, p may represent an a 9-thiol decanoic acid residue, a 10-thiol undecanoic acid average number (whole or fractional) of carbonatom ranging residue, a 11-thiol dodecanoic acid residue, a 12-thiol tride from 1 to 17; alternatively from 3 to 15; alternatively, from 5 canoic acid residue, a 13-thiol tetradecanoic acid residue, a to 11; alternatively 7 to 8; alternatively about 7; or alterna 14-thiolpentadecanoic acid residue, a 15-thiolhexadecanoic tively, about 8. Within the carboxylic acid residue structure acid residue, a 16-thiol heptadecanoic acid residue, a 17-thiol CRT 2 the dashed line is the bond to the oxygen atom of the octadecanoic acid residue, or any combination thereof, alter ester linkage. natively, a 7-thiol octanoic acid residue, a 8-thiol nonanoic 0047 Suitable the carboxylic acid residues having a thiol acid residue, a 9-thiol decanoic acid residue, a 10-thiol unde group located on the terminal carbon atom include a 4-thiol canoic acid residue, a 11-thiol undecanoic acid residue, a butanoic acid residue, a 5-thiolpentanoic acid residue, a 6-thi 12-thiol tridecanoic acid residue, a 13-thiol tetradecanoic olhexanoic acid residue, a 7-thiol heptanoic acid residue, a acid residue, or any combination thereof, or alternatively, a US 2009/0264669 A1 Oct. 22, 2009

9-thiol decanoic acid residue, a 10-undecanoic acid residue, 0053. In an embodiments, the polyol that formed the resi or any combination thereof. In other embodiment, the car due of the polyol was a diol, triol, a tetraol, pentaol, hexaol, or boxylic acid residues having a thiol group located on the combination thereof; alternatively a diol, triol, tetraolor com terminal carbon atom may be a 5-thiolhexanoic acid residue; bination thereof; or alternatively, a triol, tetraol or combina alternatively, a 6-thiol heptanoic acid residue, alternatively, a tion thereof. In some embodiments, the polyol that formed the 7-thiol octanoic acid residue; alternatively, a 8-thiol nonanoic residue of the polyol was a diol; alternatively, a triol; alterna acid residue; alternatively, a 9-thiol decanoic acid residue: tively, a tetraol; alternatively, a pentaol; or alternatively, a alternatively, a 10-thiol undecanoic acid residue, alterna hexaol. Suitable polyols that may form the residue of the tively, a 11-thiol dodecanoic acid residue; alternatively, a polyol include ethane diol, propanediol, butanediol, pen 12-thiol tridecanoic acid residue; alternatively, a 13-thiol tet tanediol, hexanediol, cyclohexane diol, phenylethane diol. radecanoic acid residue; alternatively, a 14-thiol pentade cyclohexanedimethanol, dimethyolpropane, benzene canoic acid residue; alternatively, a 15-thiolhexadecanoic dimethanol, cyclohexanetriol, trihydroxybenzene, trim acid residue, alternatively, a 16-thiol heptadecanoic acid resi ethyolethane, trimethylolpropane, trimethylolbutane, glyc due; or alternatively, a 17-thiol octadecanoic acid residue. erol, pentaerythritol, sorbitol, or any combination thereof; 0049. The residue of the polyol may be further described alternatively, cyclohexane diol, trimethylol propane, glyc by its structural features. These structural features are inde erol, pentaerythritol, or combinations thereof; alternatively, pendently described herein and may be utilized in any com glycerol, pentaerythritol, or combinations thereof. In some bination to describe the residue of the polyol of the thiol ester embodiments, the polyol that may form the residue of the molecules having ester linkages comprising, or consisting polyol include 1.2-ethanediol. 1,3-propanediol, 1,4-butane essentially of a residue of a polyol and carboxylic acid resi diol. 1,5-pentanediol, 1.6-hexanediol, dimethylolpropane, dues having a thiol group located on a terminal carbon atom neopentylglycol, 2-propyl-2-ethyl-1,3-propanediol. 1,2-pro and/or thiol group located on a carbon atom adjacent to a panediol. 1,2-butanediol. 1,3-butanediol, 1,4-butanediol, terminal carbon atom. diethylene glycol, triethylene glycol, polyethylene glycol, 0050. In an embodiment, residue of the polyol may have 2 dipropylene glycol, tripropylene glycol, polypropylene gly to 20 carbonatoms. In some embodiments, the residue of the col, 11-cyclohexanedimethanol, 1.2-cyclohexanedimetha polyol may have 2 to 12 carbon atoms; alternatively, 2 to 8 nol, 1.3-cyclohexanedimethanol, 1.4-cyclohexanedimetha carbon atoms; or alternatively, 2 to 5 carbon atoms. In some nol, 1,3-dioxane-5,5-dimethanol, 1-phenyl-1,2-ethanediol, embodiments, the polyol of the residue of the polyol may trimethylolpropane, trimethylolethane, trimethylolbutane, have had 2 to 8 hydroxyl group; alternatively, 3 to 6 hydroxyl glycerol, 1.2.5-hexanetriol, pentaerythritol, ditrimethylol groups; alternatively, 2 to 4 hydroxyl groups; alternatively, 4 propane, diglycerol, ditrimethylolethane, 1,3,5-trihydroxy to 8 hydroxyl groups; alternatively, only 3 hydroxyl groups; benzene, 1,2-benzenedimethanol. 1,3-benzenedimethanol, alternatively, only 4 hydroxyl groups; alternatively, only 5 1,4-benzenedimethanol, 1-phenyl-1,2-ethanediol, sorbitol, hydroxyl groups; or alternatively, only 6 hydroxyl groups. or any combination thereof. In other embodiments, the polyol 0051. In other embodiments, the residue of the polyol may that may be used as the polyol residue may be trimethylol be a residue of a mixture of polyols. In Such an instance the propane, glycerol, pentaerythritol, or combinations thereof. residue of the polyol may have an average of 2 to 20 carbon alternatively, trimethylolpropane; alternatively, glycerol; atoms perpolyol molecule; alternatively, an average of 2 to 12 alternatively, pentaerythritol; or alternatively sorbitol. carbon atoms per polyol molecule; alternatively, an average 0054. It should be appreciated that not all of the hydroxyl of 2 to 8 carbon atoms per polyol molecule; or alternatively, groups of the polyol that form the residue of the polyol may an average of 2 to 5 carbon atoms per polyol molecule. Fur form ester linkages. In some instances some of the hydroxyl ther, the mixture of polyols of the residues of the polyols may groups may not form ester linkages and may remain as have had an average of at least 2.5 hydroxyl groups perpolyol hydroxyl group. In an embodiment, greater than 80, 85,90, 95 molecule; alternatively, 2.5 to 8 hydroxyl groups per polyol percent of all hydroxyl groups of the residue of the polyol molecule; alternatively, an average of 2 to 6 hydroxyl groups form ester linkages. In other embodiments, Substantially all per polyol molecule; alternatively, an average of 2.5 to 5 of the hydroxyl groups of the polyol, which forms the residue hydroxyl groups per polyol molecule; alternatively, an aver of a polyol forming linkages with a carboxylic acid having a age of 2.5 to 4.5 hydroxyl group per polyol molecule; alter thiol group located on a terminal thiol atom, located on a natively, an average of 2.5 to 3.5 hydroxyl group per polyol carbon adjacent to a terminal carbon atom, or a combination molecule; alternatively, an average of 3 to 4 hydroxyl group thereof, forms ester linkages. In yet other embodiments, the per polyol molecule; alternatively, an average of about 3 thiolester molecules having ester linkages comprising a resi hydroxyl groups per polyol molecule; alternatively, an aver due of a polyol and carboxylic acid residues having a thiol age of about 4 hydroxyl groups per polyol molecule; alterna group are Substantially devoid of hydroxy groups derived tively, an average of about 5 hydroxyl groups per polyol from the polyol. In some embodiments, the average ratio of molecule; or alternatively an average of about 6 hydroxy carboxylic acid residues having a thiol group located on a groups per polyol molecule. terminal carbon atom or a carbon atom adjacent to the termi 0052. In an embodiment, the polyol that formed the resi nal carbon atom to hydroxyl groups of the polyol of the due of the polyol or mixture of polyols that formed the resi residue of the polyol is greater than 0.70:1; alternatively, dues of the polyols may have had a molecular weight or greater than 0.75:1; alternatively, greater than 0.80:1; alter average molecular weight less than 300. In other embodi natively, greater than 0.85:1, alternatively, greater than 0.90: ments, the polyol that formed the residue of the polyol or 1; alternatively, greater than 0.95:1. mixture of polyols that formed the residues of the polyols may 0055. It will be appreciated that not all of the ester linkages have had a molecular weight or average molecular weightless comprising the residue of the polyol may comprise carboxy than 250; alternatively less than 200; alternatively, less than lic acid residues having a thiol group located on a terminal 150; or alternatively, less than 100. carbon atom and/or a thiol group located on a carbon atom US 2009/0264669 A1 Oct. 22, 2009

adjacent to the terminal carbon atom. For example, some of group located on a carbonatom adjacent to a terminal carbon the ester linkages may comprise a residue of the polyol and atom, may have a thiol equivalent weight of 140 to 500 grams: carboxylic acid residue having a terminal carbon-carbon alternatively, 170 to 400 grams; alternatively, 200 to 350 double bond resulting from incomplete conversion of the grams. feedstock during the reaction with hydrogen sulfide described herein. In Such an instance, the thiol ester molecules having C.-Hydroxy Thiol Ester Compositions ester linkages comprising a residue of a polyol and a carboxy 0058. In an aspect, the present invention relates to C-hy lic acid residues having a thiol group may be further defined droxy thiol ester compositions comprising, or consisting by the average ratio of carboxylic acid residues having a essentially of C-hydroxy thiol ester molecules having termi carbon-carbon double bond to carboxylic acid residues hav nal C-hydroxy thiol groups. The C-hydroxy thiol ester mol ingathiol group. In an embodiment, average ratio of carboxy ecules may be described as comprising, consisting essentially lic acid residues having a carbon-carbon double bond to car of one or more functional group present in the C-hydroxy boxylic acid residues having a thiol group may be less than thiol ester molecules of the C-hydroxy thiol ester composi 1:5; alternatively, less than 1:7; or alternatively, less than tion. Each of the functional groups that may be present in the 1:10. Additionally or alternatively, the feedstock used to pro C-hydroxy thiol ester molecules thiol groups are indepen duce the thiol ester molecules may contain an ester linkage dently described herein and may be utilized in any combina with Saturated carboxylic acid that can not be thiolated using tion to described the C-hydroxy thiol ester molecules. the methods described herein and/or unsaturated carboxylic 0059. The independent functional groups that can be uti acid residue that were not thiolated. Considering this situa lized to describe the C-hydroxy thiol ester molecules having tion, in some embodiments, greater than 75, 80, 85, or 90 terminal C-hydroxy thiol groups include: the number of (or percent of all ester linkages comprising the residue of the average number of) ester groups per C-hydroxy thiol ester polyol comprise carboxylic acid residues having the thiol molecule, the number of (or average number of) terminal group located on a terminal carbon atom and/or a thiol group C-hydroxy thiol groups per C-hydroxy thiol ester molecule, located on a carbon atom adjacent to the terminal carbon the ratio of (or average ratio of) terminal C-hydroxy thiol atOm. groups to ester groups per C-hydroxythiolester molecule, the 0056. In an embodiment, the thiol ester molecules, number of (or average number of) unreacted carbon-carbon whether described as having particular functional groups or double bonds per C-hydroxy thiol ester molecule, the number as thiol ester molecules having ester linkages comprising a of (or average number of) unreacted epoxide per C-hydroxy residue of a polyol and carboxylic acid residuehaving a thiol thiol ester molecule, and the average thiol sulfur content of group located on a terminal carbon atom and/or thiol group the C-hydroxy thiol ester molecules. located on a carbonatom adjacent to a terminal carbon atom, 0060. The C-hydroxy thiol ester molecules having termi may have an average ratio of thiol groups to estergroups in the nal C-hydroxy thiol groups of the C-hydroxy thiol ester com thiol ester molecules of less than 1.15:1; alternatively, less positions may be produced from any epoxidized unsaturated than 1.1:1; or alternatively, less than 1.05:1. In some embodi ester composition (epoxide ester composition) comprising ments, the thiol ester molecules, whether described as having epoxidized unsaturated ester molecules (epoxide ester mol particular functional groups or as thiolester molecules having ecules) having terminal epoxide groups described herein. It ester linkages comprising a polyol residue and carboxylic should be noted that the feedstock epoxidized unsaturated acid residues having a thiol group located on a terminal car esters may have multiple epoxide and may contain many bon atom and/or thiol group located on a carbon atom adja different epoxidized unsaturated ester molecules. This fact, cent to a terminal carbon atom, may have an average ratio of combined with epoxide group reactivity and statistical prob thiol groups to ester groups in the thiol ester molecules that ability, dictate that each C.-hydroxy thiol ester molecule hav ranges from 0.75:1 to 1.15:1; alternatively, ranges from ing terminal C-hydroxy thiol groups of the C-hydroxy thiol 0.85:1 to 1.1:1; or alternatively, ranges from 0.90:1 to 1.05:1. ester composition may not have the same number of func In other embodiments, the thiol ester molecules, whether tional groups, the same ratios of functional groups, and/or the described as having particular functional groups or as thiol same additional features. Thus, the number of functional ester molecules having ester linkages comprising a polyol group, ratios of functional groups, and/or additional features residue and carboxylic acid residues having a thiol group of the O.-hydroxy thiolester molecules of the C-hydroxy thiol located on a terminal carbon atom and/or thiol group located ester composition may be referred to as an average per C-hy on a carbon atom adjacent to a terminal carbon atom, may droxy thiol ester molecules within the O-hydroxy thiol ester have an average ratio of thiol groups to ester groups in the composition. thiol ester molecules of about 1:1. 0061. In an embodiment, the O-hydroxy thiol ester mol 0057. In some embodiments, the thiol ester molecules, ecules having terminal C-hydroxy thiol groups may have at whether described as having particular functional groups or least 2 ester groups; alternatively at least 3 ester groups; or as thiol ester molecules having ester linkages comprising a alternatively, at least 4 ester groups. In other embodiments, polyol residue and carboxylic acid residues having a thiol the C-hydroxy thiol ester molecules having terminal C-hy group located on a terminal carbon atom and/or thiol group droxy thiol groups may have from 2 to 8 ester groups; alter located on a carbonatom adjacent to a terminal carbon atom, natively, 3 to 6 ester groups; alternatively, 3 to 4 ester groups; may have an average thiol sulfur content of 5 to 20 weight alternatively, only 3 ester groups; or alternatively, only 4 ester percent; alternatively, 7 to 18 weight percent; alternatively, 9 groups. In further embodiments, the C-hydroxy thiol ester to 16 weight percent. In other embodiment, the thiol ester molecules having terminal C-hydroxy thiol groups may have molecules, whether described as having particular functional an average of at least 2 ester groups per C-hydroxy thiol ester groups or as thiolester molecules having ester linkages com molecule; alternatively, an average of at least 2.5 ester groups prising a polyol residue and carboxylic acid residues having a per C-hydroxy thiol ester molecule; or alternatively, an aver thiol group located on a terminal carbon atom and/or thiol age of at least 3 ester groups per C-hydroxy thiol ester mol US 2009/0264669 A1 Oct. 22, 2009

ecule. In yet further embodiments, the C-hydroxy thiol esters droxy thiol group are independently described herein and having terminal C-hydroxy thiol groups may have an average may be utilized in any combination to further describe the of from 2 to 8 ester groups per C-hydroxy thiol ester mol O-hydroxy thiol ester molecules. ecule; alternatively, an average of from 2 to 7 ester groups per 0066. The O.-hydroxy thiol ester molecules described as C-hydroxy thiol ester molecule; alternatively, an average of having ester linkages comprising a residue of a polyol and a from 2.5 to 5 estergroups per C-hydroxythiolester molecule: carboxylic acid residue having a terminal C-hydroxy thiol or alternatively, an average of from 3 to 4 ester groups per group may be produced from any epoxidized ester molecule O-hydroxy thiol ester molecule. In yet other embodiments, having a terminal epoxide groups described herein. It should the C-hydroxy thiol ester molecules having terminal C-hy be noted that the feedstock epoxized ester molecules may droxy thiol groups may have an average of about 3 ester have multiple epoxide groups and may contain many differ groups per C-hydroxy thiol ester molecule; or alternatively, ent epoxidized ester molecules. This fact, combined with an average of about 4 ester groups per C-hydroxy thiol ester epoxide reactivity and statistical probability, dictate that each molecule. C-hydroxy thiol ester molecule having ester linkages com 0062. In an embodiment, the O-hydroxy thiol ester mol prising a residue of a polyol and a carboxylic acid residue ecules of the O-hydroxy thiol ester composition have at least having a terminal C-hydroxy thiol group may not have the 2 terminal C-hydroxy thiol groups; alternatively, at least 3 same structure. Thus, particular features of the C-hydroxy terminal C-hydroxy thiol groups; or alternatively, at least 4 thiolester molecules having ester linkages comprising a resi terminal C-hydroxy thiol groups. In other embodiments, the due of a polyol and a carboxylic acid residue having a termi O-hydroxy thiol ester molecules have from 2 to 8 terminal nal C-hydroxy thiol group may be described as an average per C-hydroxy thiol groups; alternatively, 3 to 6 terminal C-hy O-hydroxy thiol ester molecule. droxy thiol groups; alternatively, 3 to 4 terminal C-hydroxy 0067. In an embodiment, the O-hydroxy thiol ester mol thiol groups; alternatively, only 3 terminal C-hydroxy thiol ecules having ester linkages comprise a residue of a polyol groups; or alternatively, only 4 terminal C-hydroxy thiol and carboxylic acid residues having a terminal C-hydroxy groups. In further embodiments, the O-hydroxy thiol ester thiol group. The residue of the polyol and the carboxylic acid molecules have an average of at least 1.5 terminal C-hydroxy residue having a terminal C-hydroxy thiol group are indepen thiol groups per C-hydroxy thiol ester molecules; alterna dent elements of C-hydroxythiolester molecules having ester tively, an average of at least 2.5 terminal C-hydroxy thiol linkages. Consequently, the features of the residue of the groups per C-hydroxy thiol ester molecule; or alternatively, polyol and the carboxylic acid having a terminal C-hydroxy an average of at least 3 terminal O-hydroxy thiol groups per thiol group are independently described herein and may be O-hydroxy thiol ester molecule. In yet further embodiments, used in any combination to describe the C-hydroxy thiol ester the C-hydroxy thiol ester molecules have an average of from molecules having ester linkages comprising a residue of a 1.5 to 8 terminal C-hydroxy thiol groups per C-hydroxy thiol polyol and at least two carboxylic acid residues having a ester molecule; alternatively, an average of from 2 to 7 termi terminal C-hydroxy thiol group. nal C-hydroxy thiol groups per C-hydroxy thiol ester mol 0068. The carboxylic acid residuehaving a terminal C-hy ecule; alternatively, an average of from 2.5 to 5 terminal droxy thiol group may be further described by its structural C-hydroxy thiol groups per C-hydroxy thiol ester molecule: features. These structural features are independently or alternatively, an average of from 3 to 4 terminal C-hydroxy described herein and may be utilized in any combination to thiol groups per C-hydroxy thiol ester molecule. In yet other describe the carboxylic acid residue of the C-hydroxy thiol embodiments, the C-hydroxy thiol ester molecules have an ester molecules having ester linkages comprising a residue of average of about 3 terminal C-hydroxy thiol groups per C-hy a polyol and carboxylic acid residues having a terminal C-hy droxy thiol ester molecule; or alternatively, an average of droxy thiol group. about 4 terminal C-hydroxy thiol groups per C-hydroxy thiol 0069. In an embodiment, the carboxylic acid residuehav ester molecule. ing the terminal C-hydroxy thiol group is linear. In another 0063. Unless otherwise specified, either the thiol group or embodiment, the carboxylic acid residue having the terminal the hydroxyl group of the C-hydroxy thiol group may be C-hydroxy thiol group is branched. located on the terminal carbon atom. In an embodiment, the 0070. Unless otherwise specified, either the thiol group or thiol group of the terminal C-hydroxy thiol group may be the hydroxy group of the O.-hydroxy thiol group within the located on the terminal carbon atom. In other embodiments, carboxylic acid residue having a terminal C-hydroxy thiol the hydroxyl group of the terminal C-hydroxy thiol group group may be located on the terminal carbon atom. In an may be located on the terminal carbon atom. embodiment, the thiol group of the C-hydroxy thiol group 0064. In an embodiment, the O-hydroxy thiol ester mol within the carboxylic acid residue having a terminal C-hy ecules having terminal C-hydroxy thiol groups may contain droxy thiol group may be located on the terminal carbon epoxide groups. These epoxide groups may result from atom. In other embodiments, the hydroxyl group of the C-hy incomplete conversion of the feedstock during the reaction droxy thiol group within the carboxylic acid residue having a with hydrogen sulfide described herein. In some embodi terminal C-hydroxy thiol group may be located on the termi ments, the average ratio of epoxide to C-hydroxy thiol groups nal carbon atom. is less than 1:5; alternatively, less than 1:7; or alternatively, 0071. In an embodiment, the carboxylic acid residuehav less than 1:10. ing a terminal C-hydroxy thiol group may have at least 4 0065. In another aspect, the C-hydroxy thiol ester mol carbon atoms; alternatively, at least 6 carbon atoms; or alter ecules within the C-hydroxy thiol ester compositions may be natively, at least 8 carbon atoms. In some embodiments, the described as having ester linkages comprising a residue of a carboxylic acid residue having a terminal C-hydroxy thiol polyol and a carboxylic acid residue having a terminal C-hy group may have from 4 to 20 carbon atoms; alternatively, droxy thiol group. Additional features of the residue of the from 6 to 18 carbon atoms; alternatively, from 8 to 14 carbon polyol and carboxylic acid residue having a terminal C-hy atoms; alternatively, from 10 to 11 carbon atoms; alterna US 2009/0264669 A1 Oct. 22, 2009

tively, only 10 carbon atoms; or alternatively, only 11 carbon 0076. In other embodiments, the residue of the polyol may atoms. In an embodiment, the carboxylic acid residue a ter be a residue of a mixture of polyols. In Such an instance the minal C-hydroxy thiol group may have an average of at least residue of the polyol may have an average of 2 to 20 carbon 4 carbon atoms; alternatively, at least 6 carbon atoms; or atoms perpolyol molecule; alternatively, an average of 2 to 12 alternatively, at least 8 carbon atoms. In some embodiments, carbon atoms per polyol molecule; alternatively, an average the carboxylic acid residue a terminal C-hydroxy thiol group of 2 to 8 carbon atoms per polyol molecule; or alternatively, may have an average of 4 to 20 carbon atoms; alternatively, of an average of 2 to 5 carbon atoms per polyol molecule. Fur 6 to 18 carbon atoms; alternatively, of 8 to 14 carbon atoms: ther, the mixture of polyols of the residues of the polyols may alternatively, of 10 to 11 carbon atoms; alternatively, of about have had an average of at least 2.5 hydroxyl groups perpolyol 10 carbon atoms; or alternatively, of about 11 carbon atoms. molecule; alternatively, 2.5 to 8 hydroxyl groups per polyol 0072. In some embodiments, the carboxylic acid residue molecule; alternatively, an average of 2 to 6 hydroxyl groups having a terminal C-hydroxy thiol group may be substantially per polyol molecule; alternatively, an average of 2.5 to 5 devoid of other functional groups. In further embodiments, hydroxyl groups per polyol molecule; alternatively, an aver the carboxylic acid residuehaving a terminal C-hydroxy thiol age of 2.5 to 4.5 hydroxyl group per polyol molecule; alter group may be devoid of other functional groups (i.e. outside natively, an average of 2.5 to 3.5 hydroxyl group per polyol of the terminal C-hydroxy and the carbonyl group forming the molecule; alternatively, an average of 3 to 4 hydroxyl group ester linkage, the carboxylic acid residue contains only car per polyol molecule; alternatively, an average of about 3 bon and hydrogen). hydroxyl groups per polyol molecule; alternatively, an aver 0073. In an embodiment, the carboxylic acid residues hav age of about 4 hydroxyl groups per polyol molecule; alterna ing a terminal C-hydroxy thiol group may have Structure tively, an average of about 5 hydroxyl groups per polyol CRHT 1 or Structure CRHT 2. molecule; or alternatively an average of about 6 hydroxy groups per polyol molecule.

CRHT1 0077. In an embodiment, the polyol that formed the resi O OH due of the polyol or mixture of polyols that formed the resi dues of the polyols may have had a molecular weight or average molecular weight less than 300. In other embodi ---p SH CRHT2 ments, the polyol that formed the residue of the polyol or O SH mixture of polyols that formed the residues of the polyols may have had a molecular weight or average molecular weight less than 250; alternatively less than 200; alternatively, less than 150; or alternatively, less than 100. 0078. In an embodiments, the polyol that formed the resi wherein p may be positive integer ranging from 1 to 17; due of the polyol is a diol, triol, a tetraol, pentaol, hexaol, or alternatively from 3 to 15; alternatively, from 5 to 11; or combination thereof; alternatively a diol, triol, tetraolor com alternatively 7 to 8. In some embodiments, p may be 7 or bination thereof; or alternatively, a triol, tetraol or combina alternatively 8. In other embodiments, p may represent an tion thereof. In some embodiments, the polyol that formed the average number (whole or fractional) of carbonatom ranging residue of the polyol is a diol; alternatively, a triol; alterna from 1 to 17; alternatively from 3 to 15; alternatively, from 5 tively, a tetraol; alternatively, a pentaol; or alternatively, a to 11; alternatively 7 to 8; alternatively about 7; or alterna hexaol. Suitable polyols that may form the residue of the tively, about 8. Within the carboxylic acid residue structure polyol include ethane diol, propanediol, butanediol, pen CRHT 1 the dashed line is the bond to the oxygenatom of the tanediol, hexanediol, cyclohexane diol, phenylethane diol. ester linkage. In an embodiment, the carboxylic acid residues cyclohexanedimethanol, dimethyolpropane, benzene having a terminal C-hydroxy thiol group may have Structure dimethanol, cyclohexanetriol, trihydroxybenzene, trim CRHT 1. In other embodiments, the carboxylic acid residues ethyolethane, trimethylolpropane, trimethylolbutane, glyc having a terminal C-hydroxy thiol group may have Structure erol, pentaerythritol, sorbitol, or any combination thereof; CRHT 2. alternatively, cyclohexane diol, trimethylol propane, glyc 0074 The residue of the polyol may be further described erol, pentaerythritol, or combinations thereof; alternatively, by its structural features. These structural features are inde glycerol, pentaerythritol, or combinations thereof. In some pendently described herein and may be utilized in any com embodiments, the polyol that may form the residue of the bination to describe the residue of the polyol of the C-hydroxy polyol include 1.2-ethanediol. 1,3-propanediol, 1,4-butane thiol ester molecules having ester linkages comprising, or diol. 1,5-pentanediol, 1.6-hexanediol, dimethylolpropane, consisting essentially of a residue of a polyol and carboxylic neopentylglycol, 2-propyl-2-ethyl-1,3-propanediol. 1,2-pro acid residues having a terminal C-hydroxy thiol group. panediol. 1,2-butanediol. 1,3-butanediol, 1,4-butanediol, 0075. In an embodiment, the residue of the polyol may diethylene glycol, triethylene glycol, polyethylene glycol, have 2 to 20 carbonatoms. In some embodiments, the residue dipropylene glycol, tripropylene glycol, polypropylene gly of the polyol may have 2 to 12 carbon atoms; alternatively, 2 col, 11-cyclohexanedimethanol, 1.2-cyclohexanedimetha to 8 carbon atoms; or alternatively, 2 to 5 carbon atoms. In nol, 1.3-cyclohexanedimethanol, 1.4-cyclohexanedimetha some embodiments, the polyol of the residue of the polyol nol, 1,3-dioxane-5,5-dimethanol, 1-phenyl-1,2-ethanediol, may have had 2 to 8 hydroxyl group; alternatively, 3 to 6 trimethylolpropane, trimethylolethane, trimethylolbutane, hydroxyl groups; alternatively, 2 to 4 hydroxyl groups; alter glycerol, 1,2,5-hexanetriol, pentaerythritol, ditrimethylol natively, 4 to 8 hydroxyl groups; alternatively, only 3 propane, diglycerol, ditrimethylolethane, 1,3,5-trihydroxy hydroxyl groups; alternatively, only 4 hydroxyl groups; alter benzene, 1,2-benzenedimethanol. 1,3-benzenedimethanol, natively, only 5 hydroxyl groups; or alternatively, only 6 1,4-benzenedimethanol, 1-phenyl-1,2-ethanediol, sorbitol, hydroxyl groups. or any combination thereof. In other embodiments, the polyol US 2009/0264669 A1 Oct. 22, 2009 that may be used as the polyol residue may be trimethylol age ratio of C-hydroxy thiol groups to ester groups in the propane, glycerol, pentaerythritol, or combinations thereof; O-hydroxy thiol ester molecules that ranges from 0.75:1 to alternatively, trimethylolpropane; alternatively, glycerol; 1.15:1; alternatively, ranges from 0.85:1 to 1.1:1; or alterna alternatively, pentaerythritol; or alternatively sorbitol. tively, ranges from 0.90:1 to 1.05:1. In other embodiments, 0079. It should be appreciated that not all of the hydroxyl the O.-hydroxy thiol ester molecules, whether described as groups of the polyol that form the residue of the polyol may having particular functional groups or as C.-hydroxy thiol form ester linkages. In some instances some of the hydroxyl ester molecules having ester linkages comprising a polyol groups may not form ester linkages and may remain as residue and carboxylic acid residues having a terminal C-hy hydroxyl group. In an embodiment, greater than 80, 85,90,95 droxy thiol group, may have an average ratio of C-hydroxy percent of all hydroxyl groups of the residue of the polyol thiol groups to ester groups in the thiol ester molecules of form ester linkages. In other embodiments, Substantially, all about 1:1. of the hydroxyl groups of the polyol, which forms the residue I0082 In some embodiments, the C-hydroxy thiol ester of a polyol forming linkages with a carboxylic acid having a molecules, whether described as having particular functional terminal C-hydroxy thiol group, forms ester linkages. In yet groups or as C-hydroxy thiol ester molecules having ester other embodiments, the C-hydroxythiolester molecules hav linkages comprising a polyol residue and carboxylic acid ing ester linkages comprising a residue of a polyol and car residues having a terminal C-hydroxy thiol group, may have boxylic acid residues having a terminal C-hydroxy thiol an average thiol sulfur content of 5 to 20 weight percent; group are Substantially devoid of hydroxy groups derived alternatively, 7 to 18 weight percent; alternatively, 9 to 16 from the polyol. In some embodiments, the average ratio of weight percent. In other embodiment, the C-hydroxy thiol carboxylic acid residues having a terminal C-hydroxy thiol to ester molecules, whether described as having particular func hydroxyl groups of the polyol of the residue of the polyol is tional groups or as C-hydroxy thiol ester molecules having greater than 0.70:1; alternatively, greater than 0.75:1; alter ester linkages comprising a polyol residue and carboxylic natively, greater than 0.80:1; alternatively, greater than 0.85: acid residues having a terminal C-hydroxy thiol group, may 1; alternatively, greater than 0.90:1; alternatively, greater than have a thiol equivalent weight of 150 to 500 grams; alterna O.95:1. tively, 180 to 400 grams; alternatively, 200 to 350 grams per 0080. It will be appreciated that not all of the ester linkages equivalent. In other embodiment, the C-hydroxy thiol ester comprising the residue of the polyol may comprise carboxy molecules, whether described as having particular functional lic acid residues having a terminal C-hydroxy thiol group. For groups or as C-hydroxy thiol ester molecules having ester example, some of the ester linkages may comprise a residue linkages comprising a polyol residue and carboxylic acid of the polyol and carboxylic acid group having a terminal residues having a terminal C-hydroxy thiol group, may have epoxide group due to incomplete conversion of the epoxide a hydroxyl equivalent weight of 130 to 500 grams per equiva feedstock during the reaction with hydrogen sulfide described lent; alternatively, 170 to 400 grams per equivalent; alterna herein. In such an instance, the C-hydroxy thiol ester mol tively, 190 to 350 grams per equivalent. ecules having ester linkages comprising a residue of a polyol and a carboxylic acid residues having a terminal C-hydroxy Cross-Linked Thiol Ester Compositions thiol group may be further defined by the average ratio of I0083. In an aspect, the present invention relates to cross carboxylic acid residues having an terminal epoxide group to linked thiol ester compositions comprising, or consisting carboxylic acid residues having a terminal C-hydroxy thiol essentially of cross-linked thiol ester molecules. Generally, group. In an embodiment, average ratio of carboxylic acid the cross-linked thiol ester molecules are oligomers of thiol residues having a terminal epoxide group to carboxylic acid ester molecules that are connected together by polysulfide residues having a terminal C-hydroxy thiol group may be less linkages —S - wherein X is an integer greater than 1. As the than 1:5; alternatively, less than 1:7; or alternatively, less than cross-linked thiol ester may be described as an oligomer of 1:10. Additionally or alternatively, the feedstock used to pro thiol ester molecules, the thiol ester molecules may be duce the C-hydroxy thiol ester molecules may contain ester described as the monomer from which the cross-linked thiol linkages with Saturated carboxylic acid that can not be thi esters are produced. In embodiments, the cross-linked thiol olated and/or carboxylic acid residue having epoxide group ester may be produced from thiolester molecules and may be which were not thiolated. Considering this situation, in some called a cross-linked thiol ester molecule. In other embodi embodiments, greater than 75, 80, 85, or 90 percent of all ments, the cross-linked thiol ester molecules may be pro ester linkages comprising the residue of the polyol comprise duced from C-hydroxy thiol ester molecules and may be carboxylic acid residues having the terminal C-hydroxy thiol called a crossed-linked C-hydroxy thiolester molecule. Gen group. erally, any thiol ester molecule and/or hydroxy thiol ester 0081. In an embodiment, the O-hydroxy thiol ester mol molecule describe herein may be utilized as a monomer for ecules, whether described as having particular functional the cross-linked thiol ester compositions. groups or as C-hydroxy thiol ester molecules having ester I0084. In an aspect, the cross-linked thiol ester composi linkages comprising a residue of a polyol and carboxylic acid tion comprises a thiol ester oligomer having at least two thiol residues having a terminal C-hydroxy thiol group, may have ester monomers connected by a polysulfide linkage having a an average ratio of C-hydroxy thiol groups to ester groups in structure—So , wherein Qis an integergreater than 1. In an the C-hydroxy thiolester molecules of less than 1.15:1; alter aspect, the polysulfide linkage may be the polysulfide linkage natively, less than 1.1:1; or alternatively, less than 1.05:1. In —So , wherein Q is 2, 3, 4, or mixtures thereof. In other Some embodiments, the C-hydroxy thiol ester molecules, embodiments, Q can be 2: alternatively, 3; or alternatively, 4. whether described as having particular functional groups or I0085. In an aspect, the cross-linked thiol ester composi as C.-hydroxy thiol ester molecules having ester linkages tion comprises a thiol ester oligomer having at least 3 thiol comprising a polyol residue and carboxylic acid residues ester monomers connected by polysulfide linkages; alterna having a terminal C-hydroxy thiol group, may have an aver tively, 5thiol ester monomers connected by polysulfide link US 2009/0264669 A1 Oct. 22, 2009 ages; alternatively, 7 thiol ester monomers connected by percent. Further, the C-hydroxythiol ester monomers and the polysulfide linkages; or alternatively, 10 thiol ester mono O-hydroxy thiol ester oligomers may have a total thiol sulfur mers connected by polysulfide linkages. In yet other embodi content from 0.5 weight percent to 8 weight percent, from 4 ments, the cross-linked thiol ester composition comprises a weight percent to 8 weight percent or 0.5 weight percent to 4 thiolester oligomer having from 3 to 20 thiol ester monomers weight percent. connected by polysulfide linkages; alternatively, from 5 to 15 thiol ester monomers connected by polysulfide linkages; or Terminal Epoxide Compositions alternatively, from 7 to 12 thiol ester monomers connected by 0090. In an aspect, the epoxide ester compositions com polysulfide linkages. prising, or consisting essentially of epoxide ester molecules I0086. In an aspect, the cross-linked thiol ester molecules having terminal epoxide groups may be utilized as a feed may include both thiol ester monomers and thiol ester oligo stock for producing O-hydroxy thiolester compositions com mers. For example, the cross-linked thiol ester composition prising, or consisting essentially of C-hydroxy thiol ester may have a combined thiol ester monomer and thiol ester molecules having terminal C-hydroxy thiol groups. The oligomer average molecular weight greater than 2,000, epoxide ester molecules having terminal epoxide groups may greater than 5,000 or greater than 10,000. Further, the cross be described as comprising, consisting essentially of one or linked thiol ester composition may have a combined thiol more functional groups present in the epoxide ester mol ester monomer and thiol ester oligomer average molecular ecules having terminal epoxide groups of the epoxide ester weight ranging from 2,000 to 20,000, from 3,000 to 15,000 or composition. Each of the functional groups that may be from 7,500 to 12,500. In another aspect, the thiolester mono present in the epoxide ester molecules having terminal mers and thiol ester oligomers may have a total thiol Sulfur epoxide groups are independently described herein and may content greater than 0.5 weight percent, greater than 1 weight be utilized in any combination to described the epoxide ester percent, greater than 2 weight percent or greater than 4 weight molecules having terminal epoxide groups. percent. Further, the thiol ester monomers and the thiol ester 0091. The independent functional groups that can be uti oligomers may have a total thiol sulfur content from 0.5 lized to describe ester molecules having terminal epoxide weight percent to 8 weight percent, from 4 weight percent to groups include: the number of (or average number of) ester 8 weight percent or 0.5 weight percent to 4 weight percent. groups (per epoxide ester molecule), the number of (or aver 0087. In an aspect, the cross-linked C-hydroxy thiol ester age number of) terminal epoxide groups (per epoxide ester composition comprises an O-hydroxy thiol ester oligomer molecule), the ratio of (or average ratio of) terminal epoxide having at least two C-hydroxy thiol ester monomers con groups to ester groups (per epoxide ester molecule), the num nected by a polysulfide linkage having a structure —So , ber of (or average number of) unreacted carbon-carbon wherein Q is an integer greater than 1. In an aspect, the double bonds (per epoxide ester molecule), and the average polysulfide linkage may be the polysulfide linkage —So , epoxide content of the epoxide ester molecules. wherein Q is 2, 3, 4, or mixtures thereof. In other embodi 0092. The epoxide ester molecules having terminal ments, Q can be 2: alternatively, 3; or alternatively, 4. epoxide groups of the epoxide ester compositions may be 0088. In an aspect, cross-linked C.-hydroxy thiol ester produced from any unsaturated ester composition comprising composition comprises a C-hydroxythiolester oligomer hav unsaturated ester molecules having terminal carbon-carbon ing at least 3 C-hydroxy thiol ester monomers connected by double bonds described herein. It should be noted that the polysulfide linkages; alternatively, at least 5 O-hydroxy thiol feedstock unsaturated esters may have multiple terminal car ester monomers connected by polysulfide linkages; alterna bon-carbon double bonds and may contain many different tively, at least 7 C.-hydroxy thiol ester monomers connected unsaturated ester molecules. This fact, combined with car by polysulfide linkages; or alternatively, at least 10 O-hy bon-carbon double bond reactivity and statistical probability, droxy thiol ester monomers connected by polysulfide link dictate that each epoxide ester molecule having terminal ages. In yet other embodiments, the cross-linked C-hydroxy epoxide groups of the epoxide ester composition may not thiol ester composition comprises a C-hydroxy thiol ester have the same number of functional groups, the same ratios of oligomer having from 3 to 20 O-hydroxy thiol ester mono functional groups, and/or the same additional features. Thus, mers connected by polysulfide linkages; alternatively, from 5 the number of functional group, ratios of functional groups, to 15 O-hydroxy thiol ester monomers connected by polysul and/or additional features of the epoxide ester molecules fide linkages; or alternatively, from 7 to 12 C-hydroxy thiol having terminal epoxide groups of the epoxide ester compo ester monomers connected by polysulfide linkages. sition may be referred to as an average per epoxide thiol ester 0089. In an aspect, the cross-linked C-hydroxy thiol ester molecules within the epoxide ester composition. molecules may include both C.-hydroxy thiolester monomers 0093. In an embodiment, the epoxide ester molecules hav and O-hydroxy thiolester oligomers. For example, the cross ing terminal epoxide groups may have at least 2 ester groups; linked C-hydroxy thiol ester composition may have a com alternatively at least 3 ester groups; or alternatively, at least 4 bined C-hydroxy thiol ester monomer and C.-hydroxy thiol ester groups. In other embodiments, the epoxide ester mol ester oligomer average molecular weight greater than 2,000, ecules having terminal epoxide groups may have from 2 to 8 greater than 5,000 or greater than 10,000. Further, the cross ester groups; alternatively, 3 to 6 ester groups; alternatively, 3 linked C-hydroxy thiol ester composition may have a com to 4 ester groups; alternatively, only 3 ester groups; or alter bined C-hydroxy thiol ester monomer and C.-hydroxy thiol natively, only 4 ester groups. In further embodiments, the ester oligomer average molecular weight ranging from 2,000 epoxide ester molecules having terminal epoxide groups may to 20,000, from 3,000 to 15,000 or from 7,500 to 12,500. In have an average of at least 2 ester groups per epoxide ester another aspect, the C-hydroxy thiol ester monomers and molecule; alternatively, an average of at least 2.5 ester groups O-hydroxy thiol ester oligomers may have a total thiol sulfur per epoxide ester molecule; or alternatively, an average of at content greater than 0.5 weight percent, greater than 1 weight least 3 ester groups per epoxide ester molecule. In yet further percent, greater than 2 weight percent or greater than 4 weight embodiments, the epoxide ester molecules having terminal US 2009/0264669 A1 Oct. 22, 2009 epoxide groups may have an average of from 2 to 8 ester ester molecules having ester linkages comprising a residue of groups per epoxide ester molecule; alternatively, an average a polyol and a carboxylic acid residue having a terminal of from 2 to 7 ester groups per epoxide ester molecule; alter epoxide group may be described as an average per epoxide natively, an average of from 2.5 to 5 ester groups per epoxide ester molecule. ester molecule; or alternatively, an average of from 3 to 4 ester 0098. In an embodiment, the epoxide ester molecules hav groups per epoxide ester molecule. In yet other embodiments, ing ester linkages comprises a residue of a polyol and a the epoxide ester molecules having terminal epoxide groups carboxylic acid residue having a terminal epoxide group. The may have an average of about 3 ester groups per epoxide ester residue of the polyol and the carboxylic acid residue having a molecule; or alternatively, an average of about 4 ester groups terminal epoxide group are independent elements of epoxide per epoxide ester molecule. ester molecules having ester linkages. Consequently, the fea 0094. In an embodiment, the epoxide ester molecules of tures of the residue of the polyol and the carboxylic acid the epoxide ester composition have at least 2 terminal epoxide having a terminal epoxide group are independently described groups; alternatively, at least 3 terminal epoxide groups; or herein and may be used in any combination to describe the alternatively, at least 4 terminal epoxide groups. In other epoxide ester molecules having ester linkages comprising a embodiments, epoxide ester molecules have from 2 to 8 ter residue of a polyol and carboxylic acid residues having a minal epoxide groups; alternatively, 3 to 6 terminal epoxide terminal epoxide group. groups; alternatively, 3 to 4 terminal epoxide groups; alterna 0099. The carboxylic acid residue having a terminal tively, only 3 terminal epoxide groups; or alternatively, only 4 epoxide group may be further described by its structural terminal epoxide groups. In further embodiments, the features. These structural features are independently epoxide ester molecules have an average of at least 1.5 ter described herein and may be utilized in any combination to minal epoxide groups per epoxide ester molecules; alterna describe the carboxylic acid residue of the epoxide ester tively, an average of at least 2.5 terminal epoxide groups per molecules having ester linkages comprising a residue of a epoxide ester molecules; or alternatively, an average of at polyol and carboxylic acid residues having a terminal least 3 terminal epoxide groups per epoxide ester molecules. epoxide group. In yet further embodiments, the epoxide ester molecules have 0100. In an embodiment, the carboxylic acid residuehav an average of from 1.5 to 8 terminal epoxide groups per ing the terminal epoxide group is linear. In another embodi epoxide ester molecules; alternatively, an average of from 2 to ment, the carboxylic acid residuehaving the terminal epoxide 7 terminal epoxide groups per epoxide ester molecules; alter group is branched. natively, an average of from 2.5 to 5 terminal epoxide groups 0101. In an embodiment, the carboxylic acid residuehav per epoxide ester molecules; or alternatively, an average of ing a terminal epoxide group may have at least 4 carbon from 3 to 4 terminal epoxide groups per epoxide ester mol atoms; alternatively, at least 6 carbon atoms; or alternatively, ecules. In yet other embodiments, the epoxide ester mol at least 8 carbonatoms. In some embodiments, the carboxylic ecules have an average of about 3 terminal epoxide groups per acid residue having a terminal epoxide group may have from epoxide ester molecules; or alternatively, an average of about 4 to 20 carbon atoms; alternatively, from 6 to 18 carbon 4 terminal epoxide groups per epoxide ester molecules. atoms; alternatively, from 8 to 14 carbonatoms; alternatively, 0095. In an embodiment, the epoxide ester molecules hav from 10 to 11 carbon atoms; alternatively, only 10 carbon ing terminal epoxide groups may contain carbon-carbon atoms; or alternatively, only 11 carbon atoms. In an embodi double bonds. These carbon-carbon double bonds may result ment, the carboxylic acid residue a terminal epoxide group from incomplete conversion of the feedstock during the for may have an average of at least 4 carbon atoms; alternatively, mation of the epoxide molecules. In some embodiments, the at least 6 carbon atoms; or alternatively, at least 8 carbon average ratio of carbon-carbon double bonds to epoxide atoms. In some embodiments, the carboxylic acid residue a groups is less than 1:5; alternatively, less than 1:7; or alterna terminal epoxide group may have an average of 4 to 20 carbon tively, less than 1:10. atoms; alternatively, of 6 to 18 carbonatoms; alternatively, of 0096. In another aspect, the epoxide ester molecules 8 to 14 carbon atoms; alternatively, of 10 to 11 carbon atoms: within the epoxide ester compositions may be described as alternatively, of about 10 carbon atoms; or alternatively, of having ester linkages comprising a residue of a polyol and a about 11 carbon atoms. carboxylic acid residue having a terminal epoxide group. 0102. In an embodiment, the carboxylic acid residuehav Additional features of the residue of the polyol and carboxy ing a terminal epoxide group may be substantially devoid of lic acid residue having a terminal epoxide group are indepen other functional groups. In further embodiments, the car dently described herein and may be utilized in any combina boxylic acid residue having a terminal epoxide group may be tion to further describe the epoxide ester molecules. devoid of other functional groups (i.e. outside of the terminal 0097. The epoxide ester molecules described as having C-hydroxy and the carbonyl group forming the ester linkage, ester linkages comprising a residue of a polyol and a carboxy the carboxylic acid residue contains only carbon and hydro lic acid residue having a terminal epoxide group may be gen). produced from any unsaturated ester having a terminal car 0103) In an embodiment, the carboxylic acid residues hav bon-carbon double bond described herein. It should be noted ing a terminal epoxide group may have Structure CRE 1. that the feedstock unsaturated esters may have multiple car bon-carbon double bonds and may contain many different unsaturated ester molecules. This fact, combined with car CRE1 bon-carbon double reactivity differences and statistical prob ability, dictate that each epoxide ester molecule having ester linkages comprising a residue of a polyol and a carboxylic lsp acid residue having a terminal epoxide group may not have the same structure. Thus, particular features of the epoxide US 2009/0264669 A1 Oct. 22, 2009 wherein p may be positive integer ranging from 1 to 17; tively, a tetraol; alternatively, a pentaol; or alternatively, a alternatively from 3 to 15; alternatively, from 5 to 11; or hexaol. Suitable polyols that may form the residue of the alternatively 7 to 8. In some embodiments, p may be 7 or polyol include ethane diol, propanediol, butanediol, pen alternatively 8. In other embodiments, p may represent an tanediol, hexanediol, cyclohexane diol, phenylethane diol. average number (whole or fractional) of carbonatom ranging cyclohexanedimethanol, dimethyolpropane, benzene from 1 to 17; alternatively from 3 to 15; alternatively, from 5 dimethanol, cyclohexanetriol, trihydroxybenzene, trim to 11; alternatively 7 to 8; alternatively about 7; or alterna ethyolethane, trimethylolpropane, trimethylolbutane, glyc tively, about 8. Within the carboxylic acid residue structure erol, pentaerythritol, sorbitol, or any combination thereof; CRE 1 the dashed line is the bond to the oxygen atom of the alternatively, cyclohexane diol, trimethylol propane, glyc ester linkage. erol, pentaerythritol, or combinations thereof; alternatively, 0104. The residue of the polyol may be further described glycerol, pentaerythritol, or combinations thereof. In some by its structural features. These structural features are inde embodiments, the polyol that may form the residue of the pendently described herein and may be utilized in any com polyol include 1.2-ethanediol. 1,3-propanediol, 1,4-butane bination to describe the residue of the polyol of the epoxide diol. 1,5-pentanediol, 1.6-hexanediol, dimethylolpropane, ester molecules having ester linkages comprising, or consist neopentylglycol, 2-propyl-2-ethyl-1,3-propanediol. 1,2-pro ing essentially of a residue of a polyol and carboxylic acid panediol. 1,2-butanediol. 1,3-butanediol, 1,4-butanediol, residues having a terminal epoxide group. diethylene glycol, triethylene glycol, polyethylene glycol, 0105. In an embodiment, residue of the polyol may have 2 dipropylene glycol, tripropylene glycol, polypropylene gly to 20 carbonatoms. In some embodiments, the residue of the col, 11-cyclohexanedimethanol, 1.2-cyclohexanedimetha polyol may have 2 to 12 carbon atoms; alternatively, 2 to 8 nol, 1.3-cyclohexanedimethanol, 1.4-cyclohexanedimetha carbon atoms; or alternatively, 2 to 5 carbon atoms. In some nol, 1,3-dioxane-5,5-dimethanol, 1-phenyl-1,2-ethanediol, embodiments, the polyol of the residue of the polyol may trimethylolpropane, trimethylolethane, trimethylolbutane, have had 2 to 8 hydroxyl group; alternatively, 3 to 6 hydroxyl glycerol, 1,2,5-hexanetriol, pentaerythritol, ditrimethylol groups; alternatively, 2 to 4 hydroxyl groups; alternatively, 4 propane, diglycerol, ditrimethylolethane, 1,3,5-trihydroxy to 8 hydroxyl groups; alternatively, only 3 hydroxyl groups; benzene, 1,2-benzenedimethanol. 1,3-benzenedimethanol, alternatively, only 4 hydroxyl groups; alternatively, only 5 1,4-benzenedimethanol, 1-phenyl-1,2-ethanediol, sorbitol, hydroxyl groups; or alternatively, only 6 hydroxyl groups. or any combination thereof. In other embodiments, the polyol 0106. In other embodiments, the residue of the polyol may that may be used as the polyol residue may be trimethylol be a residue of a mixture of polyols. In such an instance the propane, glycerol, pentaerythritol, or combinations thereof; residue of the polyol may have an average of 2 to 20 carbon alternatively, trimethylolpropane; alternatively, glycerol; atoms perpolyol molecule; alternatively, an average of 2 to 12 alternatively, pentaerythritol; or alternatively sorbitol. carbon atoms per polyol molecule; alternatively, an average 0109. It should be appreciated that not all of the hydroxyl of 2 to 8 carbon atoms per polyol molecule; or alternatively, groups of the polyol that form the residue of the polyol may an average of 2 to 5 carbon atoms per polyol molecule. Fur form ester linkages. In some instances some of the hydroxyl ther, the mixture of polyols of the residues of the polyols may groups may not form ester linkages and may remain as have had an average of at least 2.5 hydroxyl groups perpolyol hydroxyl group. In an embodiment, greater than 80, 85,90, 95 molecule; alternatively, 2.5 to 8 hydroxyl groups per polyol percent of all hydroxyl groups of the residue of the polyol molecule; alternatively, an average of 2 to 6 hydroxyl groups form ester linkages. In other embodiments, Substantially all per polyol molecule; alternatively, an average of 2.5 to 5 of the hydroxyl groups of the polyol, which forms the residue hydroxyl groups per polyol molecule; alternatively, an aver of a polyol forming linkages with a carboxylic acid having a age of 2.5 to 4.5 hydroxyl group per polyol molecule; alter terminal epoxide group, form ester linkages. In yet other natively, an average of 2.5 to 3.5 hydroxyl group per polyol embodiments, the epoxide ester molecules having ester link molecule; alternatively, an average of 3 to 4 hydroxyl group ages that may comprise a residue of a polyol and a carboxylic per polyol molecule; alternatively, an average of about 3 acid residue having a terminal epoxide group are substan hydroxyl groups per polyol molecule; alternatively, an aver tially devoid of hydroxy groups derived from the polyol. In age of about 4 hydroxyl groups per polyol molecule; alterna Some embodiments, the average ratio of carboxylic acid resi tively, an average of about 5 hydroxyl groups per polyol dues having a terminal epoxide group to hydroxyl groups of molecule; or alternatively an average of about 6 hydroxy the polyol of the residue of the polyol is greater than 0.70:1; groups per polyol molecule. alternatively, greater than 0.75:1; alternatively, greater than 0107. In an embodiment, the polyol that formed the resi 0.80:1; alternatively, greater than 0.85:1; alternatively, due of the polyol or mixture of polyols that formed the resi greater than 0.90:1; alternatively, greater than 0.95:1. dues of the polyols may have had a molecular weight or 0110. It will be appreciated that not all of the ester linkages average molecular weight less than 300. In other embodi comprising the residue of the polyol may comprise carboxy ments, the polyol that formed the residue of the polyol or lic acid residues having a terminal epoxide group. For mixture of polyols that formed the residues of the polyols may example, some of the ester linkages may comprise a residue have had a molecular weight or average molecular weightless of the polyol and carboxylic acid group having a terminal than 250; alternatively less than 200; alternatively, less than carbon-carbon double bond due to incomplete conversion of 150; or alternatively, less than 100. the feedstock unsaturated ester molecules during the forma 0108. In an embodiments, the polyol that formed the resi tion of the epoxide ester molecules. In Such an instance, the due of the polyol is a diol, triol, a tetraol, pentaol, hexaol, or epoxide ester molecules having ester linkages comprising a combination thereof; alternatively a diol, triol, tetraolor com residue of a polyol and a carboxylic acid residues having a bination thereof; or alternatively, a triol, tetraol or combina terminal epoxide group may be further defined by the average tion thereof. In some embodiments, the polyol that formed the ratio of carboxylic acid residues having a carbon-carbon residue of the polyol is a diol; alternatively, a triol; alterna double bond to carboxylic acid residues having a terminal US 2009/0264669 A1 Oct. 22, 2009

epoxide group. In an embodiment, the average ratio of car gen Sulfide and unsaturated ester molecules having terminal boxylic acid residues having a carbon-carbon double bond to carbon-carbon double bonds (or composition comprising, or carboxylic acid residues having a terminal epoxide group consisting essentially of unsaturated ester molecules having may be less than 1:5; alternatively, less than 1:7; or alterna terminal carbon-carbon double bonds), and b) forming thiol tively, less than 1:10. Additionally or alternatively, the feed ester molecules (or the thiolester composition comprising, or stock used to produce the epoxide ester molecules may con consisting essentially of thiol ester molecules). Generally, tainesterlinkages with Saturated carboxylic acid residues that the thiolester molecules (or composition comprising, or con can not be thiolated and/or carboxylic acid residues having sisting essentially of or thiol ester molecules) are formed at carbon-carbon double bonds which were not thiolated. Con conditions capable of forming the thiol ester molecules (or sidering this situation, in Some embodiments, greater than 75, thiol ester composition comprising, or consisting essentially 80, 85, or 90 percent of all ester linkages comprising the of the thiol ester molecules). The processes described herein residue of the polyol comprise carboxylic acid residues hav can be applied to any unsaturated ester molecules having a ing the terminal epoxide group. terminal carbon-carbon double bond (or unsaturated ester 0111. In an embodiment, the epoxide ester molecules, composition comprising, or consisting essentially of unsat whether described as having particular functional groups or urated ester molecules having a terminal carbon-carbon as epoxide ester molecules having ester linkages comprising double bond) described herein. The processes described a residue of a polyol and carboxylic acid residues having a herein can be used to produce any thiol ester molecules hav terminal epoxide group, may have an average ratio of epoxide ing thiol groups located on a terminal carbon atom and/or groups to ester groups in the epoxide ester molecules of less thiol groups located on the carbon atom adjacent to the ter than 1.15:1; alternatively, less than 1.1:1; or alternatively, less minal carbonatom (or thiolester compositions comprising, or than 1.05:1. In some embodiments, the epoxide ester mol consisting essentially of thiol ester molecules having thiol ecules, whether described as having particular functional groups located on a terminal carbonatom and/or thiol groups groups or as epoxide ester molecules having ester linkages located on the carbon atom adjacent to the terminal carbon comprising a polyol residue and carboxylic acid residues atom) described herein. The process for producing the thiol having a terminal epoxide group, may have an average ratio of ester composition can also include any additional process epoxide groups to ester groups in the epoxide ester molecules steps or process conditions described herein. that ranges from 0.75:1 to 1.15:1; alternatively, ranges from 0115 The molar ratio of hydrogen sulfide to terminal alk 0.85:1 to 1.1:1; or alternatively, ranges from 0.90:1 to 1.05:1. ene groups utilized in the process to produce the thiol ester In other embodiments, the epoxide ester molecules, whether molecules (or composition) can be any molar ratio that pro described as having particular functional groups or as duces the desired thiolester molecules (or compositions). For epoxide ester molecules having ester linkages comprising a example, the thiol ester molecules may have a molar ratio of polyol residue and carboxylic acid residues having a terminal the hydrogen sulfide to terminal alkenegroups of greater than epoxide group, may have an average ratio of epoxide groups 2. In other embodiments, the molar ratio of hydrogen sulfide to ester groups in the thiol ester molecules of about 1:1. to terminal alkenegroups may be greater than 5; alternatively, 0112. In some embodiments, the epoxide ester molecules, greater than 10; alternatively, greater than 15; or alternatively, whether described as having particular functional groups or greater than 20. In other embodiments, the molar ratio of as epoxide ester molecules having ester linkages comprising hydrogen Sulfide to terminal alkene groups may be from 2 to a polyol residue and carboxylic acid residues having a termi 500; alternatively, from 5 to 200; alternatively, from 10 to nal epoxide group, may have an average epoxide oxygen 100; or alternatively, from 100 to 200. content of 2.5 to 12 weight percent; alternatively, 3.5 to 10 0116. The reaction between the unsaturated ester mol weight percent; alternatively, 4.5 to 9 weight percent. In other ecules and hydrogen sulfide may be catalyzed. The catalyst embodiment, the epoxide ester molecules, whether described may be a heterogeneous catalyst or a homogeneous catalyst. as having particular functional groups or as epoxide ester In other embodiments, the reaction of the unsaturated ester molecules having ester linkages comprising a polyol residue molecules and hydrogen sulfide may be initiated by a free and carboxylic acid residues having a terminal epoxide radical initiator or ultraviolet (UV) radiation. Free radical group, may have an epoxy equivalent weight of 140 to 500 initiators or ultraviolet (UV) radiation is preferred when thiol grams; alternatively, 170 to 400 grams; alternatively, 200 to ester molecules having a thiol group located on a terminal 350 grams. carbon atom are desired. Heterogeneous catalysts and/or homogenous acid catalysts are preferred when thiol ester Process for Making Thiol Ester Compositions molecules having a thiol group located on the carbon atom 0113. The thiol ester molecules having thiol groups adjacent to a terminal carbon atom are desired. located on a terminal carbonatom and/or thiol groups located 0117 The free radical initiator may be any free radical on the carbon atom adjacent to the terminal carbon atom or initiator capable of forming free radicals under thermal or the thiol ester compositions comprising, or consisting essen light photolysis. For example, the free radical initiator may be tially of the aforementioned thiol ester molecules may be selected from the general class of compounds having a formed or produced by contacting hydrogen Sulfide and —N=N-group or a —O—O— group. Specific classes of unsaturated ester molecules having a terminal carbon-carbon free radical initiators may include diazo compounds, dialkyl double bond or unsaturated ester composition comprising, or peroxides, hydroperoxides, and peroxy esters. Specific initia consisting essentially of the aforementioned unsaturated tors may include, but are not limited to, azobenzene, 2,2'- ester molecules having a terminal carbon-carbon double aZobis(2-methylpropionitrile, 4,4'-aZobis(4-cyanovaleric bond. acid), 1,1'-azobis(cyclohexanecarbonitrile), 2,2'-azobis(2- 0114 Generally the method for producing the thiol ester methylpropane-), 2,2'-azobis(2-methylpropionamidine)di molecules (or composition comprising, or consisting essen hydro-chloride, methylpropionitrile, azodicarboxamide, tert tially of thiolester molecules) comprises a) contacting hydro butyl hydroperoxide, di-tert-butyl peroxide, US 2009/0264669 A1 Oct. 22, 2009

octylperbenzoate. In some embodiments, the free radical ini formation of the desired thiol ester molecules. For example, tiated reaction may be performed at a reaction temperature the time required for the reaction of the unsaturated ester within 50° C. of the 1 hour half life of the free radical molecules having a terminal carbon-carbon double bond and initiator. In other embodiments, the free radical initiated reac hydrogen Sulfide may be at least 5 minutes. In some embodi tion may be performed at a reaction temperature within +25° ments, the time required for the reaction of the unsaturated C. of the 1 hour half life of the free radical initiator; alterna ester molecules having a terminal carbon-carbon double bond tively, at a reaction temperature within +20°C. of the 1 hour and hydrogen sulfide may range from 5 minutes to 72 hours; halflife of the free radical initiator; alternatively, at a reaction alternatively, from 10 minutes to 48 hours; or alternatively, temperature within +15° C. of the 1 hour half life of the free from 15 minutes to 36 hours. radical initiator, alternatively, at a reaction temperature (0123. The reaction between the unsaturated ester mol within -10° C. of the 1 hour half life of the free radical ecules having a terminal carbon-carbon double bond and initiator. In an embodiment in which the free radical initiator hydrogen sulfide may be performed at any temperature catalyst reaction of the unsaturated ester and hydrogen Sulfide capable of forming the desired thiol ester molecules. For is initiated by light photolysis, the light can be any light example, the unsaturated ester molecules having a terminal capable of creating free radicals. For example, the light may carbon-carbon double bond and hydrogen sulfide may be be ultraviolet (UV) or visible radiation. reacted at a temperature greater than -20°C. In other embodi 0118. The reaction of the unsaturated ester molecules hav ments, the unsaturated ester molecules having a terminal ing terminal carbon-carbon double bonds and hydrogen Sul carbon-carbon double bond and hydrogen sulfide may be fide may be initiated by UV radiation. In these embodiments, reacted at a temperature greater than 0° C.; alternatively, the UV radiation can be any UV radiation capable of initiating greater than 20° C.; alternatively, greater than 50° C.; alter the reaction of the terminal alkene group and hydrogen Sul natively, greater than 80° C.; or alternatively, greater than fide. In some embodiments, the UV radiation may be gener 100°C. In yet other embodiments, the unsaturated ester mol ated by a medium pressure mercury lamp. Although UV ecules having a terminal carbon-carbon double bond and radiation has been described as the light source, other suitable hydrogen sulfide may be reacted at a temperature from -20° types of light sources will be apparent to those of skill in the C. to 200° C.; alternatively, from 120° C. to 240° C.; alterna art and are to be considered within the scope of the present tively, from 170° C. to 210°C.; alternatively, from 185°C. to invention. 195°C.; alternatively, from 20° C. to 200° C.; alternatively, 0119 The heterogeneous catalyst may comprise one or a from 20° C. to 170° C.; or alternatively, from 80° C. to 140° mixture of acid clays (such as Filtrol(R)-24, which is commer C cially available from Englehard), acid Zeolites (such as LZY 0.124. The reaction between the unsaturated ester mol 84, which is commercially available from UOP), cobalt/mo ecules having a terminal carbon-carbon double bond and lybdenum oxide supported catalysts (such as TK-554, which hydrogen sulfide may be performed at any pressure that main is commercially available from Haldor-Topsoe), and nickel/ tains a portion of the hydrogen sulfide in a liquid state. For molybdenum supported oxide catalysts (such as TK-573, example, the unsaturated ester molecules having a terminal which is commercially available from Haldor-Topsoe). The carbon-carbon double bond and hydrogen sulfide reaction homogeneous acid catalyst may be an organic Sulfonic acid. may be performed at a pressure ranging from 100 psig to 2000 Non-limiting examples of organic Sulfonic acids which may psig. In other embodiments, the unsaturated ester molecules be utilized separately or in any combination include meth having a terminal carbon-carbon double bond and hydrogen anesulfonic acid and toluenesulfonic acid. Other suitable Sulfide reaction may be performed at a pressure ranging from types of heterogeneous and homogeneous catalysts will be 150 psig to 1000 psig; or alternatively, from 200 psig to 600 apparent to those of skill in the art and are to be considered psig. within the scope of the present invention. 0.125. In some aspects, the reaction between hydrogensul 0120. The reaction of the and hydrogen sulfide may be fide and the unsaturated ester molecules may occur in the performed in a batch reactor or a continuous reactor. Continu presence of a solvent. In other aspects, the reaction between ous reactors that may be utilized include continuous stirred the unsaturated ester molecules and hydrogen Sulfide occurs reactors, fixed bed reactors, and the like. Batch reactors that in the substantial absence of a solvent. When the solvent is may be utilized include UV batch reactors. Other types of present, the solvent may be a selected from aromatic hydro batch and continuous reactors that can be used in embodi carbons, aliphatic hydrocarbons, organic alcohols, organic ments of the present invention will be apparent to those of ethers, organic carbonates, organic esters, halogenated ali skill in the art and are to be considered within the scope of the phatic hydrocarbons, aromatic hydrocarbons, halogenated present invention. aromatic hydrocarbons, and combinations thereof. Aliphatic 0121. If a continuous reactor is used for the reaction, an hydrocarbons, which may be useful as a solvent, include C to hourly space velocity feed weight of the terminal alkene Cohydrocarbons, or alternatively, Cs to Co. hydrocarbons, composition ranging from 0.1 to 5 may be used to produce the and may be cyclic or acyclic and include linear or branched desired thiol ester molecules. Alternatively, the hourly space isomers, unless otherwise specified. Non-limiting examples velocity feed weight may range from 0.1 to 5; alternatively, of suitable acyclic aliphatic solvents include pentane, hexane, from 0.1 to 2. Alternatively, the unsaturated ester molecule heptane, octane, and combinations thereof. Non-limiting weight hourly space velocity may be about 0.1; alternatively, examples of Suitable cyclic aliphatic solvents include cyclo the unsaturated ester weight hourly space Velocity may be hexane, methyl cyclohexane, and combinations thereof. Aro about 0.25; or alternatively, the feed unsaturated ester weight matic hydrocarbons, which may be useful as a solvent, hourly space Velocity may be about 2. include C to Cao aromatic hydrocarbons; or alternatively, C 0122 The reaction time used for the reaction of the unsat to Co aromatic hydrocarbons. Non-limiting examples of urated ester molecules having a terminal carbon-carbon Suitable aromatic hydrocarbons include benzene, toluene, double bond and hydrogen sulfide may be determined by the Xylene (including ortho-Xylene, meta-xylene, para-Xylene, or US 2009/0264669 A1 Oct. 22, 2009

mixtures thereof), and ethylbenzene, or combinations a terminal carbon-carbon double bond. For example, the thiol thereof. Organic alcohols, organic ethers, organic carbonates, ester composition may be vacuum stripped at a temperature organic esters, which may be useful as a solvent include C to ranging between 25° C. and 250° C.; or, alternatively, Co organic alcohols, organic ethers, organic carbonates, between 50° C. and 200°C. In some embodiments, the thiol organic esters, organic ketones, or organic aldehydes; alter ester composition may be subjected to wiped film evapora natively, C2 to Co organic alcohols, organic ethers, organic tion. In other embodiments, the thiol ester composition may carbonates, organic esters, organic ketones, or organic alde be sparged with an inert gas to remove hydrogen sulfide, at a hydes; or alternatively, C to Cs organic alcohols, organic temperature between 25° C. and 250° C.; or, alternatively, ethers, organic carbonates, organic esters, organic ketones, or between 50° C. and 200°C. The inert gas may be nitrogen, or organic aldehydes. Non-limiting examples of suitable alcohol any other suitable inert gas. Such as argon. Generally, the Solvents include methanol. 1-propanol, 2-propanol, 1-bu stripped or sparged thiol ester composition may include less tanol, 2-butanol, 2-methyl-2-propanol, or mixtures thereof. than 0.1 weight percent hydrogen sulfide. In other embodi Suitable ether solvents may be cyclic or acyclic. Non-limiting ments, the Stripped or sparged thiol ester composition may examples of suitable ethers which may be useful as a solvent include less than 0.05 weight percent hydrogen sulfide; alter include dimethyl ether, diethyl ether, methyl ethyl ether, natively, less than 0.025 weight percent hydrogen sulfide; or monoethers or diethers of glycols (e.g., dimethyl glycol alternatively, less than 0.01 weight percent hydrogen sulfide. ether), furans, substituted furans, dihydrofuran, substituted dihydrofurans, tetrahydrofuran (THF), substituted tetrahy Process for Making C.-Hydroxy Thiol Ester Compositions drofurans, tetrahydropyrians, Substituted tetrahydropyrians, I0128. The C-hydroxy thiol ester molecules having termi 1,3-dioxanes, Substituted 1,3-dioxanes, 1,4-dioxanes, Substi nal C-hydroxy thiol ester groups or the C-hydroxy thiol ester tuted 1,4-dioxanes, or mixtures thereof. In an embodiment, compositions comprising, or consisting essentially of the each substituent of a substituted furan, substituted dihydro aforementioned C-hydroxy thiol ester molecules may be furan, substituted tetrahydrofuran, substituted tetrahydropy formed or produced by contacting hydrogen Sulfide and ran, Substituted 1,3-dioxane, or Substituted 1,4-dioxane, can epoxide ester molecules having a terminal epoxide groups or be a C to Cs alkyl group. Non-limiting examples of Suitable epoxide ester composition comprising, or consisting essen organic carbonates, which may be utilized as a solvent, tially of epoxide ester molecules having a terminal epoxide include ethylene carbonate, propylene carbonate, diethyl car groups. bonate, diethyl carbonate, and combinations thereof. Non I0129 Generally the method for producing the O.-hydroxy limiting examples of suitable esters, which may be utilized as thiolester molecules (or composition comprising, or consist a solvent, include ethyl acetate, propyl acetate, butyl acetate, ing essentially of C-hydroxy thiolester molecules) comprises isobutyl isobutyrate, and combinations thereof. Halogenated a) contacting hydrogen sulfide and epoxide ester molecules aliphatic hydrocarbons, which may be useful as a solvent, having a terminal epoxide group (or composition comprising, include C to Cs halogenated aliphatic hydrocarbons; alter or consisting essentially of epoxide ester molecules having natively, C to Co halogenated aliphatic hydrocarbons; or terminal epoxide groups), and b) forming O-hydroxy thiol alternatively, C to Cs halogenated aliphatic hydrocarbons. ester molecules having terminal C-hydroxy thiol groups (or Non-limiting examples of such halogenated aliphatic hydro the C-hydroxythiolester composition comprising, or consist carbons, which may be utilized as a solvent, include carbon ing essentially of C-hydroxy thiol ester molecules having tetrachloride, chloroform, methylene chloride, dichloroet terminal C-hydroxy thiol groups). Generally, the C-hydroxy hane, trichloroethane, and combinations thereof. Haloge thiol ester molecules having C-hydroxy thiol groups (or the nated aromatic hydrocarbons, which may be useful as a sol C-hydroxy thiol ester composition comprising, or consisting vent, include C to Cao halogenated aromatic hydrocarbons; essentially of C-hydroxy thiol ester molecules having termi or alternatively, C to Co halogenated aromatic hydrocar nal C-hydroxy thiol groups) are formed at conditions capable bons. Non-limiting examples of Suitable halogenated aro of forming C-hydroxy thiol ester molecules having C-hy matic hydrocarbons include chlorobenzene, dichloroben droxy thiol groups (or the C-hydroxy thiol ester composition Zene, and combinations thereof. comprising, or consisting essentially of C-hydroxy thiol 0126. If a solvent is used for the reaction between the ester molecules having terminal C-hydroxythiol groups). The unsaturated ester and hydrogen Sulfide, the quantity of Sol processes described herein can be applied to any epoxide vent can be any amount that facilitates the reaction. In some ester molecules having a terminal epoxide group (or epoxide embodiments, the mass of the solvent is less than 30 times the ester composition comprising, or consisting essentially of mass of the unsaturated ester. In other embodiments, the mass epoxide ester molecules having a terminal epoxide group) of the solvent is less than 20 times the mass of the unsaturated described herein. The processes described herein can be used ester; alternatively, less than 15 times the mass of the unsat to produce any O-hydroxy thiol ester molecules having ter urated ester; alternatively, less than 10 times the mass of the minal C-hydroxy thiol groups (or C-hydroxy thiol ester com unsaturated ester, or alternatively, less than 5 times the mass positions comprising, or consisting essentially of C-hydroxy of the unsaturated ester. In other embodiments, the mass of thiol ester molecules having terminal C-hydroxy thiol the solvent is from 2 times to 20 times the mass of the unsat groups) described herein. The process for producing the and urated ester; alternatively, from 3 times to 15 times the mass O-hydroxy thiol molecules (or the C-hydroxythiolester com of the unsaturated ester; alternatively, 4 times to 15 times the position) can also include any additional process steps or mass of the unsaturated ester; or alternatively, from 5 times to process conditions described herein. 10 times the mass of the unsaturated ester. 0.130. The molar ratio of hydrogen sulfide to terminal 0127. The process to produce the desired thiol ester com epoxide groups utilized in the process to produce the C-hy position may include a step to remove excess or residual droxy thiol ester molecules (or C-hydroxy thiolester compo hydrogen Sulfide and/or the optional Solvent after reacting the sition) can be any molar ratio that produces the desired C-hy hydrogen Sulfide and the unsaturated ester molecules having droxy thiol ester molecules (or C-hydroxy thiol ester US 2009/0264669 A1 Oct. 22, 2009

composition). For example, the process may use a molar ratio sulfide is at least 15 minutes. In some embodiments, the time of the hydrogen Sulfide to terminal epoxide groups greater required for the reaction of the epoxide ester molecules and than 2. In other embodiments, the molar ratio of hydrogen hydrogen sulfide ranges from 15 minutes to 72 hours; alter Sulfide to terminal epoxide groups may be greater than 5: natively, from 30 minutes to 48 hours; alternatively, from 45 alternatively, greater than 10; alternatively, greater than 15; or minutes to 36 hours. alternatively, greater than 20. In other embodiments, the molar ratio of hydrogen sulfide to terminal epoxide groups 0.137 The reaction between the hydrogen sulfide and the may be from 2 to 500; alternatively, from 5 to 200; alterna epoxide ester molecules having terminal epoxide groups may tively, from 10 to 100; or alternatively, from 100 to 200. occur in the presence of a solvent. However, the reaction may also be performed in the substantial absence of a solvent. 0131 The reaction between the epoxide ester molecules When the solvent is present, the solvent may be a selected and hydrogen Sulfide may be catalyzed. In some embodi from aromatic hydrocarbons, aliphatic hydrocarbons, organic ments, the catalyst may be a heterogeneous catalyst; alterna alcohols, organic ethers, organic carbonates, organic esters, tively, or a homogeneous catalyst. Examples of suitable cata halogenated aliphatic hydrocarbons, aromatic hydrocarbons, lysts are described herein. Additional types of suitable halogenated aromatic hydrocarbons, and combinations catalysts will be apparent to those of skill in the art and are to thereof. Aliphatic hydrocarbons, which may be useful as a be considered within the scope of the present invention. Solvent, include C to Cohydrocarbons, or alternatively, Cs 0132) The reaction of the epoxide ester molecules having to Cohydrocarbons, and may be cyclic oracyclic and include a terminal epoxide group and hydrogen Sulfide may be per linear or branched isomers, unless otherwise specified. Non formed in a batch reactor or a continuous reactor. Continuous limiting examples of Suitable acyclic aliphatic solvents reactors that may be utilized include continuous stirred reac include pentane, hexane, heptane, octane, and combinations tors, fixed bed reactors, and the like. Batch reactors that may thereof. Non-limiting examples of suitable cyclic aliphatic be utilized include autoclave reactors. Other types of batch Solvents include cyclohexane, methyl cyclohexane, and com and continuous reactors that can be used in embodiments of binations thereof. Aromatic hydrocarbons, which may be use the present invention will be apparent to those of skill in the ful as a solvent, include C to Cao aromatic hydrocarbons; or art and are to be considered within the scope of the present alternatively, C to Co aromatic hydrocarbons. Non-limiting invention. examples of Suitable aromatic hydrocarbons include ben 0133. If a continuous reactor is used for the reaction, an Zene, toluene, Xylene (including ortho-Xylene, meta-xylene, hourly space velocity feed weight of the epoxide ester mol para-Xylene, or mixtures thereof), and ethylbenzene, or com ecules having terminal epoxide group may range from 0.1 to binations thereof. Organic alcohols, organic ethers, organic 5. Alternatively, the hourly space velocity feed weight may carbonates, organic esters, which may be useful as a solvent range from 0.1 to 5; alternatively, from 0.1 to 2. Alternatively, include C2 to Cao organic alcohols, organic ethers, organic the unsaturated ester molecule weight hourly space Velocity carbonates, organic esters, organic ketones, or organic alde may be about 0.1; alternatively, the weight hourly space hydes; alternatively, C to Co organic alcohols, organic Velocity of the epoxide ester molecules having terminal ethers, organic carbonates, organic esters, organic ketones, or epoxide groups may be about 0.25; or alternatively, about 2. organic aldehydes; or alternatively, C to Cs organic alcohols, 0134. The reaction between the hydrogen sulfide and the organic ethers, organic carbonates, organic esters, organic epoxide ester molecules having terminal epoxide groups may ketones, or organic aldehydes. Non-limiting examples of suit be performed at any temperature capable of forming the able alcohol solvents include methanol. 1-propanol. 2-pro desired C.-hydroxy thiol ester molecules (O-hydroxy thiol panol. 1-butanol, 2-butanol, 2-methyl-2-propanol, or mix ester composition). In some embodiments, the epoxide ester tures thereof. Suitable ether solvents may be cyclic or acyclic. molecules having terminal epoxide groups and hydrogen Sul Non-limiting examples of suitable ethers which may be use fide may be reacted at a temperature greater than -20°C. In ful as a solvent include dimethyl ether, diethyl ether, methyl other embodiments, the reaction temperature may be greater ethyl ether, monoethers or diethers of glycols (e.g., dimethyl than 0° C.; alternatively, greater than 20° C.; alternatively, glycol ether), furans, Substituted furans, dihydrofuran, Sub greater than 50° C.; or alternatively, greater than 80°C. In yet stituted dihydrofurans, tetrahydrofuran (THF), substituted other embodiments, the reaction temperature may range from tetrahydrofurans, tetrahydropyrians, substituted tetrahydro –20° C. to 200° C.; alternatively, from 20° C. to 170° C.; or pyrans, 1,3-dioxanes, Substituted 1,3-dioxanes, 1,4-dioxanes, alternatively, from 80° C. to 140° C. substituted 1,4-dioxanes, or mixtures thereof. In an embodi 0135 The reaction between the hydrogen sulfide and the ment, each substituent of a substituted furan, substituted epoxide ester molecules having terminal epoxide groups may dihydrofuran, substituted tetrahydrofuran, substituted tet be performed at any reaction pressure that maintains a Sub rahydropyran, Substituted 1,3-dioxane, or Substituted 1,4-di stantial portion of the hydrogen sulfide in a liquid State. In oxane, can be a C to Cs alkyl group. Non-limiting examples Some embodiments, the reaction pressure may range from of Suitable organic carbonates, which may be utilized as a 100 psig to 2000 psig. In other embodiments, the reaction Solvent, include ethylene carbonate, propylene carbonate, pressure may range from 150 to 1000 psig; or alternatively, diethyl carbonate, diethyl carbonate, and combinations from 200 to 600 psig. thereof. Non-limiting examples of suitable esters, which may 0136. The time required for the reaction of the epoxide be utilized as a solvent, include ethyl acetate, propyl acetate, ester molecules having terminal epoxide group and hydrogen butyl acetate, isobutyl isobutyrate, and combinations thereof. sulfide can be any time required to form the desired C-hy Halogenated aliphatic hydrocarbons, which may be useful as droxy thiol molecules having a terminal C-hydroxy thiol a solvent, include C to Cs halogenated aliphatic hydrocar group (or C-hydroxy thiol composition comprising, or con bons; alternatively, C to Cohalogenated aliphatic hydrocar sisting essentially of C-hydroxy thiol molecules having a bons; or alternatively, C to Cs halogenated aliphatic hydro terminal C-hydroxy thiol group). Generally, the time required carbons. Non-limiting examples of Such halogenated for the reaction of the epoxide ester molecules and hydrogen aliphatic hydrocarbons, which may be utilized as a solvent, US 2009/0264669 A1 Oct. 22, 2009

include carbon tetrachloride, chloroform, methylene chlo ester composition comprises contacting a C-hydroxy thiol ride, dichloroethane, trichloroethane, and combinations ester composition comprising with an oxidizing agent and thereof. Halogenated aromatic hydrocarbons, which may be reacting the C-hydroxy thiol ester composition and an oxi useful as a solvent, include C to Co halogenated aromatic dizing agent to form the C-hydroxy thiol ester oligomer hav hydrocarbons; or alternatively, C to Co halogenated aro ing at least two thiolester monomers connected by a polysul matic hydrocarbons. Non-limiting examples of suitable halo fide linkage having the structure —So , wherein Q is an genated aromatic hydrocarbons include chlorobenzene, integer greater than 1. The disclosed methods may be applied dichlorobenzene, and combinations thereof. to any thiol ester composition (or thiol ester composition) or 0138. When a solvent is used for the reaction between the hydroxy thiol ester molecules (or C-hydroxy thiolester com hydrogen Sulfide and the epoxide ester molecules having position) described herein to produce any cross-linked thiol terminal epoxide groups, any amount that may facilitate the ester molecules (or cross-linked thiol ester composition) or reaction may be used. In some embodiments, the mass of the cross-linked C-hydroxy thiolester molecules (or cross-linked solvent may be less than 30 times the mass of the epoxide O-hydroxy thiol ester composition) described herein. The ester molecules having terminal epoxide groups. In other process to produce the cross-linked thiol ester molecules (or embodiments, the mass of the solvent may be less than 20 cross-linked thiol ester composition) or cross-linked C-hy times the mass of the epoxide ester molecules having terminal droxy thiol ester (or cross-linked C-hydroxy thiol ester com epoxide groups; alternatively, less than 15 times the mass of position) can also include any additional process steps or epoxide ester molecules having terminal epoxide groups; process conditions as described herein. alternatively, less than 10 times the mass of the epoxide ester 0.141. In an aspect, the oxidizing agent can be elemental molecules having terminal epoxide groups; or alternatively, Sulfur, oxygen, or hydrogen peroxide. In some embodiments, less than 5 times the mass of the epoxide ester molecules the oxidizing agent can be elemental Sulfur. In other embodi having terminal epoxide groups. In other embodiments, the ments, the oxidizing agent can be oxygen. In some oxygen mass of the solvent is from 2 times to 20 times the mass of the oxidizing agent embodiments, the oxidizing agent is air. In epoxide ester molecules having terminal epoxide groups; further embodiments, the oxidizing agent is hydrogen peroX alternatively, from 3 times to 15 times the mass of the epoxide ide. ester molecules having terminal epoxide groups; alterna 0142. When elemental sulfur is used as the oxidizing tively; 4 times to 15 times the mass of the epoxide ester agent, the quantity of elemental Sulfur utilized to form the molecules having terminal epoxide groups; or alternatively, cross-linked thiol ester molecules (or cross-linked thiol ester from 5 times to 10 times the mass of the epoxide ester mol composition) or cross-linked C-hydroxy thiol ester (or cross ecules having terminal epoxide groups. linked C-hydroxy thiolester composition) is determined as a 0.139. The process to produce the C-hydroxy thiol ester function of the thiol sulfur content of the cross-linked thiol molecules having a terminal C-hydroxy thiol group may ester molecules (or cross-linked thiol ester composition) or include a step to remove excess or residual hydrogen Sulfide cross-linked C-hydroxy thiol ester (or cross-linked C-hy and/or the optional solvent after reacting the hydrogen Sulfide droxy thiol ester composition), respectively. In an aspect, the and the epoxide ester molecules having a terminal epoxide weight ratio of elemental sulfur to thiol sulfur in the thiolester group. For example, the C-hydroxy thiol ester composition composition or C-hydroxy thiol ester composition is at least may be vacuum stripped at a temperature ranging between 0.5. In some embodiments, the weight ratio of elemental 25° C. and 250° C.; or, alternatively, between 50° C. and 200° sulfur to thiol sulfur in the thiol ester composition or C-hy C. In some embodiments, the C-hydroxy thiol ester compo droxy thiol ester composition is at least 5; alternatively, at sition may be subjected to wiped film evaporation. In other least 10, alternatively, at least 15, or alternatively, at least 20. embodiments, the C-hydroxy thiol ester composition may be In other embodiments, the weight ratio of elemental sulfur to sparged with an inert gas to remove hydrogen Sulfide, at a thiol sulfur in the thiol ester composition or O-hydroxy thiol temperature between 25° C. and 250° C.; or, alternatively, ester composition ranges from 0.5 to 32; alternatively, ranges between 50° C. and 200°C. The inert gas may be nitrogen, or from 1 to 24, alternatively, ranges from 2 to 16; or alterna any other suitable inert gas. Such as argon. Generally, the tively, ranges from 3 to 10. stripped or sparged C-hydroxythiol thiol ester composition 0143. In an aspect, the reaction of the thiolester molecule may include less than 0.1 weight percent hydrogen sulfide. In or C-hydroxy thiol ester molecules and elemental sulfur other embodiments, the stripped or sparged C-hydroxy thiol occurs in the presence of a catalyst. The catalyst can be any ester composition may include less than 0.05 weight percent catalyst that catalyzes the formation of the polysulfide link hydrogen sulfide; alternatively, less than 0.025 weight per age between at least two thiol ester monomers. In some cent hydrogen sulfide; or alternatively, less than 0.01 weight embodiments, the catalyst is an amine. In further embodi percent hydrogen sulfide. ments, the catalyst is a tertiary amine. 0144. The formation of the cross-linked thiol ester mol Process for Making Cross-Linked Thiol Ester Compositions ecules (or cross-linked thiol ester composition) or cross 0140. As an embodiment of the present invention, a pro linked C.-hydroxy thiol ester (or cross-linked C-hydroxy thiol cess for producing a cross-linked thiol ester composition is ester composition) can occur in a batch reactor or a continu advantageously provided. In some embodiments, the process ous reactor, as described herein. The formation of the cross to produce the cross-linked thiolester composition comprises linked thiol ester molecules (or cross-linked thiol ester com contacting a thiol ester composition with an oxidizing agent position) or cross-linked C-hydroxy thiol ester (or cross and reacting the thiol ester composition and an oxidizing linked C-hydroxy thiol ester composition) can occur at any agent to form the thiolester oligomer having at least two thiol temperature capable of forming the thiol ester. In some ester monomers connected by a polysulfide linkage having embodiments, the formation of the cross-linked thiol ester the structure —So , wherein Q is an integer greater than 1. molecules (or cross-linked thiol ester composition) or cross Alternatively, the process to produce the cross-linked thiol linked C.-hydroxy thiol ester (or cross-linked C-hydroxy thiol US 2009/0264669 A1 Oct. 22, 2009 20 ester composition) can occurata temperature greater than 25° Sulfide. In other embodiments, the Stripped or sparged thiol C. In other embodiments, the formation of the cross-linked containing ester composition or cross-linked C-hydroxy thiol thiol ester composition or cross-linked C.-hydroxy thiol ester ester composition comprises less than 0.05 weight percent composition can occurs at a temperature greater than 50° C.; hydrogen sulfide; alternatively, less than 0.025 weight per alternatively, greater than 70° C.; or alternatively, greater than cent hydrogen sulfide; or alternatively, less than 0.01 weight 80°C. In yet other embodiments, the formation of the cross percent hydrogen Sulfide. linked thiol ester molecules (or cross-linked thiol ester com position) or cross-linked C-hydroxy thiol ester (or cross Process for Making Terminal Epoxide Ester Compositions linked C-hydroxy thiol ester composition) occurs at a 0.148. The unsaturated ester composition comprising, or temperature from 25°C. to 150° C.; alternatively, from 50° C. consisting essentially of unsaturated ester molecules having to 150° C.; alternatively, from 70° C. to 120° C.; or alterna a terminal carbon-carbon double bond may be used to form tively, from 80° C. to 110° C. epoxide ester composition comprising epoxide ester mol 0145 The time required to form the c cross-linked thiol ecules having a terminal epoxide group by reacting the unsat ester molecules (or cross-linked thiol ester composition) or urated ester molecules having a terminal carbon-carbon cross-linked C-hydroxy thiol ester (or cross-linked C-hy double bond with an oxygen containing compound, option droxy thiol ester composition) can be any time required to ally in the presence of a catalyst. Generally the method for form the desired cross-linked thiol ester molecules or C-hy producing the epoxide ester molecules (or composition com droxy thiol ester molecules. Generally, the time required to prising, or consisting essentially of epoxide ester molecules) form the cross-linked thiol ester molecules (or cross-linked comprises a) contacting unsaturated ester molecules having thiolester composition) or cross-linked C-hydroxy thiol ester terminal carbon-carbon double bonds (or composition com (or cross-linked C-hydroxy thiolester composition) is at least prising, or consisting essentially of unsaturated ester mol 15 minutes. In some embodiments, the time required to form ecules having terminal carbon-carbon double bonds) and an the cross-linked thiol ester molecules (or cross-linked thiol oxygen containing compound and b) forming epoxide ester ester composition) or cross-linked C-hydroxy thiol ester (or molecules having terminal epoxide groups (or the epoxide cross-linked C.-hydroxy thiolester composition) is at least 30 ester composition comprising, or consisting essentially of minutes; alternatively, at least 1 hour, or alternatively, at least epoxide ester molecules having terminal epoxide groups). 2 hours. In yet other embodiments, the time required to form Generally, the epoxide ester molecules having epoxide the cross-linked thiol ester molecules (or cross-linked thiol groups (or the epoxide ester composition comprising, or con ester composition) or cross-linked C-hydroxy thiol ester (or sisting essentially of epoxide ester molecules having termi cross-linked C-hydroxy thiol ester composition) ranges from nal epoxide groups) are formed at conditions capable of form 15 minutes to 72 hours; alternatively, from 30 minutes to 48 ing epoxide ester molecules having epoxide groups (or the hours; alternatively, from 1 hour minutes to 36 hours; or epoxide ester composition comprising, or consisting essen alternatively, from 2 hours and 24 hours. tially of epoxide ester molecules having terminal epoxide 0146 In embodiments, the process to produce the cross groups). The method of producing the epoxide ester mol linked thiol ester molecules (or cross-linked thiol ester com ecules having terminal epoxide groups (or epoxide estercom position) or cross-linked C-hydroxy thiol ester (or cross position comprising, or consisting essentially of the epoxide linked C-hydroxy thiol ester composition) further comprises ester molecules having terminal epoxide groups) can also a step to remove residual hydrogen Sulfide. In some embodi include any additional process steps or process conditions ments the cross-linked thiolester composition or cross-linked described herein. C-hydroxy thiol ester composition is vacuum stripped. In 0149. A number of techniques that are well known in the Some embodiments, the cross-linked thiol ester composition art may be used to perform the epoxidation. Some exemplary or cross-linked C-hydroxy thiol ester composition is vacuum techniques include reaction of the compounds having the striped at a temperature between 25°C. and 250° C.; alterna unsaturated ester molecules having a terminal carbon-carbon tively, between 50° C. and 200° C.; or alternatively, 75 and double bond with a peracid (e.g. peracetic acid or performic 150° C. In some embodiments, the cross-linked thiol ester acid, or the reaction of the compounds having terminal alkene composition or cross-linked C-hydroxy thiol ester composi groups with a peracid generated in situ (e.g. peracetic acid or tion is sparged with an inert gas to remove residual hydrogen performic acid created by reacting acetic, or formic acid, with sulfide. In other embodiments, the cross-linked thiol ester hydrogen peroxide in the presence of a strong acid Such as composition or cross-linked C-hydroxy thiol ester composi Sulfur acid or methanesulfonic acid). tion is sparged with an inert gas at a temperature between 25° 0150. For example, the cross-counter flow process C. and 250° C.; alternatively, between 50° C. and 200° C.; or described in U.S. Pat. No. 4,584,390, herein included by alternatively, between 75 and 150° C. In yet other embodi reference in its entirety, may be used. This process uses a ments, the vacuum stripping is performed while sparging the sequence of tank reactors to implement a countercurrent cross-linked thiol ester composition or cross-linked C-hy staged reaction in which, at each stage, two phases (e.g., droxy thiol ester composition with an inert gas. In yet other organic and aqueous) are stirred together and then separated embodiments, the vacuum stripping is performed while in a phase separator before being sent (in opposite directions) sparging the cross-linked thiol ester composition or cross to the next reactor. The organic phase at each stage includes linked C-hydroxy thiol ester composition an inert gas at a the terminal alkene composition which is being sequentially temperature between 25° C. and 250° C.; alternatively, epoxidized, while the aqueous phase includes hydrogen per between 50° C. and 200° C.; or alternatively, 75 and 150° C. oxide and a formic acid (e.g., a performic acid). Each reaction In some embodiments, the inert gas is nitrogen. is carried out at a temperature of about 50° C. to about 80°C., 0147 Generally, the stripped or sparged cross-linked thiol while each phase separation is carried out at a temperature in ester composition or cross-linked C-hydroxy thiol ester com the range of 15° C. to 60°C. One of ordinary skill in the art position comprises less than 0.1 weight percent hydrogen will recognize that other carboxylic acids (e.g., acetic acid, US 2009/0264669 A1 Oct. 22, 2009

among others) may be used in this process, forming percar have many different structures. Thus, each unsaturated thiol boxylic acids. Further, Small amounts of other materials (e.g., ester molecule having terminal carbon-carbon double bonds Sulfuric acid, among others) may be added as catalysts. may not have the same number of functional groups, the same 0151. A mixture of epoxide ester molecules having a ter ratios of functional groups, and/or the same additional fea minal epoxide group may be formed in the epoxidation reac tures. Consequently, the number of functional group, ratios of tion. The epoxide ester molecules (or epoxide ester compo functional groups, and/or additional features of the unsatur sition comprising, or consisting essentially of epoxide ester ated ester molecules having terminal carbon-carbon double molecules having a terminal epoxide group), may have any bonds may be referred to as an average within the unsaturated feature described herein and may be produced form any ester composition. unsaturated ester molecules having a terminal carbon-carbon 0156. In an embodiment, the unsaturated ester molecules double bond (or unsaturated ester composition comprising, or having terminal carbon-carbon double bonds may have at consisting essentially of unsaturated ester molecules having a least 2 ester groups; alternatively at least 3 ester groups; or terminal carbon-carbon double bond) described herein. alternatively, at least 4 ester groups. In other embodiments, the unsaturated ester molecules having terminal carbon-car Unsaturated Ester Molecules Having Terminal Carbon-Car bon double bonds have from 2 to 8 ester groups; alternatively, bon Double Bonds and Processes for Making Them 3 to 6 ester groups; alternatively, 3 to 4 ester groups; alterna 0152. An intermediate in producing the products tively, only 3 ester groups; or alternatively, only 4 ester described herein are unsaturated ester molecules having ter groups. In further embodiments, the unsaturated ester mol minal carbon-carbon double bonds and unsaturated ester ecules having terminal carbon-carbon double bonds have an composition comprising unsaturated ester molecules having average of at least 2 ester groups per unsaturated ester mol terminal carbon-carbon double bonds. The unsaturated ester ecule; alternatively, an average of at least 2.5 estergroups per molecules having terminal carbon-carbon double bonds (or unsaturated ester molecule; or alternatively, an average of at unsaturated ester composition comprising, or consisting least 3 ester groups per unsaturated ester molecule. In yet essentially of unsaturated ester molecules having terminal further embodiments, the unsaturated ester molecules having carbon-carbon double bonds) are described herein along with terminal carbon-carbon double bonds have an average of a process by which they may be prepared. from 2 to 8 ester groups per unsaturated ester molecule: alternatively, an average of from 2 to 7 ester groups per Unsaturated Ester Molecules Having Terminal Carbon-Car unsaturated ester molecule; alternatively, an average of from bon Double Bonds 2.5 to 5 ester groups per unsaturated ester molecule; or alter natively, an average of from 3 to 4 ester groups per unsatur 0153. In an aspect, the present invention relates to unsat ated ester molecule. In yet other embodiments, the unsatur urated ester compositions comprising, or consisting essen ated ester molecules having terminal carbon-carbon double tially of unsaturated ester molecules having terminal carbon bonds have an average of about 3 estergroups perunsaturated carbon double bonds. In an aspect the unsaturated ester ester molecule; or alternatively, an average of about 4 ester molecules having terminal carbon-carbon double bonds may groups per unsaturated ester molecule. be described as comprising, consisting essentially of one or 0157. In an embodiment, the unsaturated ester molecules more functional group present in the unsaturated ester mol having terminal carbon-carbon double bonds of the thiolester ecules of the unsaturated ester composition. Each of the func composition have at least 2 terminal carbon-carbon double tional groups that may be present in the unsaturated ester bonds; alternatively, at least terminal carbon-carbon double molecules having terminal carbon-carbon double bonds are bonds; or alternatively, at least 4 terminal carbon-carbon independently described herein and may be utilized in any double bonds. In other embodiments, the unsaturated ester combination to described the unsaturated ester molecules molecules having terminal carbon-carbon double bonds have having terminal carbon-carbon double bonds. from 2 to 8 terminal carbon-carbon double bonds; alterna 0154 The independent functional groups that can be uti tively, 3 to 6 terminal carbon-carbon double bonds; alterna lized to describe the thiol ester molecules having terminal tively, 3 to 4 terminal carbon-carbon double bonds; alterna carbon-carbon double bonds include the number of (or aver tively, only 3 terminal carbon-carbon double bonds; or age number of) ester groups per unsaturated ester molecule, alternatively, only 4 terminal carbon-carbon double bonds. In the number of (or average number of) terminal carbon-carbon further embodiments, the unsaturated ester molecules having double bonds per unsaturated ester molecule, and the ratio of terminal carbon-carbon double bonds have an average of at (or average ratio of) terminal carbon-carbon double bonds to least 1.5 terminal carbon-carbon double bonds per unsatur ester group. In some embodiments, the unsaturated ester mol ated ester molecule; alternatively, an average of at least 2.5 ecules having terminal carbon-carbon double bonds may be terminal carbon-carbon double bonds per unsaturated ester substantially devoid of hydroxyl groups. In other embodi molecule; or alternatively, an average of at least 3 terminal ments, the unsaturated ester molecules having terminal car carbon-carbon double bonds per unsaturated ester molecule. bon-carbon double bonds may be substantially devoid of In yet further embodiments, the unsaturated ester molecules functional groups other than ester groups and carbon-carbon having terminal carbon-carbon double bonds have an average double bonds (terminal or otherwise). of from 1.5 to 8 terminal carbon-carbon double bonds per 0155 The unsaturated ester molecules having terminal unsaturated ester molecule; alternatively, an average of from carbon-carbon double bonds may be produced using the 2 to 7 terminal carbon-carbon double bonds per unsaturated methods described herein. It should be noted that the produc ester molecule; alternatively, an average of from 2.5 to 5 tion method may utilize feedstocks containing more than one terminal carbon-carbon double bonds per unsaturated ester structure. This fact, combined with feedstock reactivity dif molecule; or alternatively, an average of from 3 to 4 terminal ferences and statistical probability, dictate that the unsatur carbon-carbon double bonds per unsaturated ester molecule. ated esters having terminal carbon-carbon double bonds may In yet other embodiments, the unsaturated ester molecules US 2009/0264669 A1 Oct. 22, 2009 22 having terminal carbon-carbon double bonds have an average embodiments, the carboxylic acid residuehaving the terminal of about 3 terminal carbon-carbon double bonds per unsatur carbon-carbon double bond is branched. ated ester molecule; or alternatively, an average of about 4 0164. In an embodiment, the carboxylic acid residuehav terminal carbon-carbon double bonds per unsaturated ester ing the terminal carbon-carbon double bond may have at least molecule. 4 carbon atoms; alternatively, at least 6 carbon atoms; or alternatively, at least 8 carbon atoms. In some embodiments, 0158. In an embodiment, the unsaturated ester molecules the carboxylic acid residue having the terminal carbon-car having terminal carbon-carbon double bonds may contain bon double bond may have from 4 to 20 carbon atoms; alter internal carbon-carbon double bonds. These internal carbon natively, from 6 to 18 carbonatoms; alternatively, from 8 to 14 carbon double bonds may result from incomplete conversion carbon atoms; alternatively, from 10 to 11 carbon atoms: of the feedstock. In some embodiments, the average ratio of alternatively, only 10 carbon atoms; or alternatively, only 11 terminal carbon-carbon double bonds to internal carbon-car carbon atoms. In some embodiments, the carboxylic acid bon double bonds is less than 1:5; alternatively, less than 1:7; equivalent having a terminal carbon-carbon double bond may or alternatively, less than 1:10. be a mixture of carboxylic acid residues having a terminal 0159. In an aspect, the unsaturated ester molecules within carbon-carbon double bond. In such embodiments, the car the unsaturated ester compositions may be described as hav boxylic acid residues having a terminal carbon-carbon double ing ester linkages comprising a residue of a polyol and a bond may have an average of at least 6 carbon atoms; or carboxylic acid residue having a terminal carbon-carbon alternatively, at least 8 carbon atoms; alternatively, from 6 to double bond. Additional features of the residue of the polyol 18 carbon atoms; alternatively, from 8 to 14 carbon atoms: and carboxylic acid residue having a terminal carbon-carbon alternatively, from 10 to 11 carbonatoms; alternatively, about double bond are independently describe herein and may be 10 carbon atoms; or alternatively, about 11 carbon atoms. utilized in any combination to further describe the unsatur 0.165. In an embodiment, the carboxylic acid residuehav ated ester molecules. ing the terminal carbon-carbon double bond is substantially 0160 The unsaturated ester molecules described as hav devoid of other functional groups. In further embodiments, ing ester linkages comprising a residue of a polyol and a the carboxylic acid residue having the terminal carbon-car carboxylic acid residue having a terminal carbon-carbon bon double bond is devoid of other functional groups (i.e. that double bond may be produced from any unsaturated esters outside of the terminal carbon-carbon double bond and the described herein. It should be noted that the feedstock unsat carbonyl group forming the ester linkage, the carboxylic acid urated esters may have multiple double bonds, have double contains only carbon and hydrogen). bonds at different positions, and may contain many different 0166 In an embodiment, the carboxylic acid residues hav unsaturated ester molecules. This fact, combined with car ing a terminal carbon-carbon double bond epoxide group may bon-carbon double bond reactivity and/or statistical probabil have Structure CRU 1. ity, dictate that each unsaturated thiol ester molecule having ester linkages comprising a residue of a polyol and a carboxy lic acid residue having a terminal carbon-carbon double bond CRU 1 may not have the same structure. Thus, particular features of the unsaturated ester molecules having ester linkages com prising a residue of a polyol and a carboxylic acid residue having a terminal carbon-carbon double bond may be described as an average per unsaturated ester molecule. wherein p may be positive integer ranging from 1 to 17; 0161. In an embodiment, the unsaturated ester molecules alternatively from 3 to 15; alternatively, from 5 to 11; or having ester linkages comprising a residue of a polyol and alternatively 7 to 8. In some embodiments, p may be 7 or carboxylic acid residues having a terminal carbon-carbon alternatively 8. In other embodiments, p may represent an double bond. The residue of the polyol and the carboxylic average number (whole or fractional) of carbonatom ranging acid residue having a terminal carbon-carbon double bond from 1 to 17; alternatively from 3 to 15; alternatively, from 5 independent elements of unsaturated ester molecules having to 11; alternatively 7 to 8; alternatively about 7; or alterna ester linkages. Consequently, the features of the residue of the tively, about 8. Within the carboxylic acid residue structure polyol and the carboxylic acid having a terminal carbon CRU 1 the dashed line is the bond to the oxygen atom of the carbon double bond are independently described herein and ester linkage. may be used in any combination to describe the unsaturated 0.167 Suitable carboxylic acid residues having a terminal ester molecules having ester linkages comprising a residue of carbon-carbon double bond include 3-butenoic acid residue, a a polyol and at least two carboxylic acid residues having a 4-pentenoic acid residue, a 5-hexenoic acid residue, a 6-hep terminal carbon-carbon double bond. tenoic acid residue, a 7-octenoic acid residue, a 8-nonenoic 0162 The carboxylic acid residue having a terminal car acid residue, a 9-decenoic acid residue, a 10-undecenoic acid bon-carbon double bond may be further described by its residue, a 11-dodecenoic acid residue, a 12-tridecenoic acid structural features. These structural features are indepen residue, a 13-tetradecenoic acid residue, a 14-pentadecenoic dently described herein and may be utilized in any combina acid residue, a 15-hexadecenoic acid residue, a 16-heptade tion to describe the carboxylic acid residue having a terminal cenoic acid residue, a 17-octadecenoic acid residue, a carbon-carbon double bond of the unsaturated ester mol 18-nonadecenoic acid residue, a 19-eicosene, or any combi ecules having ester linkages comprising a residue of a polyol nation thereof. In some embodiments, the carboxylic acid and carboxylic acid residues having a terminal carbon-carbon residues having a thiol group located on the terminal carbon double bond. atom include a 5-hexenoic acid residue, a 6-heptenoic acid 0163. In an embodiment, the carboxylic acid residuehav residue, a 7-octenoic acid residue, a 8-nonenoic acid residue, ing the terminal carbon-carbon double bond is linear. In some a 9-decenoic acid residue, a 10-undecenoic acid residue, a US 2009/0264669 A1 Oct. 22, 2009

11-dodecenoic acid residue, a 12-tridecenoic acid residue, a average molecular weight less than 300. In other embodi 13-tetradecenoic acid residue, a 14-pentadecenoic acid resi ments, the polyol that formed the residue of the polyol or due, a 15-hexadecenoic acid residue, a 16-heptadecenoic acid mixture of polyols that formed the residues of the polyols may residue, a 17-octadecenoic acid residue, or any combination have had a molecular weight or average molecular weightless thereof, alternatively, a 7-octenoic acid residue, a 8-nonenoic than 250; alternatively less than 200; alternatively, less than acid residue, a 9-decenoic acid residue, a 10-undecenoic acid 150; or alternatively, less than 100. residue, a 11-dodecenoic acid residue, a 12-tridecenoic acid residue, a 13-tetradecenoic acid residue, or any combination 0172. In an embodiments, the polyol that formed the resi thereof; or alternatively, 9-decenoic acid residue, a 10-unde due of the polyol is a diol, triol, a tetraol, pentaol, hexaol, or cenoic acid residue, or any combination thereof. In other combination thereof; alternatively a diol, triol, tetraolor com embodiments, the carboxylic acid residues having a terminal bination thereof; or alternatively, a triol, tetraol or combina carbon-carbon double bond may be a 5-hexenoic acid resi tion thereof. In some embodiments, the polyol that formed the due; alternatively, a 6-heptenoic acid residue, alternatively, a residue of the polyol is a diol; alternatively, a triol; alterna 7-octenoic acid residue; alternatively, a 8-nonenoic acid resi tively, a tetraol; alternatively, a pentaol; or alternatively, a due; alternatively, a 9-decenoic acid residue; alternatively, a hexaol. Suitable polyols that may form the residue of the 10-undecenoic acid residue; alternatively, a 11-dodecenoic polyol include ethane diol, propanediol, butanediol, pen acid residue; alternatively, a 12-tridecenoic acid residue; tanediol, hexanediol, cyclohexane diol, phenylethane diol. alternatively, a 13-tetradecenoic acid residue, alternatively, a cyclohexanedimethanol, dimethyolpropane, benzene 14-pentadecenoic acid residue; alternatively, a 15-hexade dimethanol, cyclohexanetriol, trihydroxybenzene, trim cenoic acid residue, alternatively, a 16-heptadecenoic acid ethyolethane, trimethylolpropane, trimethylolbutane, glyc residue, or alternatively, a 17-octadecenoic acid residue. erol, pentaerythritol, sorbitol, or any combination thereof; 0168 The residue of the polyol may be further described alternatively, cyclohexane diol, trimethylol propane, glyc by its structural features. These structural features are inde erol, pentaerythritol, or combinations thereof; alternatively, pendently described herein and may be utilized in any com glycerol, pentaerythritol, or combinations thereof. In some bination to describe the residue of the polyol of the unsatur embodiments, the polyol that may form the residue of the ated ester molecules having ester linkages comprising a polyol include 1.2-ethanediol. 1,3-propanediol, 1,4-butane residue of a polyol and carboxylic acid residues having a diol. 1,5-pentanediol, 1.6-hexanediol, dimethylolpropane, terminal carbon-carbon double bond. neopentylglycol, 2-propyl-2-ethyl-1,3-propanediol. 1,2-pro 0169. In an embodiment, residue of the polyol may have panediol. 1,2-butanediol. 1,3-butanediol, 1,4-butanediol, had 2 to 20 carbon atoms. In some embodiments, the residue diethylene glycol, triethylene glycol, polyethylene glycol, of the polyol may have 2 to 12 carbon atoms; alternatively, 2 dipropylene glycol, tripropylene glycol, polypropylene gly to 8 carbon atoms; or alternatively, 2 to 5 carbon atoms. In col, 11-cyclohexanedimethanol, 1.2-cyclohexanedimetha further embodiments, the polyol may be a mixture of polyols nol, 1.3-cyclohexanedimethanol, 1.4-cyclohexanedimetha having an average of 2 to 20 carbon atoms per polyol mol ecule; alternatively, an average of from 2 to 12 carbon atoms nol, 1,3-dioxane-5,5-dimethanol, 1-phenyl-1,2-ethanediol, perpolyol molecule; alternatively, an average of2 to 8 carbon trimethylolpropane, trimethylolethane, trimethylolbutane, atoms; alternatively an average of 2 to 5 carbon atoms per glycerol, 1,2,5-hexanetriol, pentaerythritol, ditrimethylol polyol molecule. propane, diglycerol, ditrimethylolethane, 1,3,5-trihydroxy 0170 In an embodiment, the polyol of the residue of the benzene, 1,2-benzenedimethanol. 1,3-benzenedimethanol, polyol may have had 2 to 8 hydroxyl group; alternatively, 3 to 1,4-benzenedimethanol, 1-phenyl-1,2-ethanediol, sorbitol, 6 hydroxyl groups; alternatively, 2 to 4 hydroxyl groups; or any combination thereof. In other embodiments, the polyol alternatively, 4 to 8 hydroxyl groups; alternatively, only 3 that may be used as the polyol residue may be trimethylol hydroxyl groups; alternatively, only 4 hydroxyl groups; alter propane, glycerol, pentaerythritol, or combinations thereof. natively, only 5 hydroxyl groups; or alternatively, only 6 alternatively, trimethylolpropane; alternatively, glycerol; hydroxyl groups. In other embodiments, mixtures of residue alternatively, pentaerythritol; or alternatively sorbitol. of polyol may be used and the mixture of polyols of the 0173 It should be appreciated that not all of the hydroxyl residues of the polyols may have had an average at least 2 groups of the polyol that form the residue of the polyol of the hydroxyl groups per polyol molecule; alternatively, at least unsaturated ester molecule having ester linkages must form 2.5 hydroxyl groups perpolyol molecule; alternatively, 2.5 to ester linkages. In some instances some of the hydroxyl groups 8 hydroxyl groups perpolyol molecule; alternatively, an aver may not form ester linkages and may remain as hydroxyl age of 2 to 6 hydroxyl groups per polyol molecule; alterna group. In an embodiment, greater than 80, 85,90, 95 percent tively, an average of 2.5 to 5 hydroxyl groups per polyol of all hydroxyl groups of the residue of the polyol form ester molecule; alternatively, an average of 2.5 to 4.5 hydroxyl linkages. In an embodiment, the unsaturated ester molecules group per polyol molecule; alternatively, an average of 2.5 to having ester linkages that may comprise a residue of a polyol 3.5 hydroxyl group per polyol molecule; alternatively, an and carboxylic acid residues having a terminal carbon-carbon average of 3 to 4 hydroxyl group per polyol molecule; alter double bond are substantially devoid of hydroxy groups natively, an average of about 3 hydroxyl groups per polyol derived from the polyol. In other embodiments, substantially molecule; alternatively, an average of about 4 hydroxyl all of the hydroxyl groups of the polyol that forms the residue groups perpolyol molecule; alternatively, an average of about of a polyol form ester linkages with a carboxylic acid residue 5 hydroxyl groups per polyol molecule; or alternatively an having a terminal carbon-carbon double bond. In some average of about 6 hydroxy groups per polyol molecule. embodiments, the average ratio of carboxylic acid residues 0171 In an embodiment, the polyol that formed the resi having a terminal carbon-carbon double bond to hydroxyl due of the polyol or mixture of polyols that formed the resi groups of the polyol of the residue of the polyol is greater than dues of the polyols may have had a molecular weight or 0.70:1; alternatively, greater than 0.75:1; alternatively, US 2009/0264669 A1 Oct. 22, 2009 24 greater than 0.80:1; alternatively, greater than 0.85:1; alter 0177. The choice of the technique utilized to produce the natively, greater than 0.90:1; alternatively, greater than 0.95: unsaturated esters having a terminal carbon-carbon double 1 bond may depend on the purity of the Source composition, the 0.174. It will be appreciated that not all of the ester linkages cost of the process, the identity of the Source composition, and the desired purity of the final composition. For example, the comprising the residue of the polyol may comprise carboxy metathesis process may provide a higher purity composition, lic acid residues having a terminal carbon-carbon double e.g., due to a higher yield, but may have a higher cost of bond. For example, Some of methods of producing the unsat implementation due to catalyst costs and purification costs for urated ester having ester linkages comprising a residue of a the source compound. In contrast, thermal cracking may be polyol and a carboxylic acid residues having a terminal car easier to implement and function on a wider variety of spe bon-carbon double bond may have ester linkages with Satu cies. However, the yields associated with thermal cracking rated carboxylic acid residues. Considering this situation, the may be low, e.g., 50% or less, and, thus, the costs associated unsaturated ester molecules having ester linkages comprising with purifying the terminal alkene composition may be any residue of a polyol described herein and any carboxylic higher. acid residue having a terminal carbon-carbon double bond described herein may have an average of greater than 75, 80. Metathesis of Unsaturated Esters Having Internal Carbon 85, or 90 percent of hydroxyl units of the polyol forming the Carbon Double Bonds residue of the polyol residue having an ester linkage with a carboxylic acid having a terminal carbon-carbon double 0.178 Inanaspect, the unsaturated esters having a terminal bond. carbon-carbon double bonds (or the unsaturated esters com 0175. In an embodiment, the unsaturated ester molecules, positions comprising or consisting essentially of unsaturated whether described as having particular functional groups or esters having a terminal carbon-carbon double bonds) may be as unsaturated ester molecules having ester linkages compris produced by a) contacting ethylene and unsaturated ester ing a residue of a polyol and at least two carboxylic acid molecules having internal carbon-carbon double bonds (oran residues having a terminal carbon-carbon double bond may unsaturated ester composition comprising, or consisting have an average ratio ofterminal carbon-carbon double bonds essentially of unsaturated ester molecules having internal to ester groups in the unsaturated ester molecules less than carbon-carbon double bonds) with a metathesis catalyst com 1.15:1; alternatively, less than 1.1:1; or alternatively, less than position and b) forming unsaturated ester molecules having 1.05:1. In some embodiments, the thiol ester molecules, terminal carbon-carbon double bonds (or composition com whether described as having particular functional groups or prising, or consisting essentially of unsaturated ester mol as unsaturated ester molecules having ester linkages compris ecules having terminal carbon-carbon double bonds). Gener ing a residue of a polyol and at least two carboxylic acid ally, the unsaturated ester molecules having terminal carbon residues having a terminal carbon-carbon double bond may carbon double bonds (or composition comprising, or have an average ratio ofterminal carbon-carbon double bonds consisting essentially of unsaturated ester molecules having to estergroups in the unsaturated ester molecules ranges from terminal carbon-carbon double bonds) are formed at condi 0.75:1 to 1.15:1; alternatively, ranges from 0.85:1 to 1.1:1; or tions capable of forming the unsaturated ester molecules hav alternatively, ranges from 0.90:1 to 1.05:1. In other embodi ing terminal carbon-carbon double bonds (or the unsaturated ments, the thiol ester molecules, whether described as having ester composition comprising, or consisting essentially of particular functional groups oras unsaturated ester molecules unsaturated ester molecules having terminal carbon-carbon having ester linkages comprising a residue of a polyol and double bonds). Generally, any unsaturated ester composition carboxylic acid residues having a terminal carbon-carbon comprising unsaturated ester molecules having internal car double bond may have an average ratio of terminal carbon bon-carbon double bonds described herein may be utilized. In carbon double bonds to ester groups in the unsaturated ester Some embodiments, the unsaturated ester composition com molecules of about 1:1. prising unsaturated ester molecules having an internal car bon-carbon double bond may be any unsaturated natural source oil described herein. Furthermore, the method may be Processes for Producing Unsaturated Ester Molecules Hav utilized to produce any unsaturated ester composition com ing Terminal Carbon-Carbon Double Bonds prising, or consisting essentially of unsaturated ester mol 0176 The unsaturated esters having terminal carbon-car ecules having a terminal carbon-carbon double bond bon double bonds may be produced via various methods. In described herein. The metathesis process for producing the an aspect, the unsaturated ester having terminal carbon-car unsaturated ester composition comprising, or consisting bon double bonds may be produced by metathesis of an essentially of unsaturated ester molecules having terminal unsaturated ester having internal carbon-carbon double carbon-carbon double bonds can also include any additional bonds with ethylene. In another aspect, the unsaturated esters process steps or process conditions described herein. having terminal carbon-carbon double bonds may be pro 0179 Metathesis Scheme 1 provides a general metathesis duced by reacting a polyol with a carboxylic acid having a reaction for one particular unsaturated ester having internal terminal carbon-carbon double bond, a simple ester of a car carbon-carbon bonds found within Some unsaturated ester boxylic acid having a terminal carbon-carbon double bond, or compositions (e.g. a natural source oil such as soybean oil). an anhydride of a carboxylic acid having a terminal carbon One having ordinary skill in the art will recognize Metathesis carbon double bond. In yet another aspect, the unsaturated Scheme 1 is not limiting. The unsaturated ester compositions esters having terminal carbon-carbon double bonds may be comprising, or consisting essentially of unsaturated ester produced via the thermal cracking of unsaturated esters hav molecules having internal carbon-carbon double bonds ing an internal carbon-carbon double bond and a hydroxy described herein may contain additional unsaturated ester group separated from a carbon atom of the internal carbon having internal carbon-carbon double bonds or may contain carbon double bond by a methylene group. totally different unsaturated esters having internal carbon US 2009/0264669 A1 Oct. 22, 2009 25 carbon double bonds than is shown in Metathesis Reaction comprising, or consisting essentially of unsaturated esters Scheme 1. Metathesis Scheme 1 is merely a sample, non having an internal carbon-carbon double bond. Often the true limiting, representation of the metathesis reaction between catalytic species may be difficult to determine because the ethylene and an unsaturated ester molecule having internal initial catalytic specie is transformed to other species once the carbon-carbon double bonds. Additionally, one having ordi metathesis reaction is initiated. One of ordinary skill in the art nary skill in the art will appreciated that Metathesis Scheme 1 will readily recognize the type of metathesis catalyst or met only provides some of the expected by-product that would be athesis catalyst system based upon the compound(s) con produced by the metathesis reaction between ethylene and an tacted with the unsaturated ester composition comprising, or unsaturated ester molecule having internal carbon-carbon consisting essentially of unsaturated esters having an internal double bonds. Depending upon the actual composition of the carbon-carbon double bond. In some instances, a precursor of unsaturated ester compositions comprising, or consisting the metathesis catalyst or metathesis catalyst system may be essentially of unsaturated ester molecules having internal contacted with the unsaturated ester composition comprising, carbon-carbon double bonds and the metathesis reaction con or consisting essentially of unsaturated esters having an ditions, other products, by-products, and impurities may be internal carbon-carbon double bond to create the metathesis produced. catalyst or metathesis catalyst system in situ. One of skill in

Metathesis Scheme 1 O H CH Cs 3 MO C 1. CH HC HC 7 6 O CH CH-O C C C

7 6 O

ethylene, metathesis catalyst O Hs HC2 N CH33 HC2 S. 1C CH O C CH2 C C C na / H H H H H HC 7 6 O H H C S. 2 C CH CH-O , CH2 HC2 f C Fiscs 1 7 6 H O HC H C S. Y H$1. Sch, 7

0180 Generally, any metathesis catalyst that is capable of the art will readily recognize the particular type of metathesis producing unsaturated ester molecules having a terminal car catalyst and/or metathesis catalyst system from the materials bon-carbon double bond from an unsaturated ester composi added/contacted with the unsaturated ester composition com tion comprising, or consisting essentially of unsaturated prising, or consisting essentially of unsaturated esters having esters having an internal carbon-carbon double bond may be an internal carbon-carbon double bond. used. However, depending upon other metathesis reaction 0182. In an embodiment, the metathesis catalyst can be a parameters (e.g. unsaturated ester composition characteris metal oxide based metathesis catalyst system, a metal halide tics and/or the metathesis reaction conditions), particular based metathesis catalyst system, or a metal carbene based class(es) of metathesis catalyst(s) may be selected in particu metathesis catalyst system. In some embodiments, the met lar instances. athesis catalyst can be a metal oxide based metathesis catalyst 0181 Metathesis catalysts and/or metathesis catalyst sys system or a metal halide based metathesis catalyst system. In tems can be classified by the compound(s) of the metathesis other embodiments, the metathesis catalyst may be a metal catalyst contacted with the unsaturated ester composition oxide based metathesis catalyst system; alternatively, a metal US 2009/0264669 A1 Oct. 22, 2009 26 halide based metathesis catalyst system; or alternatively, a group for the metal alkyl can be a methyl group, ethyl group, metal carbene based metathesis catalyst system. n-propyl group, iso-propyl group, n-butyl group, Sec-butyl 0183 For example, the metal oxide based metathesis cata group, or tert-butyl group; alternatively, a methyl group, ethyl lysts or catalyst systems (hereafter referred to as “metal oxide group, n-butyl group, sec-butyl group, or tert-butyl group; metathesis catalyst(s)) may include cobalt oxide, molybde alternatively, a methyl group; alternatively, an ethyl group; num oxide, tungsten oxide, rhenium oxide, or combinations alternatively, an n-butyl group; alternatively, a sec-butyl thereof. In various embodiments, the metal oxide metathesis group; or alternatively, a tert-butyl group. The choice of the catalyst may include a Support, or, alternatively, the metal alkyl group may depend on the activity desired. Examples of oxide metathesis catalyst may be unsupported. Supports that Suitable trialkyl aluminum compound include trimethyl alu may be useful include alumina, Silica, silica-alumina, and minum, triethylaluminum, and tributyl aluminum. The halide aluminum-phosphate. In embodiments, the metal oxide met of the alkyl aluminum halide compounds can be can be chlo athesis catalyst may include a metal alkyl activator, as ride, bromide, or iodide alternatively, bromide; or alterna described herein. Non-limiting examples of metal oxide met tively, iodide. Examples of suitable alkyl aluminum halides athesis catalysts that may be used in embodiments include include ethyl aluminum dichloride, diethylaluminum chlo molybdenum oxide on alumina (MoC)/Al2O), tungsten ride, and ethylaluminum sesquichloride. Suitable alkyl tin oxide on silica (WO/SiO), rhenium oxide on alumina compounds include tetramethyl tin, tetraethyl tin, and tet (ReO/Al2O), cobalt oxide and molybdenum oxide on alu rabutyl tin. mina (CoO/MoC)/Al2O), and rhenium oxide on alumina 0186 Metal carbene metathesis catalysts and/or catalyst activated with tetramethyl tin (ReO/Al2O/SnMe). Other systems (hereafter referred to as “metal carbene metathesis Suitable metal oxide metathesis catalysts are known to those catalyst(s)) may be characterized by the presence of a metal skilled in the art. carbon double bond. As opposed to the metal oxide and the 0184 Metal halide based metathesis catalysts and/or cata metalhalide metathesis catalysts, the metal carbene metathe lyst systems (hereafter referred to as “metal halide metathesis sis catalysts are compounds which have a stable metal-carbon catalyst(s)) may include a halide oftungsten, molybdenum, double bond or can form a metal-carbon double bond in situ or a mixture thereof. In various embodiments, the halide of from a metal precursor having a stable metal-carbon single the metal halide metathesis catalyst may be chloride, bro bond. mide, or iodide. In one embodiment, the halide is chloride. In 0187. The metal of suitable metal carbene metathesis cata another embodiment, the halide is bromide. In another lysts may include, or consist essentially of tungsten, tanta embodiment, the halide is iodide. In various embodiments, lum, osmium, molybdenum, or ruthenium. In an embodi the metal halide metathesis catalyst may include tungsten ment, the metal carbene metathesis catalyst may be a tungsten chloride, molybdenum chloride, or mixtures thereof. In one carbene metathesis catalyst, a molybdenum carbene metathe embodiment, the metal halide metathesis catalyst includes sis catalyst, or a ruthenium carbene metathesis catalyst, or a tungsten chloride. In another embodiment, the metal halide combination thereof. In some embodiments, the metal car metathesis catalyst includes molybdenum chloride. Typi bene metathesis catalyst may be a ruthenium carbene met cally, the metalhalide metathesis catalyst may include a metal athesis catalysts or molybdenum carbene metathesis catalyst. alkyl activator, as described herein. The metalhalide metathe In an embodiment, the metal carbene metathesis catalyst may sis catalyst may include other agents in addition to the metal be a ruthenium carbene metathesis catalysts. In another halide and metal alkyl activator, for example, alcohol or oxy embodiment, the metal carbene metathesis catalyst may be a gen, to provide and/or increase metathesis activity. Non-lim molybdenum carbene metathesis catalyst. In some embodi iting examples of metal halide metathesis catalysts include ments, the metal carbene metathesis catalyst may be a tung tungsten chloride/tetrabutyl tin (WCl/SnMe), tungsten Sten carbene metathesis catalyst. In another embodiment, the chloride/ethylaluminum dichloride (WCl/EtAICl), tung metal carbene metathesis catalyst may be an osmium carbene sten chloride/ethylaluminum dichloride/ethyl alcohol (WCl/ metathesis catalyst. In another embodiment, the metal car EtAlCl/EtOH), molybdenum chloride/triethyl aluminum bene metathesis catalyst may be a ruthenium carbene met (MoCls/AlEt), and molybdenum chloride/triethyl alumi athesis catalyst. In another embodiment, the metal carbene num/O (MoCls/AlEt/O). Other suitable metal halide met metathesis catalyst may be a molybdenum carbene metathe athesis catalysts are known to those skilled in the art. sis catalyst. 0185. Typically, the metal alkyl activator for the metal 0188 In an embodiment, the ruthenium carbene metathe oxide metathesis catalysts or the metalhalide metathesis cata sis catalyst may have the structure L'LX-Ru=CHR lysts may include, or consist essentially of any metal alkyl. wherein L' and Li may bean organic ligand. X is a halide, and Suitable metal alkyl compounds may include alkyl lithium, R represents hydrogen or a hydrocarbyl group. Further alkyl magnesium, alkyl aluminum, alkyl tin compounds, and embodiments of the groups L', L, X, and R are indepen mixtures thereof. In an embodiment, the metal alkyl com dently described herein. Generally, the ruthenium carbene pound may be an alkyl lithium compound. In another embodi metathesis catalyst having the structure L'LX-Ru=CHR ment, the metal alkyl compound may be an alkyl magnesium can be described using any combination of L', L, X, or R, as compound. In another embodiment the metal alkyl compound described herein. may be an alkylaluminum compound. In yet another embodi (0189 In an embodiment, L' and L of the ruthenium car ment, the metal alkyl compound may be an alkyl tin com bene metathesis catalyst having the structure pound. Non-limiting examples of alkyl aluminum com L'LX-Ru=CHR can independently be R', P, an imidazoli pounds, which may be used as the metal alkyl activator, may nylidene group, or an imidazolidinylidene group. In some include trialkyl aluminum compounds and/or alkyl aluminum embodiments, L' and L are R'P; alternatively, L' is R'Pand halide compounds. The alkyl groups on the metal alkyl may L is an imidazolinylidene group or an imidazolidinylidene include any C to Cohydrocarbyl group; or alternatively, a C group; alternatively, L' is R'P and L is an imidazolinylidene to a Cs hydrocarbyl group. In various embodiments, the alkyl group; alternatively, L' is R'P and L is an imidazolidi US 2009/0264669 A1 Oct. 22, 2009 27 nylidene group; alternatively, L' and L are imidazoli 2,6-disubstituted phenyl group; or alternatively, a 2.4.6- nylidene groups; or alternatively, L' and L are imidazolidi trisubstituted phenyl group. Suitable substituents for the sub nylidene groups. stituted phenyl group(s) within the 1,3-disubstituted imida (0190. In an embodiment, R' of R'P can be a hydrocarbyl Zolinylidene group or 1,3-disubstituted imidazolidinylidene group. In some embodiments, each R' of R'P can be the group include any C to Co. hydrocarbyl group; or alterna same; alternatively, each R' of R'P can be different; or alter tively, any C to Cs hydrocarbyl group. In some embodi natively, one R' of R'P can be different from the other two ments, each hydrocarbyl group(s) of the Substituted phenyl R's. In some embodiments, each R' of R'P can be a C to Cs group(s) within the 1,3-disubstituted imidazolinylidene hydrocarbyl group; or alternatively, a C to Cohydrocarbyl group or 1,3-disubstituted imidazolidinylidene group can group. In other embodiments, each hydrocarbyl R' of R'P can independently be a methyl group, ethyl group, n-propyl independently be an alkyl group or an aromatic group; alter group, iso-propyl group, n-butyl group, sec-butyl group, or natively, an alkyl group; or alternatively, an aromatic group. tert-butyl group; alternatively, a methyl group, ethyl group, In an embodiment each alkyl R' of R'P can independently be n-butyl group, sec-butyl group, or tert-butyl group; alterna a methyl group, ethyl group, n-propyl group, isopropyl group, tively, a methyl group; alternatively, an ethyl group, alterna tert-butyl group, neo-pentyl group, cyclopentyl group, or tively, an isopropyl group; or alternatively, a tert-butyl group. cyclohexyl group. In some embodiments, one or more R's of In some embodiments, the 13-substitutents of the 1,3-disub R'P can be a phenyl group; or alternatively a substituted stituted imidazolinylidene group or 1,3-disubstituted imida phenyl group. In an embodiment, the Substituents of the Sub Zolidinylidenegroup can be a 2,6-diisopropylphenyl group or stituted phenyl group(s) within RP can be a C-Cs organyl group(s); or alternatively, C-C hydrocarbyl group(s). In a 2,4,6-trimethylphenyl group; alternatively, a 2,6-diisopro some embodiments, R'P can be a trialkyl phosphine or triph pylphenyl group; or alternatively, a 2,4,6-trimethylphenyl enyl phosphine; alternatively, trialkyl phosphine; or alterna group. tively, triphenyl phosphine. In an embodiment, RP can be 0.192 In various embodiments, each X of the ruthenium trimethyl phosphine, triethyl phosphine, triisopropyl phos carbene metathesis catalyst having the structure phine, tri-tert-butyl phosphine, tri-neopentyl phosphine, tri L'LX-Ru=CHR can independently be chloride, bromide, cyclopentyl phosphine, tricyclohexyl phosphine, or triphenyl or iodide. In an embodiment, X can be chloride. In another phosphine; alternatively, triisopropyl phosphine, tri-tert-bu embodiment, X can be bromide. In another embodiment, X tyl phosphine, tri-neopentyl phosphine, tricyclopentyl phos can be iodide. phine, tricyclohexyl phosphine, or triphenylphosphine; alter 0193 In an embodiment, Rof the ruthenium carbene met natively, tricyclopentyl phosphine, tricyclohexyl phosphine, athesis catalyst having the structure L'LX-Ru=CHR can be or triphenyl phosphine; alternatively, tricyclopentyl phos hydrogen or a C to Cohydrocarbyl group. In some embodi phine or tricyclohexyl phosphine; alternatively, tricyclopen ments, hydrocarbyl group R can be a methyl group (-CH), tyl phosphine; alternatively, tricyclohexyl phosphine; or an ethyl group (-CH2CH), an isopropyl group (-CH alternatively triphenyl phosphine. (CH)), a tert-butyl group (-COCH)), a phenyl group 0191 In an embodiment, the imidazolinylidene group or (—CHs), a 2-methyl-2-propene group (-CH=C(CH)), imidazolidinylidene group can be a C to Cso imidazoli or a 2.2-diphenylethene group (-CH=C(CHs)). In other nylidene group or imidazolidinylidene group; alternatively, a embodiments, R can be a tert-butyl group (-COCH), a C. to Cso imidazolinylidene group or imidazolidinylidene phenyl group (-CHs), a 2-methyl-2-propene group group; alternatively, a Cs to Cao imidazolinylidene group or (—CH=C(CH)), or a 2.2-diphenylethene group imidazolidinylidene group. In some embodiments, the imi (—CH=C(CHS)); alternatively, hydrogen; alternatively, a dazolinylidene group may be a 1,3-disubstituted imidazoli tert-butyl group (-COCH)); alternatively, a phenyl group nylidene group. In some embodiments, the imidazolidi (—CHs); alternatively, a tert-butyl group (-COCH)); nylidene group may be a 1,3-disubstituted alternatively, a phenyl group (-CHs); alternatively, a 2-me imidazolidinylidene group. In an embodiment, each 1.3-Sub thyl-2-propene group (-CH=C(CH)); or alternatively, a stitutents of the 1,3-disubstituted imidazolinylidene group or 2,2-diphenylethene group (-CH=C(CHS)). 1,3-disubstituted imidazolidinylidene group can be a hydro 0194 In some non-limiting embodiments, the ruthenium carbyl group. In an embodiment, the 1.3-substitutents of the carbene metathesis catalyst can be di-chloro(phenylmethyl 1,3-disubstituted imidazolinylidene group or 1,3-disubsti ene)bis(tricyclohexyl phosphine)ruthenium, dichloro(3-me tuted imidazolidinylidene group can be a C to Cohydrocar thyl-2-butenylidene)bis(tricyclohexyl phosphine)ruthenium, byl group. In some embodiments, each 1.3-substitutent of the dichloro(3-methyl-2-butenylidene)bis(tricyclopentyl phos 1,3-disubstituted imidazolinylidene group or 1,3-disubsti phine) ruthenium, 1,3-bis-(2,4,6-trimethylphenyl)-2-(imida tuted imidazolidinylidenegroup can independently be a C to Zolidinylidene)(phenylmethylene)dichloro(tricyclo-hexyl Co aromatic group or a C to Co alkyl groups. In other phosphine)ruthenium, or 1,3-bis-(2,6-diisopropylphenyl)-2- embodiments, the 13-substitutents of the 1,3-disubstituted (imidazolidinylidene)(phenylmethyl-ene)dichloro(tricyclo imidazolinylidene group or 1,3-disubstituted imidazolidi hexyl phosphine)ruthenium. In some embodiments, the nylidene group can be C to Cao aromatic groups; or alterna ruthenium metal carbene metathesis catalyst can be dichloro tively, C to Coalkyl groups. In an embodiment, the aromatic (phenylmethylene)bis(tricyclohexyl phosphine)ruthenium; group(s) of the 1,3-disubstituted imidazolinylidene group or alternatively, dichloro(3-methyl-2-butenylidene)bis(tricy 1,3-disubstituted imidazolidinylidene group can be a substi clohexyl phosphine)ruthenium; alternatively, 1,3-bis-(2,4,6- tuted aromatic group. In some embodiments, the Substituted trimethylphenyl)-2-(imidazolidinylidene)(phenylmethyl aromatic group of the 1,3-disubstituted imidazolinylidene ene)dichloro(tricyclohexyl phosphine) ruthenium; or group or 1,3-disubstituted imidazolidinylidene group can be alternatively, 1,3-bis-(2,6-diisopropylphenyl)-2-(imidazo a 2-disubstituted phenyl group, a 2,6-disubstituted phenyl lidinylidene)(phenyl-methylene)dichloro(tricyclohexyl group, or, a 2,4,6-trisubstituted phenyl group; alternatively, a phosphine)ruthenium. US 2009/0264669 A1 Oct. 22, 2009 28

0.195. In an embodiment, the molybdenum carbene met (NAr)(OR") can independently be a C to Co organic group; athesis catalyst can have the structure Mo(=CHR)(NAr) or alternatively a C to Cs organic group. In some embodi (OR") wherein R is a hydrogen or hydrocarbyl group, Aris a ments, the C to Co or C to Cs organic group can be a Substituted aromatic ring, and R is a hydrocarbyl group or a hydrocarbylhalyl group (a group consisting of hydrogen, car halogenated hydrocarbyl group. Further embodiments of the bon, and halogen atoms); alternatively, a hydrocarbylfluoryl groups R, Arand R' are independently described herein. Gen group (a group consisting of hydrogen, carbon, and fluorine erally, the molybdenum carbene metathesis catalyst having atoms); or alternatively, a hydrocarbyl group. In an embodi the structure Mo(=CHR)(NAr)(OR") can be described ment, the halogenatoms of the hydrocarbylhalyl group can be using any combination of R described herein, Ar described fluorine, chlorine, bromine, iodine or combinations thereof; herein, and R' described herein. alternatively fluorine; alternatively, chlorine; alternatively, 0196. In some embodiments, R of the molybdenum car bromine; or alternatively, iodine. In some embodiments, each bene metathesis catalyst having the structure Mo(=CHR) R" of the molybdenum carbene metathesis catalyst having the (NAr)(OR") can be hydrogen or a C to Co. hydrocarbyl structure Mo(=CHR)(NAr)(OR") can independently be group; or alternatively, a C to Co. hydrocarbyl group. In tert-butyl group ( C(CH)), or a hexafluoro-tert-butyl Some embodiments, the hydrocarbyl group R can be a methyl group (-COCF)(CH)) group. In other embodiments, group (-CH-), an ethyl group (-CH2CH), an isopropyl (OR") can represent a single organic group wherein the two group (-CH(CH)), a tert-butyl group (-COCH)), a phe R" groups attached to the oxygen atoms are connected via a nyl group (-CH3), a 2-methyl-2-propenegroup (-CH=C bond between any divalent, trivalent, or tetravalent atom with (CH)), or a 2,2-diphenylethene group (-CH=C(CHs)). in the R'groups. In furtherembodiments, (OR") can represent In other embodiments R can be a tert-butyl group ( C(CH) a single organic group wherein the two R' groups attached to ), a phenyl group (-CHs), a 2-methyl-2-propene group the oxygen atoms are connected via a carbon-carbon bond (—CH=C(CH)), or a 2.2-diphenylethene group between any carbon atom of the two R' groups. (—CH=C(CHS)); alternatively, a tert-butyl group (-C 0199. In an embodiment, the molybdenum carbene met (CH)) or a phenyl group (-CHs); alternatively, hydrogen; athesis catalyst can be Mo(=CH-C(CH))(N-2,6-diiso alternatively, a tert-butyl group (-COCH)); alternatively, a propylphenyl)(OC(CH)), Mo(=CH-C(CH)(CHs)) phenyl group (-CHs); alternatively, a 2-methyl-2-propene (N-2,6-diisopropyl-phenyl)(OC(CH)), Mo(=CH-C group (-CH=C(CH)); or alternatively, a 2,2-diphe (CH))(N-2,6-diisopropylphenyl)(OC(CH)(CF)), O nylethene group (-H=C(CHs)). Mo(=CH-C(CH)(CH3))(N-2,6-diisopropylphenyl) 0.197 In an embodiment, the substituted aromatic ring, Ar. (OC(CH)(CF)). In other embodiments, the molybdenum of the molybdenum carbene metathesis catalyst having the metathesis catalyst can be Mo(=CH-C(CH))(N-2,6-di structure Mo(=CHR)(NAr)(OR") can be a C to Co. aro isopropylphenyl)(OC(CH)); alternatively, Mo(=CH-C matic group; alternatively, a C to Cao aromatic group. In (CH3)2(CHS))-2,6-diisopropylphenyl)(OC(CH)); alterna Some embodiments, the Substituted aromatic ring, Ar, is a C tively, Mo(=CH-C(CH))-2,6-diisopropylphenyl)(OC to Cohydrocarbyl group. In an embodiment, each substituent (CH)(CF)); or alternatively, Mo(=CH-C(CH)(CHs)) of the Substituted aromatic ring, Ar., of the molybdenum car (N-2,6-diisopropyl-phenyl)(OC(CH)(CF)). bene metathesis catalyst having the structure Mo(=CHR) 0200. In some embodiments, the metal carbene metathesis (NAr)(OR") can independently be a C to Co. hydrocarbyl catalyst can be tethered to a Support. The metal carbene met group; or alternatively, a C to Cs hydrocarbyl group. In some athesis catalyst can be tethered to the Support via any of the embodiments, the Substituted aromatic ring, Ar., of the molyb ligands which do not contain the metal-carbon double bond. denum carbene metathesis catalyst having the structure In an embodiment the metal carbene catalyst Support may be Mo(=CHR)(NAr)(OR") can be a 2-substituted phenyl a polymer. group, a 2,6-disubstituted phenyl group, or alternatively, a 0201 Minimally, the metathesis catalyst composition 2,4,6-trisubstituted phenyl group. In an embodiment, each comprises the metathesis catalyst (and/or the metathesis cata Substituent of the Substituted aromatic ring can independently lyst system components). In an embodiment, the metathesis be a methyl group (-CH), an ethyl group (-CH2CH), an catalyst composition may consist essentially of the metathe isopropyl group (-CH(CH)), a tert-butyl group (-C sis catalyst (or the metathesis catalyst system components). In (CH)), or a neopentyl group (-CHC(CH)); alterna an embodiment, the metathesis catalyst composition com tively; a methyl group (-CH), an isopropyl group (-CH prising the metathesis catalyst can further comprise a solvent (CH)), or a tert-butyl group (-COCH)); alternatively a or diluent. In some embodiments, the metathesis catalyst methyl group (-CH-) or an isopropyl group (-CH(CH)). composition comprising the metathesis catalyst consists In some embodiments, each substituent of the substituted essentially of the metathesis catalyst (or the metathesis cata aromatic ring can independently be a methyl group (-CH-); lyst system components); or alternatively, consists essentially alternatively, an isopropyl group (-CH(CH)), or alterna of the metathesis catalyst (or the metathesis catalyst system tively, a tert-butyl group (-COCH)). In some non-limiting components) and a solvent or diluent. Solvents or diluents embodiments, the Substituted aromatic ring, Ar., of the molyb which may be utilized in the catalyst composition comprising denum carbene metathesis catalyst having the structure the metathesis catalyst are described herein. In other embodi Mo(=CHR)(NAr)(OR") can be a 2-tert-butylphenyl group, ments, the metathesis catalyst composition comprising the a 2,6-dimethylphenyl group, a 2,6-diisopropylphenyl group, metathesis catalyst (or the metathesis catalyst system com or a 2,4,6-trimethyl phenyl group; alternatively, a 2-tert-bu ponents) is substantially devoid of solvent or diluent. tylphenyl group; alternatively, a 2,6-dimethylphenyl group; 0202 In an embodiment, the unsaturated ester composi alternatively, a 2,6-diisopropylphenyl group; or alternatively, tion comprising, or consisting essentially of unsaturated a 2.4.6-trimethyl phenyl group. ester molecules having internal carbon-carbon double bonds 0198 In an embodiment, each R' of the molybdenum car may be purified before being subjected to the metathesis bene metathesis catalyst having the structure Mo(=CHR) reaction to form unsaturated esters having terminal carbon US 2009/0264669 A1 Oct. 22, 2009 29 carbon double bonds. Purification may help extend the life of ing, or consisting essentially of unsaturated esters having the metathesis catalyst system and/or increase the number of internal carbon-carbon double bonds. In an embodiment, the turnovers by removing catalyst poisons that may be present in molar ratio of the metathesis catalyst to the carbon-carbon a unsaturated ester composition comprising, or consisting double bonds may be less than 1:10, less than 1:50, or less essentially of unsaturated ester molecules having internal than 1:100. Further, the molar ratio of carbon-carbon double carbon-carbon double bond. These poisons include water, bonds to metathesis catalyst may be greater than 500,000:1; alcohols, oxygen, organic hydroperoxides, organic peroX alternatively, greater than 1,000,000:1; or alternatively, ides, ketones, and aldehydes, among other compounds. Some greater than 10,000,000:1. of the poisons, e.g. organic peroxides may be generated by the 0206 Generally, a molar excess of ethylene, in relation to contact of the unsaturated ester composition with oxygen in the number of moles of internal carbon-carbon bonds in the air. Many of the metathesis catalysts may be less sensitive to unsaturated ester composition comprising, or consisting these materials, e.g., less prone to deactivation when placed in essentially of unsaturated esters having an internal carbon contact with these groups. Accordingly, the purification per carbon double bond, may be needed to have high conversion formed by a Supplier of a material used as a source composi of the internal carbon-carbon double bonds to terminal car tion may be sufficient. However, even in these cases, purifi bon-carbon double bonds. The molar excess of ethylene may cation may provide a longer better process economics. be ensured by maintaining a high partial pressure of ethylene 0203 Purification may be performed by any number of in the reactor. In an embodiment, the partial pressure of eth techniques. For example, in an embodiment, purification may ylene may be greater than 10 psig, alternatively, greater than start with purging the unsaturated ester composition compris 50 psig; alternatively, greater than 100 psig; or alternatively ing, or consisting essentially of unsaturated ester molecules greater than 150 psig. In some embodiments, the partial pres having internal carbon-carbon double bonds with an inert gas Sure of ethylene may range from 10 psig to 4000 psig, alter which may remove oxygen and part of the water. Water may natively, range from 50 psig to 3000 psig, alternatively, range be removed by contacting the unsaturated ester composition from 100 psig to 2000 psig; or alternatively, range from 150 comprising, or consisting essentially of unsaturated ester psig to 1000 psig. molecules having internal carbon-carbon double bonds with 0207. The temperature of metathesis reaction between an adsorbent. Similar, impurities which have polar groups ethylene and the unsaturated ester composition comprising, may be removed by contacting the unsaturated ester compo or consisting essentially of unsaturated esters having an sition comprising, or consisting essentially of unsaturated internal carbon-carbon double bond may influence by the ester molecules having internal carbon-carbon double bonds desired conversion, the desired reaction time, and the amount with an adsorbent. Adsorbents which may be used in the of impurities and/or by products that can be tolerated, among present techniques include, for example, aluminas, silicas, other factors. In an embodiment, the temperature of the met activated carbons, clays, magnesias, aluminosilicates, athesis reaction between ethylene and the unsaturated ester molecular sieves, titanosilicates, and combinations thereof. composition comprising, or consisting essentially of unsat The unsaturated ester composition comprising, or consisting urated esters having an internal carbon-carbon double bond essentially of unsaturated ester molecules having internal may range from 0°C. to 120° C. In other embodiments, the carbon-carbon double bonds with an adsorbent may be temperature of the metathesis reaction between ethylene and flowed over the adsorbent, e.g., in a drying bed, or may be the unsaturated ester composition comprising, or consisting mixed with the adsorbent and filtered. Once the adsorbent has essentially of unsaturated esters having an internal carbon been removed from the Source composition, the source com carbon double bond may range from 5°C. to 100° C.; alter position may be stored under an inert gas to prevent further natively, range from 10° C. to 80° C.; alternatively, range poisons from developing. One of ordinary skill in the art will from 15° C. to 70° C.; or alternatively, range from 20° C. to recognize that any number of other Suitable techniques may 60° C. be used for purification of the unsaturated ester composition 0208. The time for the metathesis reaction between ethyl comprising, or consisting essentially of unsaturated ester ene and the unsaturated ester composition comprising, or molecules having internal carbon-carbon double bonds with consisting essentially of unsaturated esters having an internal an adsorbent. carbon-carbon double bond may influence by the desired 0204 The metathesis reaction conditions may include conversion, the reaction temperature, and the amount of various factors, for example, the molar ratio of carbon-carbon impurities and/or by products that can be tolerated, among double bonds to metathesis catalyst moieties, the temperature other factors. In an embodiment, the temperature of the met of the metathesis reaction, the ethylene partial pressure in the athesis reaction between ethylene and the unsaturated ester metathesis reaction, the duration of the metathesis reaction, composition comprising, or consisting essentially of unsat and the presence or absence of a solvent. The factors are urated esters having an internal carbon-carbon double bond described independently herein and may be utilized in any may range from 10 minutes to 48 hours. In other embodi combination to further describe the process to produce unsat ments, the temperature of the metathesis reaction between urated ester compositions comprising unsaturated ester com ethylene and the unsaturated ester composition comprising, position comprising, or consisting essentially of unsaturated or consisting essentially of unsaturated esters having an esters having an internal carbon-carbon double bond via met internal carbon-carbon double bond may range from 20 min athesis. utes to 36 hours; alternatively, 30 minutes to 24 hours; or 0205 The amount of metathesis catalyst utilized for the alternatively, 40 minutes to 12 hours. metathesis reaction between ethylene and the unsaturated 0209. The metathesis reaction between ethylene and the ester composition comprising, or consisting essentially of unsaturated ester composition comprising, or consisting unsaturated esters having an internal carbon-carbon double essentially of unsaturated esters having an internal carbon bond may be expressed as a molar ratio of carbon-carbon carbon double bond may be performed in a batch reactor or a double bonds in the unsaturated ester composition compris continuous reactor. Non-limiting examples of continuous US 2009/0264669 A1 Oct. 22, 2009 30 reactors may be utilized include continuous stirred tank reac form, methylene chloride, dichloroethane, trichloroethane, tors, continuous flow fixed bed reactors, slurry reactors, flu and combinations thereof. Halogenated aromatic hydrocar idized bed reactors, continuous plug flow reactors, and cata bons, which may be useful as a solvent, include C to Co lytic distillation reactors, among others. Non-limiting halogenated aromatic hydrocarbons; or alternatively, C to examples of batch reactors that may be utilized include auto Co halogenated aromatic hydrocarbons. Non-limiting clave reactors. Other types of batch and continuous reactors examples of Suitable halogenated aromatic hydrocarbons that can be used in embodiments of the present invention will include chlorobenzene, dichlorobenzene, and combinations be apparent to those of skill in the art and are to be considered thereof. within the scope of the present invention. 0211. If a solvent is used for the metathesis reaction 0210. In some aspects, the metathesis reaction metathesis between ethylene and the unsaturated ester composition com reaction between ethylene and the unsaturated ester compo prising, or consisting essentially of unsaturated esters having sition comprising, or consisting essentially of unsaturated an internal carbon-carbon double bond, the quantity of Sol esters having an internal carbon-carbon double bond may vent can be any amount that facilitates the metathesis reac occur in the presence of a solvent. In other aspects, the reac tion. In some embodiments, the mass of the Solvent is less tion between the metathesis reaction metathesis reaction than 30 times the mass of the unsaturated ester composition. between ethylene and the unsaturated ester composition com prising, or consisting essentially of unsaturated esters having In other embodiments, the mass of the solvent is less than 20 an internal carbon-carbon double bond occurs in the Substan times the mass of the unsaturated ester composition; alterna tial absence of a solvent. When the solvent is present, the tively, less than 15 times the mass of the unsaturated ester Solvent may be selected from aromatic hydrocarbons, ali composition; alternatively, less than 10 times the mass of the phatic hydrocarbons, organic ethers, organic carbonates, unsaturated ester composition; or alternatively, less than 5 organic esters, halogenated aliphatic hydrocarbons, aromatic times the mass of the unsaturated ester composition. In other hydrocarbons, halogenated aromatic hydrocarbons, and com embodiments, the mass of the solvent is from 2 times to 20 binations thereof. Aliphatic hydrocarbons, which may be use times the mass of the unsaturated ester composition; alterna ful as a solvent, include C to Co. hydrocarbons, or alterna tively, from 3 times to 15 times the mass of the unsaturated tively, Cs to Co. hydrocarbons, and may be cyclic or acyclic ester composition; alternatively, 4 times to 15 times the mass and include linear or branched isomers, unless otherwise of the unsaturated ester composition; or alternatively, from 5 specified. Non-limiting examples of suitable acyclicaliphatic times to 10 times the mass of the unsaturated ester composi solvents include pentane, hexane, heptane, octane, and com tion. binations thereof. Non-limiting examples of suitable cyclic 0212. The process to produce the unsaturated ester com aliphatic solvents include cyclohexane, methyl cyclohexane, position comprising, or consisting essentially of unsaturated and combinations thereof. Aromatic hydrocarbons, which esters having an terminal carbon-carbon double bonds by the may be useful as a solvent, include C to Cao aromatic hydro metathesis reaction may include steps to remove by products, carbons; or alternatively, C to Co aromatic hydrocarbons. impurities, and/or the optional solvent. An advantage of the Non-limiting examples of Suitable aromatic hydrocarbons present technique may lie in the potentially easy purification include benzene, toluene, Xylene (including ortho-Xylene, of the final products. Metathesis Scheme 1 provides an exem meta-xylene, para-Xylene, or mixtures thereof), and ethyl plary metathesis reaction between a single unsaturated ester benzene, or combinations thereof. Organic ethers or organic molecule having internal carbon-carbon double bonds, which carbonates, which may be useful as a solvent, include C to may be present in an unsaturated ester composition. It can be Co, organic ethers or organic carbonates; alternatively, C to appreciated that the product mixture resulting from the met Co organic ethers or organic carbonates; or alternatively, C athesis reaction between ethylene and the unsaturated ester to Cs organic ethers or organic carbonates. Suitable ether composition comprising, or consisting essentially of unsat Solvents may be cyclic or acyclic. Non-limiting examples of urated esters having an internal carbon-carbon double bond suitable ethers which may be useful as a solvent include generally contains byproducts which have lower boiling dimethyl ether, diethyl ether, methyl ethyl ether, monoethers points than the desired unsaturated esters having terminal or diethers of glycols (e.g., dimethyl glycol ether), furans, carbon-carbon double bonds. It can also be appreciated that substituted furans, dihydrofuran, substituted dihydrofurans, the unsaturated ester molecule having terminal carbon-car tetrahydrofuran (THF), substituted tetrahydrofurans, tetrahy bon double bonds has a lower boiling point that the uncon dropyrians, Substituted tetrahydropyrans, 1,3-dioxanes, Sub Verted or partially converted unsaturated ester having internal stituted 1,3-dioxanes, 1,4-dioxanes, Substituted 1,4-diox carbon-carbon double bonds. For example, the materials hav anes, or mixtures thereof. In an embodiment, each Substituent ing a boiling point lower that the unsaturated ester molecules of a substituted furan, substituted dihydrofuran, substituted having terminal carbon-carbon double bonds may be tetrahydrofuran, substituted tetrahydropyran, substituted 1,3- removed by flashing them off of the reaction mixture in a dioxane, or Substituted 1,4-dioxane, can be a C to Cs alkyl vacuum stripping process. The unconverted or partially con group. Non-limiting examples of suitable organic carbonates, Verted unsaturated esters having an internal carbon-carbon which may be utilized as a solvent, include ethylene carbon double bond may then be separated from the unsaturated ate, propylene carbonate, diethyl carbonate, diethyl carbon esters having terminal carbon-carbon double bonds via dis ate, and combinations thereof. Halogenated aliphatic hydro tillation and/or wiped film evaporation. Alternatively, the carbons, which may be useful as a solvent, include C to Cs lower boiling by products and unconverted (or partially con halogenated aliphatic hydrocarbons; alternatively, C to Co Verted) unsaturated esters having an internal carbon-carbon halogenated aliphatic hydrocarbons; or alternatively, C to Cs double bonds may be separated from the desired unsaturated halogenated aliphatic hydrocarbons. Non-limiting examples esters having an terminal carbon-carbon double bonds via of Such halogenated aliphatic hydrocarbons, which may be distillation and/or wiped film evaporation. Other techniques utilized as a solvent, include carbon tetrachloride, chloro may be used in addition to or place of vacuum stripping, US 2009/0264669 A1 Oct. 22, 2009 including, for example, column chromatography, column dis One having ordinary skill in the art will appreciate that Ther tillation, and/or phase separation, among other techniques. mal Cracking Scheme 1 is not limiting. The unsaturated ester 0213. In an embodiment, the vacuum stripping process compositions comprising, or consisting essentially of unsat may be run under a vacuum of about 0.001 atmospheres (atm) urated ester molecules having internal carbon-carbon double to 0.5 atm, or under a vacuum of about 0.05 atm to 0.4 atm, or bonds described herein may contain additional unsaturated under a vacuum of 0.25 atm. In embodiments, the vacuum ester having internal carbon-carbon double bonds or may distillation may be run at a temperature of between about 15° contain totally different unsaturated esters having internal C. to 150° C., at a temperature of 15° C. to a temperature of carbon-carbon double bonds than what is shown in Thermal 100° C., or at a temperature of around 25°C. The time for the Cracking Scheme 1. Thermal Cracking Scheme 1 is merely a distillation depends on the molecular weights and vapor pres sample, non-limiting, representation of the thermal cracking Sures of the components. If material having low boiling points reaction that may be utilized to produce a unsaturated ester are present (e.g., 1,3-propadiene resulting from the metathe molecule having terminal carbon-carbon double bonds. sis of two alkenegroups separated by a methylene group) the Additionally, one having ordinary skill in the art will appre vacuum distillation may only take a few minutes. In contrast, ciate that Thermal Cracking Scheme 1 only provides one of if there are lower vapor pressure components present (e.g., many expected by-products that would be produced by the 1-decene) adequate separation may take several hours. In an thermal cracking reaction. Depending upon the actual com embodiment, the vacuum distillation may be run for 5 min position of the unsaturated ester compositions comprising, or utes, 15 minutes, 1 hour, 2 hours, 6 hours, or longer. Alterna consisting essentially of unsaturated ester molecules having tively or additionally, the unsaturated esters having an termi internal carbon-carbon double bonds and the thermal crack nal carbon-carbon double bonds may be sparged with an inert ing reaction conditions, other products, by-products, and gas to remove low boiling components, at a temperature impurities may be produced. between 25°C. and 250° C.; or, alternatively, between 50° C. and 200° C. The inert gas may be nitrogen, or any other Suitable inert gas, such as argon. Thermal Cracking Scheme 1 O OH Thermal Cracking of Unsaturated Natural Source Oils Hav H H ing a Hydroxy Group Cs-C CH CH O C C 0214 Inanaspect, the unsaturated ester composition com M H H HC 7 5 prising, or consisting essentially of unsaturated ester mol O OH ecules having terminal carbon-carbon double bonds may be H H produced via thermal cracking. In a thermal cracking process, CH-O C Cs-C-CH CH the source composition may be heated to a relatively high H temperature under an inert atmosphere, potentially in the 7 presence of a catalyst (e.g. a free radical initiator). Generally, O the unsaturated esters having a terminal carbon-carbon HCV Cs-CH H CS, CH, double bonds (or the unsaturated esters compositions com O C C prising or consisting essentially of unsaturated esters having H H terminal carbon-carbon double bonds) may be produced by a) 7 5 contacting the unsaturated ester molecules having internal heat carbon-carbon double bonds (or an unsaturated ester compo peroxide sition comprising, or consisting essentially of unsaturated O ester molecules having internal carbon-carbon double bonds) Sa and heat, and b) forming unsaturated ester molecules having O C Sch, terminal carbon-carbon double bonds (or composition com / H prising, or consisting essentially of unsaturated ester mol HC 8 ecules having terminal carbon-carbon double bonds). Gener O ally, the unsaturated ester molecules having terminal carbon O CH 3 CH-O C n CH, No C carbon double bonds (or composition comprising, or H H H consisting essentially of unsaturated ester molecules having 8 5 terminal carbon-carbon double bonds) are formed at condi O HC tions capable of forming the unsaturated ester molecules hav Sa ing terminal carbon-carbon double bonds (or the unsaturated O C Sch, ester composition comprising, or consisting essentially of H unsaturated ester molecules having terminal carbon-carbon Yor double bonds). 0215 Generally, thermal cracking reaction works best 0216. The reaction may be run in a tubular reactor, a stirred with unsaturated ester composition comprising, or consisting tank reactor, a fixed bed reactor, a fluidized bed reactor, and a essentially of unsaturated ester molecules having a internal fractionation reactor, among others. The reactor may be carbon-carbon double bond and a hydroxy group separated packed to increase the Surface area, for example, with stain from the carbon-carbon double bond by a methylene group. less Steelballs, milling pieces, or other materials. The packing One such unsaturated ester composition that may be utilized material may also function as a catalyst, for example, alumina is castor oil. Thermal Cracking Scheme 1 provides a general balls. The reaction may be carried out at a temperature of thermal cracking reaction for one particular unsaturated ester between about 250° C. to 700° C., or from 300° C. to 650° C., having internal carbon-carbon bonds found within castor oil. or from 400° C. to 600° C. One of ordinary skill in the art will US 2009/0264669 A1 Oct. 22, 2009 32 recognize that different temperatures may lead to charring of to 0.5 atm, or under a vacuum of about 0.05 atm to 0.4 atm, or the source composition, which may lower yields. under a vacuum of 0.25 atm. In embodiments, the vacuum 0217. The free radical initiator may be any free radical distillation may be run at a temperature of between about 15° initiator capable of forming free radicals under thermal con C. to 150°C., at a temperature of 15° C. to a temperature of ditions. For example, the free radical initiator may be selected 100° C., or at a temperature of around 25°C. The time for the from the general class compounds having a N=N-group distillation depends on the molecular weights and vapor pres or a -O-O-group. Suitable classes of free radical initia Sures of the components. If material having low boiling points tors may include diazo compounds, dialkyl peroxides, hydro are present the vacuum distillation may only take a few min peroxides, and peroxy esters. For example, initiators that may utes. In contrast, if there are lower vapor pressure components be used in embodiments may include azobenzene, 2,2'-azobis present adequate separation may take several hours. In (2-methylpropionitrile, 4,4'-azobis(4-cyanovaleric acid), 1.1'-azobis(cyclohexanecarbonitrile), 2,2'-azobis(2-methyl embodiments, the vacuum distillation may be run for 5 min propane-), 2,2'-azobis(2-methylpropionamidine)dihydro utes, 15 minutes, 1 hour, 2 hours, 6 hours, or longer. Alterna chloride, methylpropionitrile, azodicarboxamide, tert-butyl tively or additionally, the terminal alkene composition may be hydroperoxide, di-tert-butyl peroxide, octylperbenzoate and sparged with an inert gas to remove material having a low benzoyl peroxide. In an embodiment, benzoyl peroxide may boiling points, at a temperature between 25° C. and 250° C.: be used as the initiator. or, alternatively, between 50° C. and 200° C. The inert gas 0218. The thermal cracking reaction may be run for about may be nitrogen, or any other suitable inert gas, such as argon. 5 minutes, 10 minutes, 30 minutes, 60 minutes, 2 hours, or Reaction of a Polyol with an Unsaturated Carboxylic Acid or longer. Generally, the yield of thermal cracking reactions may an Unsaturated Carboxylic Acid Equivalent be low, e.g., about 30% to 50%. Particular types of source 0221. In an aspect, the unsaturated ester molecules having compositions, such as the castor bean oil discussed above a terminal carbon-carbon double bonds (or the unsaturated (structure 4) may provide higher yields, as the hydroxyl group esters compositions comprising or consisting essentially of within one methylene group of the internal carbon-carbon unsaturated esters having a terminal carbon-carbon double double bond may assist the reaction. In this case, the yield bonds) may be produced by a) contacting a polyol (or a may be about 50%. The low yields of this reaction may make composition comprising, consisting essentially of a polyol) purification desirable prior to forming thiolester molecules or and a carboxylic acid having a terminal carbon-carbon double thiol ester compositions. bond and/or carboxylic acid derivative having a terminal car 0219. The process to produce the unsaturated ester com bon-carbon double bond (or composition comprising or con position comprising, or consisting essentially of unsaturated sisting essentially of a carboxylic acid having a terminal esters having terminal carbon-carbon double bonds by a ther carbon-carbon double bond and/or a carboxylic acid deriva mal cracking reaction may include steps to remove by-prod tive having a terminal carbon-carbon double bond) and b) ucts, impurities, and/or the optional solvent. Thermal Crack forming unsaturated esters having a terminal carbon-carbon ing Reaction Scheme 1 provides an exemplary thermal double bonds (or unsaturated ester composition comprising. cracking reaction between a single unsaturated ester mol or consisting essentially of unsaturated ester molecules hav ecule having internal carbon-carbon double bonds which may ing terminal carbon-carbon double bonds). Generally, the be present in an unsaturated ester composition. It can be unsaturated ester molecules having terminal carbon-carbon appreciated that the product mixture resulting from the ther double bonds (or composition comprising, or consisting mal cracking reaction produces by-products which have essentially of unsaturated ester molecules having terminal lower boiling points than the desired unsaturated esters hav carbon-carbon double bonds) are formed at conditions ing terminal carbon-carbon double bonds. It can also be capable of forming the unsaturated ester molecules having appreciated that the unsaturated ester molecule having termi terminal carbon-carbon double bonds (or the unsaturated nal carbon-carbon double bonds has a lower boiling point ester composition comprising, or consisting essentially of than the unconverted or partially converted unsaturated ester unsaturated ester molecules having terminal carbon-carbon having internal carbon-carbon double bonds. For example, double bonds). This process can be applied to any polyol. the materials having a boiling point lower than the unsatur carboxylic acid having a terminal carbon-carbon double ated ester molecules having terminal carbon-carbon double bond, or carboxylic acid derivative having a terminal carbon bonds may be removed by flashing them off of the reaction carbon double bond described herein. The process for pro mixture in a vacuum stripping process. The unconverted or ducing the unsaturated ester molecules having a terminal partially converted unsaturated esters having an internal car carbon-carbon double bonds (or the unsaturated esters com bon-carbon double bonds may then be separated from the positions comprising or consisting essentially of, unsaturated unsaturated esters having an terminal carbon-carbon double esters having terminal carbon-carbon double bonds) can also bonds via distillation and/or wiped film evaporation. Alterna include any additional process steps or process conditions tively, the lower boiling by-products and unconverted (or described herein. Additionally, the process for producing the partially converted) unsaturated esters having an internal car unsaturated ester molecules having a terminal carbon-carbon bon-carbon double bonds may be separated from the desired double bonds (or the unsaturated esters compositions com unsaturated esters having an terminal carbon-carbon double prising or consisting essentially of unsaturated esters having bonds via distillation and/or wiped film evaporation. Other terminal carbon-carbon double bonds) described herein. techniques may be used in addition to or place of vacuum 0222. The polyol that may be utilized in producing the Stripping, including, for example, column chromatography, unsaturated ester molecules having a terminal carbon-carbon column distillation, and/or phase separation, among other double bonds (or the unsaturated esters compositions com techniques. prising, or consisting essentially of unsaturated esters having 0220. In an embodiment, the vacuum stripping process terminal carbon-carbon double bonds) may be further may be run under a vacuum of about 0.001 atmospheres (atm) described by its structural features. These structural features US 2009/0264669 A1 Oct. 22, 2009

are independently described herein and may be utilized in any tially of unsaturated esters having a terminal carbon-carbon combination to describe the polyol. double bonds include ethane diol, propanediol, butanediol, 0223) In one aspect, the polyol used to produce the unsat pentanediol, hexanediol, cyclohexane diol, phenylethane urated ester molecules having a terminal carbon-carbon diol, cyclohexanedimethanol, dimethyolpropane, benzene double bonds (or the unsaturated esters compositions com dimethanol, cyclohexanetriol, trihydroxybenzene, trim prising, or consisting essentially of unsaturated esters having ethyolethane, trimethylolpropane, trimethylolbutane, glyc terminal carbon-carbon double bonds) may have 2 to 20 car erol, pentaerythritol, sorbitol, or any combination thereof; bonatoms. In other embodiments, the polyol may have 2 to 12 alternatively, cyclohexane diol, trimethylol propane, glyc carbon atoms; alternatively from 2 to 8 carbon atoms; alter erol, pentaerythritol, or combinations thereof; alternatively, natively from 2 to 5 carbon atoms. In further embodiments, glycerol, pentaerythritol, or combinations thereof. In some the polyol may be a mixture of polyols having an average of embodiments, the polyol used to produce the unsaturated 2 to 20 carbon atoms per polyol molecule; alternatively, an esters compositions comprising or consisting essentially of average of from 2 to 12 carbon atoms per polyol molecule: unsaturated esters having a terminal carbon-carbon double alternatively, an average of 2 to 8 carbonatoms; alternatively bonds include 1.2-ethanediol. 1,3-propanediol. 1,4-butane an average of 2 to 5 carbon atoms per polyol molecule. diol. 1,5-pentanediol, 1.6-hexanediol, dimethylolpropane, 0224. In an embodiment, the polyol used to produce the neopentylglycol, 2-propyl-2-ethyl-1,3-propanediol. 1,2-pro unsaturated ester molecules having a terminal carbon-carbon panediol. 1,2-butanediol. 1,3-butanediol, 1,4-butanediol, double bonds (or the unsaturated esters compositions com diethylene glycol, triethylene glycol, polyethylene glycol, prising or consisting essentially of unsaturated esters having dipropylene glycol, tripropylene glycol, polypropylene gly a terminal carbon-carbon double bonds) can have any number col, 11-cyclohexanedimethanol, 1.2-cyclohexanedimetha of hydroxy groups needed to produce the unsaturated esters nol, 1.3-cyclohexanedimethanol, 1.4-cyclohexanedimetha compositions comprising or consisting essentially of unsat nol, 1,3-dioxane-5,5-dimethanol, 1-phenyl-1,2-ethanediol, urated esters having a terminal carbon-carbon double bonds trimethylolpropane, trimethylolethane, trimethylolbutane, as described herein. In some embodiments, the polyol may glycerol, 1,2,5-hexanetriol, pentaerythritol, ditrimethylol have 2 to 8 hydroxyl group; alternatively, 3 to 6 hydroxyl propane, diglycerol, ditrimethylolethane, 1,3,5-trihydroxy groups; alternatively, 2 to 4 hydroxyl groups; alternatively, 4 benzene, 1,2-benzenedimethanol. 1,3-benzenedimethanol, to 8 hydroxyl groups; alternatively, only 3 hydroxyl groups; 1,4-benzenedimethanol, 1-phenyl-1,2-ethanediol, sorbitol, alternatively, only 4 hydroxyl groups; alternatively, only 5 or any combination thereof. In other embodiments, the polyol hydroxyl groups; or alternatively, only 6 hydroxyl groups. In that may be used to produce the unsaturated esters composi an embodiment, mixtures of polyols may be used and the tions comprising or consisting essentially of unsaturated polyols may have an average at least 2 hydroxyl groups per esters having a terminal carbon-carbon double bonds may be polyol molecule; alternatively, at least 2.5 hydroxyl groups trimethylolpropane, glycerol, pentaerythritol, or combina per polyol molecule; alternatively, 2.5 to 8 hydroxyl groups tions thereof; alternatively, trimethylolpropane; alternatively, per polyol molecule; alternatively, an average of 2 to 6 glycerol; alternatively, pentaerythritol; or alternatively sorbi hydroxyl groups per polyol molecule; alternatively, an aver tol. age of 2.5 to 5 hydroxyl groups per polyol molecule; alterna 0227. The unsaturated carboxylic acid having a terminal tively, an average of 2.5 to 4.5 hydroxyl group per polyol carbon-carbon double bond used to produce the unsaturated molecule; alternatively, an average of 2.5 to 3.5 hydroxyl ester molecules having a terminal carbon-carbon double group per polyol molecule; alternatively, an average of 3 to 4 bonds (or the unsaturated esters compositions comprising or hydroxyl group perpolyol molecule; alternatively, an average consisting essentially of unsaturated esters having terminal of about 3 hydroxyl groups perpolyol molecule; alternatively, carbon-carbon double bonds) via reaction with the polyol can an average of about 4 hydroxyl groups per polyol molecule: be any unsaturated carboxylic acid having a terminal carbon alternatively, an average of about 5 hydroxyl groups per carbon double bond. Alternatively, the unsaturated carboxy polyol molecule; or alternatively an average of about 6 lic acid equivalent having a terminal carbon-carbon double hydroxy groups per polyol molecule. bond may be any unsaturated carboxylic acid equivalent hav 0225. In an embodiment, the polyol or mixture of polyols ing a terminal carbon-carbon double bond. The unsaturated used to produce the unsaturated ester molecules having a carboxylic acid or carboxylic acid equivalent having a termi terminal carbon-carbon double bonds (or the unsaturated nal carbon-carbon double bond may be further described by esters compositions comprising or consisting essentially of their structural features. These structural features are inde unsaturated esters having a terminal carbon-carbon double pendently described herein and may be utilized in any com bonds) has a molecular weight or average molecular weight bination to describe the unsaturated carboxylic acid or unsat less than 300. In other embodiments, the polyol or mixture of urated carboxylic acid equivalent having a terminal carbon polyols have a molecular weight or average molecular weight carbon double bond. less than 250; alternatively less than 200; alternatively, less 0228. In an embodiment, the unsaturated carboxylic acid than 150; or alternatively, less than 100. equivalent having terminal carbon-carbon double bond may 0226. In an embodiments, the polyol that formed the resi be a simple ester of a carboxylic acid having a terminal due of the polyol is a diol, triol, a tetraol, pentaol, hexaol, or carbon-carbon double bond. In some embodiments, the car combination thereof; alternatively a diol, triol, tetraolor com boxylic acid equivalent is a methyl ester, ethyl ester, n-propyl bination thereof; or alternatively, a triol, tetraol or combina ester, iso-propyl ester, n-butyl ester, or t-butyl ester of the tion thereof. In some embodiments, the polyol that formed the carboxylic acid having a terminal carbon-carbon double residue of the polyol is a diol; alternatively, a triol; alterna bond. In other embodiments, the carboxylic acid equivalent is tively, a tetraol; alternatively, a pentaol; or alternatively, a a methyl ester or ethyl ester of the carboxylic acid having a hexaol. Suitable polyols that may used to produce the unsat terminal carbon-carbon double bond. In some embodiments, urated esters compositions comprising or consisting essen the carboxylic acid equivalent is a methyl ester of a carboxylic US 2009/0264669 A1 Oct. 22, 2009 34 acid having a terminal carbon-carbon double bond. In other acid, a 13-tetradecenoic acid, a 14-pentadecenoic acid, a embodiments, the carboxylic acid equivalent is a ethyl ester 15-hexadecenoic acid, a 16-heptadecenoic acid, a 17-octade of a carboxylic acid having a terminal carbon-carbon double cenoic acid, a 18-nonadecenoic acid, a 19-eicosenoic acid, or bond. In another embodiment, the carboxylic acid equivalent any combination thereof. In some embodiments, the carboxy is an anhydride of a carboxylic acid having a terminal carbon lic acid residues having a thiol group located on the terminal carbon double bond. carbon atom include a 5-hexenoic acid, a 6-heptenoic acid, a 0229 When discussing the structural features of the unsat 7-octenoic acid, a 8-nonenoic acid, a 9-decenoic acid, a urated carboxylic acid equivalent having a terminal carbon 10-undecenoic acid, a 11-dodecenoic acid, a 12-tridecenoic carbon double bond, the structural features will be described acid, a 13-tetradecenoic acid, a 14-pentadecenoic acid, a as those of the parent carboxylic acid having a terminal car 15-hexadecenoic acid, a 16-heptadecenoic acid, a 17-octade bon-carbon double bond. For example, an unsaturated car cenoic acid, or any combination thereof, alternatively, a boxylic acid equivalent having a terminal carbon-carbon 7-octenoic acid, a 8-nonenoic acid, a 9-decenoic acid, a double bond and 7 carbon atoms refers to the same compo 10-undecenoic acid, a 11-dodecenoic acid, a 12-tridecenoic nent forming the ester group with the polyol as a carboxylic acid, a 13-tetradecenoic acid, or any combination thereof; or acid having a terminal double bond and 7 carbon atoms. alternatively, 9-decenoic acid, a 10-undecenoic acid, or any 0230. The unsaturated carboxylic acid or unsaturated car combination thereof. In other embodiments, the carboxylic boxylic acid equivalent having a terminal carbon-carbon acid residues having a terminal carbon-carbon double bond double bond may be further described by its structural fea may be a 5-hexenoic acid; alternatively, a 6-heptenoic acid; tures. These structural features are independently described alternatively, a 7-octenoic acid; alternatively, a 8-nonenoic herein and may be utilized in any combination to describe the acid; alternatively, a 9-decenoic acid; alternatively, a 10-un carboxylic acid or carboxylic acid equivalent having a termi decenoic acid; alternatively, a 11-dodecenoic acid; alterna nal carbon-carbon double bond. tively, a 12-tridecenoic acid; alternatively, a 13-tetradecenoic 0231. In an embodiment, the unsaturated carboxylic acid acid; alternatively, a 14-pentadecenoic acid; alternatively, a or unsaturated carboxylic equivalent having a terminal car 15-hexadecenoic acid; alternatively, a 16-heptadecenoic bon-carbon double bond is linear. In some embodiments, the acid; or alternatively, a 17-octadecenoic acid. Suitable unsat unsaturated carboxylic acid or unsaturated carboxylic urated carboxylic acid equivalents having a terminal carbon equivalent having a terminal carbon-carbon double bond is carbon double bond may be described as those based upon branched. In further embodiments, the unsaturated carboxy any unsaturated carboxylic acid equivalent having a terminal lic acid or unsaturated carboxylic equivalent having a termi carbon-carbon double bond described herein (e.g. methyl nal carbon-carbon double bond is substantially devoid of 9-decanoate or methyl 10-undecenoate). other functional groups. In further embodiments, the unsat 0234. The equivalent ratio of unsaturated carboxylic acid urated carboxylic acid or unsaturated carboxylic equivalent or unsaturated carboxylic equivalent having a terminal car having a terminal carbon-carbon double bond is devoid of bon-carbon double bond to equivalents of polyol hydroxyl other functional groups. groups (hereinafter "unsaturated carboxylic acid group to 0232. In an embodiment, the unsaturated carboxylic acid polyol hydroxyl group equivalent ratio’) utilized in the pro or unsaturated carboxylic equivalent having a terminal car cess to produce the unsaturated ester molecules having a bon-carbon double bond may have at least 4 carbon atoms; terminal double bond (or the desired unsaturated ester com alternatively, at least 6 carbon atoms; or alternatively, at least position comprising unsaturated ester molecules having ter 8 carbon atoms. In some embodiments, the unsaturated car minal carbon-carbon double bonds) may be any unsaturated boxylic acid or unsaturated carboxylic equivalent having a carboxylic acid group to polyol hydroxyl group equivalent terminal carbon-carbon double bond may have from 4 to 20 ratio that produces the unsaturated ester molecules having a carbonatoms; alternatively, from 6 to 18 carbonatoms; alter terminal carbon-carbon double bonds (or the desired unsat natively, from 8 to 14 carbon atoms; alternatively, from 10 to urated ester composition comprising unsaturated ester mol 11 carbon atoms; alternatively, only 10 carbon atoms; or ecules having terminal carbon-carbon double bonds). In some alternatively, only 11 carbon atoms. In some embodiments, a embodiments, the unsaturated carboxylic acid group to mixture of unsaturated carboxylic acid having a terminal polyol hydroxyl group equivalent ratio is greater than 1:1. In carbon-carbon double bond may be used; or alternatively, a other embodiments, the unsaturated carboxylic acid group to mixture of unsaturated carboxylic acid equivalents having a polyol hydroxyl group molar ratio is greater than 1.1:1; alter terminal carbon-carbon double bond may be used. When natively, greater than 1.2:1. In other embodiments, the car mixtures of unsaturated carboxylic acid or unsaturated car boxylic acid group to polyol hydroxyl group molar ratio boxylic equivalents having a terminal carbon-carbon double ranges from 1:1 to 2:1; alternatively, from 1.1:1 to 1.8, or bond are used the unsaturated carboxylic acid or unsaturated alternatively, from 1.2:1 to 1.6:1. carboxylic equivalent having a terminal carbon-carbon 0235. In an embodiment, the reaction between the polyol double bond may have an average of at least 6 carbonatoms; and the unsaturated carboxylic acid or unsaturated carboxylic or alternatively, at least 8 carbon atoms; alternatively, alter equivalent having a terminal carbon-carbon double bond is natively, from 6 to 18 carbonatoms; alternatively, from 8 to 14 catalyzed. In some embodiments, the catalyst is a mineral carbon atoms; alternatively, from 10 to 11 carbon atoms: acid, Such as Sulfuric or phosphoric acid. In other embodi alternatively, about 10 carbon atoms; or alternatively, about ments, the catalyst is an organic acid. Non-limiting examples 11 carbon atoms. of organic acids, which may be utilized as a catalyst, include 0233 Suitable unsaturated carboxylic acid having a termi methane Sulfonic acid and toluene Sulfonic acid. In other nal carbon-carbon double bond may be 3-butenoic acid, a embodiments, the catalyst may be an organic base. One class 4-pentenoic acid, a 5-hexenoic acid, a 6-heptenoic acid, a of organic bases, which may be utilized to catalyst the reac 7-octenoic acid, a 8-nonenoic acid, a 9-decenoic acid, a tion between the polyol and the unsaturated carboxylic acid 10-undecenoic acid, a 11-dodecenoic acid, a 12-tridecenoic or unsaturated carboxylic equivalent having a terminal car US 2009/0264669 A1 Oct. 22, 2009

bon-carbon double bond, are metal alkoxides. Non-limiting to Cs halogenated aliphatic hydrocarbons. Non-limiting example of suitable metal alkoxides include Sodium methox examples of such halogenated aliphatic hydrocarbons, which ide, Sodium ethoxide, potassium methoxide, potassium may be utilized as a solvent, include carbon tetrachloride, ethoxide, sodium t-butoxide, and potassium t-butoxide. chloroform, methylene chloride, dichloroethane, trichloroet Another class of organic catalysts, which may be utilized to hane, and combinations thereof. Halogenated aromatic catalyst the reaction between the polyol and the unsaturated hydrocarbons, which may be useful as a solvent, include C to carboxylic acid or unsaturated carboxylic equivalent having a Co halogenated aromatic hydrocarbons; or alternatively, C terminal carbon-carbon double bond, is metal carboxylates to Co halogenated aromatic hydrocarbons. Non-limiting Such as Sodium acetate of potassium acetate. In yet other examples of Suitable halogenated aromatic hydrocarbons embodiments, the catalyst may be organometallic catalyst. include chlorobenzene, dichlorobenzene, and combinations Examples of organic metallic catalyst, which may be utilized thereof. to catalyst the reaction between the polyol and the unsatur 0237 When a solvent is used for the reaction between the ated carboxylic acid or unsaturated carboxylic equivalent polyol and the unsaturated carboxylic acid or carboxylic acid having a terminal carbon-carbon double bond, are organotin catalyst such as dibutyltin oxide. Other suitable types of cata equivalent having a terminal carbon-carbon double bond, the lyst will be apparent to those of skill in the art and are to be quantity of solvent can be any amount that facilitates the considered within the scope of the present invention. reaction. In some embodiments, the mass of the solvent is less 0236. In an embodiment, the reaction between the polyol than 30 times the mass of the unsaturated carboxylic acid or and the unsaturated carboxylic acid or carboxylic acid carboxylic acid equivalent having a terminal carbon-carbon equivalent having a terminal carbon-carbon double bond double bond. In other embodiments, the mass of the solvent is occurs in the presence of a solvent. In some embodiments the less than 20 times the mass of the unsaturated carboxylic acid reaction between the polyol and the unsaturated carboxylic or carboxylic acid equivalent having a terminal carbon-car acid or carboxylic acid equivalent having a terminal carbon bon double bond; alternatively, less than 15 times the mass of carbon double bond occurs in the substantial absence of a the unsaturated carboxylic acid or carboxylic acid equivalent solvent. In an embodiment, wherein the reaction between the having a terminal carbon-carbon double bond; alternatively, polyol and the unsaturated carboxylic acid or carboxylic acid less than 10 times the mass of the unsaturated carboxylic acid equivalent having a terminal carbon-carbon double bond or carboxylic acid equivalent having a terminal carbon-car occurs in the presence of a solvent, the solvent may be bon double bond; or alternatively, less than 5 times the mass selected from aromatic hydrocarbons, aliphatic hydrocar of the unsaturated carboxylic acid or carboxylic acid equiva bons, organic ethers, halogenated aliphatic hydrocarbons, lent having a terminal carbon-carbon double bond. In other aromatic hydrocarbons, halogenated aromatic hydrocarbons, embodiments, the mass of the solvent is from 2 times to 20 and combinations thereof. Aliphatic hydrocarbons, which times the mass of the unsaturated carboxylic acid or carboxy may be useful as a solvent, include Cato Cohydrocarbons, or lic acid equivalent having a terminal carbon-carbon double alternatively, Cs to Co. hydrocarbons, and may be cyclic or bond; alternatively, from 3 times to 15 times the mass of the acyclic and include linear or branched isomers, unless other unsaturated carboxylic acid or carboxylic acid equivalent wise specified. Non-limiting examples of Suitable acyclic having a terminal carbon-carbon double bond; or alterna aliphatic solvents include pentane, hexane, heptane, octane, tively, from 5 times to 10 times the mass of unsaturated and combinations thereof. Non-limiting examples of suitable carboxylic acid or carboxylic acid equivalent having a termi cyclic aliphatic solvents include cyclohexane, methyl cyclo nal carbon-carbon double bond. hexane, and combinations thereof. Aromatic hydrocarbons, 0238. The reaction of the polyol and the unsaturated car which may be useful as a solvent, include C to Co aromatic boxylic acid or unsaturated carboxylic equivalent having a hydrocarbons; or alternatively, C to Co aromatic hydrocar terminal carbon-carbon double bond can occur in a batch bons. Non-limiting examples of Suitable aromatic hydrocar reactor or a continuous reactor, as described herein. bons include benzene, toluene, Xylene (including ortho-Xy 0239. The reaction between the polyol and unsaturated lene, meta-xylene, para-Xylene, or mixtures thereof), and carboxylic acid or unsaturated carboxylic equivalent having a ethylbenzene, or combinations thereof. Organic ethers which terminal carbon-carbon double bond can be performed at any may be uses as a solvent include C to Co organic ethers; temperature capable of forming the unsaturated ester mol alternatively, C to Co organic ethers; or alternatively, C to ecules having terminal carbon-carbon double bonds (or the Cs organic ethers. Suitable ether solvents may be cyclic or desired unsaturated ester composition comprising unsatur acyclic. Non-limiting examples of suitable ethers which may ated ester molecules having terminal carbon-carbon double be useful as a solvent include dimethyl ether, diethyl ether, bonds). In some embodiments, the polyol and the unsaturated methyl ethyl ether, monoethers or diethers of glycols (e.g., carboxylic acid or unsaturated carboxylic equivalent having a dimethylglycol ether), furans, substituted furans, dihydrofu terminal carbon-carbon double bond can be reacted at a tem ran, substituted dihydrofurans, tetrahydrofuran (THF), sub perature greater than 80°C. In other embodiments, the polyol stituted tetrahydrofurans, tetrahydropyrans, substituted tet and the unsaturated carboxylic acid or unsaturated carboxylic rahydropyrans, 1,3-dioxanes, Substituted 1,3-dioxanes, 1,4- equivalent having a terminal carbon-carbon double bond can dioxanes, Substituted 1,4-dioxanes, or mixtures thereof. In an be reacted at a temperature greater than 100°C.; alternatively, embodiment, each substituent of a substituted furan, Substi greater than 120° C.; or alternatively, greater than 140°C. In tuted dihydrofuran, substituted tetrahydrofuran, substituted yet other embodiments, the polyol and the unsaturated car tetrahydropyran, substituted 1,3-dioxane, or substituted 1,4- boxylic acid or unsaturated carboxylic equivalent having a dioxane, can be a C to Cs alkyl group. Halogenated aliphatic terminal carbon-carbon double bond can be reacted at a tem hydrocarbons, which may be useful as a solvent, include C to perature from 80°C. to 300° C.; alternatively, from 100° C. to Cs halogenated aliphatic hydrocarbons; alternatively, C to 290° C.; alternatively, from 120° C. to 280° C.; or alterna Co halogenated aliphatic hydrocarbons; or alternatively, C tively, from 140° C. to 260° C. US 2009/0264669 A1 Oct. 22, 2009 36

0240. In an embodiment, the reaction between the polyol wiped film evaporation. Alternatively, the low boiling mate and the unsaturated carboxylic acid or unsaturated carboxylic rials and unconverted polyol (if present) and unreacted unsat equivalent having a terminal carbon-carbon double bond is urated carboxylic acid or unsaturated carboxylic equivalent performed under conditions which allow water (for carboxy having a terminal carbon-carbon double bond may be sepa lic acid and carboxylic acids having terminal carbon-carbon rated from the desired unsaturated esters having an terminal double bonds) or a simple alcohols (for simple esters of the carbon-carbon double bonds via distillation and/or wiped carboxylic acid having terminal carbon-carbon double film evaporation. Other techniques may be used in addition to bonds) to be removed from the reaction solution as reaction or place of vacuum stripping, including, for example, column between the polyol and the unsaturated carboxylic acid or chromatography, column distillation, and/or phase separa unsaturated carboxylic equivalent having a terminal carbon tion, among other techniques. carbon double bond progresses. One such method the may be 0245. In an embodiment, the vacuum stripping process utilized is reactive distillation. In some embodiments, the may be run under a vacuum of about 0.001 atmospheres (atm) Solvent, if utilized, is chosen so that it may assist in the to 0.5 atm, or under a vacuum of about 0.05 atm to 0.4 atm, or removal of the water or simple alcohol by forming an azeo under a vacuum of 0.25 atm. In embodiments, the vacuum trope. Other techniques are known to those having ordinary distillation may be run at a temperature of between about 15° skill in the art. C. to 150° C., at a temperature of 15° C. to a temperature of 0241 The time required for the reaction between the reac 100° C., or at a temperature of around 25°C. In an embodi tion between the polyol and the unsaturated carboxylic acid ment, the vacuum distillation may be run for 5 minutes, 15 or unsaturated carboxylic equivalent having a terminal car minutes, 1 hour, 2 hours, 6 hours, or longer. Alternatively or bon-carbon double bond can be any time required to form the additionally, the unsaturated esters having an terminal car unsaturated ester molecules having terminal carbon-carbon bon-carbon double bonds may be sparged with an inert gas to double bonds (or the desired unsaturated ester composition remove low boiling components, at a temperature between comprising unsaturated ester molecules having terminal car 25° C. and 250° C.; or, alternatively, between 50° C. and 200° bon-carbon double bonds). Generally, the reaction time is at C. The inert gas may be nitrogen, or any other Suitable inert least 5 minutes. In some embodiments, the reaction time is at gas, such as argon. least 15 minutes; alternatively, at least 30 minutes; or alter natively, at least 45 minutes. In some embodiments, the reac Polythiourethane Compositions tion time ranges from 5 minutes to 48 hours; alternatively, 0246. In an aspect, the thiol ester molecules described from 15 minutes to 36 hours; alternatively, from 30 minutes to herein and the thiolester compositions described herein may 24 hours; or alternatively, from 45 minutes and 12 hours. be utilized to produce polythiourethanes. The polythioure 0242. When a continuous reactor is used for the reaction thanes can be described as a reaction product of anythiolester between the polyol and the unsaturated carboxylic acid or molecule (or thiol ester composition) described herein and unsaturated carboxylic equivalent having a terminal carbon isocyanate molecule (or isocyanate composition) described carbon double bond, a polyol weight space Velocity may herein. Generally, the polythiourethane of the present inven range from 0.1 to 5. Alternatively, the polyol weight hourly tion comprises multiple thiourethane groups having structure space Velocity may range from 0.15 to 4, alternatively, from U1: 0.2 to 3.5; or alternatively, from 0.25 to 3. 0243 The reaction between the polyol and the unsaturated carboxylic acid or unsaturated carboxylic equivalent having a terminal carbon-carbon double bond can be performed at any reaction pressure that maintains the polyol and the thiol con taining carboxylic acid and/or thiol containing carboxylic acid derivative in a liquid state. In some embodiments, the --> reaction between the polyol and the unsaturated carboxylic O acid or unsaturated carboxylic equivalent having a terminal carbon-carbon double bond is performed at a pressure rang where the undesignated Valancies represent the remainder of ing from 0 psia to 2000 psia; from 0 psia to 1000 psia; the structure of the polythiourethane including additional alternatively, from 0 psia and 500 psia; or alternatively, 0 psia thiourethane groups having structure U1. The presence of the to 300 psia. thiourethane group U1 can be determined using techniques 0244. The process to produce unsaturated ester molecules known to those skilled in the art (for example Infrared Spec having terminal carbon-carbon double bonds (or the unsatur troscopy, Raman Spectroscopy, and or 'C NMR). ated ester composition comprising, or consisting essentially 0247 The polythiourethane of the present invention can of unsaturated esters having an terminal carbon-carbon be described as having a repeating unit PTU1: double bonds) by the reaction between the polyol and the unsaturated carboxylic acid or unsaturated carboxylic equivalent having a terminal carbon-carbon double bond may PTU 1 include steps to remove by products, impurities, and/or the optional Solvent. Materials having low boiling point may be S S N N : removed by flashing them off of the reaction mixture in a -k N11 N21 r vacuum stripping process. Unreacted polyol, if present and unreacted unsaturated carboxylic acid or unsaturated car O O boxylic equivalent having a terminal carbon-carbon double bond may be separated from the unsaturated esters having where the undesignated Valancies represent the remainder of terminal carbon-carbon double bonds via distillation and/or the structure of the polymer including additional repeating US 2009/0264669 A1 Oct. 22, 2009 37 units PTU1. In embodiments, the backbone of the polythio thiolester composition and an isocyanate composition. Addi urethane having repeating unit PTU1 is linear; or alterna tional embodiments regarding the number or average number tively, the backbone of the polythiourethane having repeating of isocyanate groups present in the isocyanate molecules of unit PTU 1 is crosslinked. When the backbone of the poly the isocyanate composition are described herein and are gen thiourethane having repeating unit PTU1 is crosslinked, A' erally applicable to the description of the polythiourethane as and/or A further comprise additional repeating units PTU1. a reaction product of a thiol ester composition and an isocy The repeating unit PTU 1 of the polythiourethane is com anate composition. prised of two different units: T1 and 12. 0251. In embodiments, the thiol ester molecules compo sition utilized to produce the polythiourethane composition can comprise a hydroxy thiol ester molecules (hydroxy thiol S S ester composition); or alternatively, a crosslinked thiol ester -k N11 ). molecules (crosslinked thiol ester composition). Additional aspects of the thiol ester molecules (e.g. average number of thiol groups per thiol ester molecule, thiol Sulfur content etc. : | : . . . ) are described herein and can be utilized to further describe the thiol esters of the thiol ester compositions. t’s Y Besides the thiolester molecules described herein, other suit O O able thiolester compositions will be apparent to those persons having ordinary skill in the art, can be used, and are to be 0248 Generally, unit T1 of the polythiourethane is derived considered within the scope of the present invention. from a thiol ester molecule of a thiol ester composition and 0252 Generally the isocyanates can comprise, singly or in unit I1 of the polythiourethane is derived from an isocyanate any combination, any isocyanate described herein. In of an isocyanate composition. Thus, A' represents the embodiments, the isocyanate can comprise aliphatic isocyan remainder of the thiol ester molecule (including ester groups, ates, cycloaliphatic isocyanates, aromatic isocyanates, or any other groups present in the thiol ester molecule, and mixtures thereof. In some embodiments, the isocyanate can optionally additional repeating units PTU1), and A repre comprise an aliphatic isocyanate; alternatively, a sents the remainder of the isocyanate molecule (including any other groups present in the isocyanate molecule and option cycloaliphatic isocyanate; or alternatively, an aromatic isocy ally additional repeating units PTU 1). Because units T1 and anate composition. Particular isocyanates having at least two I1 are derived from two different materials, the structures of isocyanate groups are described herein and can generally be these units are independent of each other. Therefore, the utilized in the isocyanate compositions describing the poly polythiourethanes having the repeating unit PTU1 can be thiourethane as a reaction product of a thiolester composition comprised of any combination of units T1 and I1. Thus, the and an isocyanate composition. Additionally, other aspects of polythiourethane having the repeating unit PTU1 can be the isocyanates (e.g. number or average number of isocyanate described as the reaction product of a thiol ester molecules groups per isocyanate molecule, etc. ...) are described herein and an isocyanate where unit T1 can be derived from anythiol and can be utilized to further describe the isocyanate. ester described herein and unit I1 can be derived from any 0253 Generally, the thiol ester composition and the iso isocyanate described herein. cyanate composition are independent elements of the poly 0249. The polythiourethane of the present invention can thiourethane described as the reaction product of a thiol ester alternatively be described as a reaction product of a thiolester composition and an isocyanate composition. Therefore, the composition and an isocyanate composition. The thiol ester polythiourethane can be described as the reaction product of composition and the isocyanate are independent elements of any combination of the thiol ester composition described the polythiourethane. Therefore, the polythiourethane can be herein and the isocyanate composition described herein. In described as a polythiourethane product of any combination embodiments, the polythiourethane can be described as the of the thiolester composition described herein and the isocy reaction product of a thiol ester composition with isocyanate anate composition described herein. In aspects, the polythio composition comprising an isocyanate having at least two urethane can be linear. In other aspects, the polythiourethane isocyanate groups. In embodiments, the polythiourethane can can be crosslinked. When the polythiourethane is crosslinked, be described as the reaction product of a hydroxy thiol ester either the thiol ester molecules have greater than 2 thiol composition and an isocyanate composition. Therefore, the groups per thiol ester molecule or the isocyanates have polythiourethane composition can be described as the reac greater than 2 isocyanate groups per isocyanate molecule. tion product of any combination of the hydroxy thiol ester Alternatively, when the polythiourethane is crosslinked the composition described herein and the isocyanate composition thiolester molecules have greater than 2 thiol groups per thiol described herein. ester molecule and the isocyanates have greater than 2 isocy 0254. In some embodiments, the polythiourethane can be anate groups per isocyanate molecule. described as the reaction product of a crosslinked thiol ester 0250 Generally, the thiol ester composition comprises composition and an isocyanate composition. Therefore, the thiol ester molecules having at least 2 thiol groups and the polythiourethane composition can be described as the reac isocyanate composition comprises isocyanate molecules hav tion product of any combination of the crosslinked thiol ester ing at least 2 isocyanate groups. Additional embodiments composition described herein and the isocyanate composition regarding the number or average number of thiol groups described herein. present in the thiol ester molecules of the thiol ester compo 0255. In some embodiments, the polythiourethanes of the sition are described herein and are generally applicable to the present invention can be described as a product produced by description of the polythiourethane as a reaction product of a any process described herein capable of producing the poly US 2009/0264669 A1 Oct. 22, 2009

thiourethane composition and can be further described as anate composition. Other isocyanate compositions are being produced using any embodiments of the processes described herein and can generally be utilized to form the described herein. mixture comprising the thiol ester composition and the iso 0256 In embodiments, the polythiourethane of the present cyanate composition. Additional aspects of the isocyanates invention can be further described by its properties. In some (e.g. number or average number of isocyanate groups per embodiments, the polythiourethane described as the reaction isocyanate molecule etc. ...) are described herein and can be product of a thiol ester composition and an isocyanate com utilized to further describe the isocyanates. position can have a glass transition temperature ranging from 0261 Generally, the thiol ester composition and the iso -100° C. to 250° C. In other embodiments, the polythioure cyanate ester composition are independent elements of the thane of the present invention has a glass transition tempera mixture comprising a thiol ester composition and an isocy ture ranging from -50° C. to 150° C.; or alternatively, ranging anate composition. Therefore, the mixture comprising a thiol from -.50° C. to 100° C. ester composition and an isocyanate composition can com 0257. In an aspect, the polythiourethanes can have other prise any thiol ester composition described herein and any desirable properties. For example, the polythiourethanes of isocyanate composition described herein. In embodiments, the present invention can have desirableYoung's modulus and the mixture can comprise a thiol ester composition and an elongations at break, which can be measured using ASTM isocyanate composition comprising an isocyanate having at D638-03. In embodiments, the polythiourethanes can have a least two isocyanate groups. In embodiments, the mixture can Young's modulus greater than 0.1 MPa: or alternatively, rang comprise a thiolester composition and an isocyanate compo ing from 0.1 MPa to 7,000 MPa. In some embodiments, the sition comprising an aliphatic isocyanate having at least two polythiourethanes have a Young's modulus ranging from 2 to isocyanate groups, a cycloaliphatic isocyanate having at least 6 MPa: alternatively, from 6 MPa to 60 MPa: alternatively, 60 two isocyanate groups, an aromatic isocyanate having at least MPa to 600 MPa: or alternatively, from 600 MPa to 4,500 two isocyanate groups, or mixtures thereof. In some embodi MPa. In an aspect, the polythiourethanes can have an elon ments, the mixture can comprise athiolester composition and gation at break less than 100 percent; or alternatively, greater an isocyanate composition comprising an aliphatic isocyan than 100 percent. In an embodiment, the greater than 150 ate having at least two isocyanate groups; alternatively, a percent; alternatively, greater than 200 percent; alternatively, cycloaliphatic isocyanate having at least two isocyanate ranging from 100 percent to 900 percent, or alternatively, group; or alternatively, an aromatic isocyanate having at least ranging from 200 to 700 percent. In some embodiments, the two isocyanate groups. Particular aliphatic, cycloaliphatic, polythiourethanes can have an elongation at break less than and aromatic isocyanates having at least two isocyanate 10 percent; or alternatively, ranging from 10 percent to 100 groups are described herein and can generally be utilized in percent. In embodiments, the polythiourethanes can have any the isocyanate compositions describing the polythiourethane combination of theYoung's modulus described herein and the as a reaction product of a thiol ester composition and an elongation at break as described herein. isocyanate composition. Additionally, other aspects of the isocyanate materials (e.g. number or average number of iso Process of Making Polythiourethane cyanate groups per isocyanate molecule, etc. . . . ) are 0258. In an aspect, a method of making the polythioure described herein and can be utilized to further describe the thane of the present invention comprises contacting a thiol isocyanate composition utilized in describing the polythio ester composition and an isocyanate composition. In an urethane as a reaction product of a thiolester composition and embodiment of the present invention, the method of produc an isocyanate composition. ing the polythiourethane composition comprises contacting 0262 Generally, the thiol ester composition and the iso the thiolester composition and the isocyanate composition to cyanate composition can be combined in any functional produce a mixture and curing the mixture to produce the group equivalent ratio that can produce a polythiourethane. polythiourethane. The functional group equivalent ratio relates the ratio of the 0259 Generally, the thiol ester composition utilized to number of functional groups in the thiol ester composition form the mixture can be anythiolester composition described capable of reacting with an isocyanate of the isocyanate com herein. In embodiments, the thiolester composition can com position to form a thiourethane group to the number of iso prise the hydroxy thiol ester molecules (hydroxy thiol ester cyanate groups in the isocyanate composition. Generally, the composition); or alternatively, the crosslinked thiolester mol functional group equivalent ratio is provided by the term ecules (crosslinked thiol ester composition. Additional “XH:NCO equivalent ratio' where XH represents the equiva aspects of the thiol ester molecules (e.g. average number of lents of thiol groups and the alcohol groups present in the thiol thiol groups per thiol ester molecule, thiol Sulfur content etc. ester composition and NCO represent the equivalents of iso . . . ) are described herein and can be utilized to further cyanate groups present in the isocyanate composition. One describe the thiol ester compositions. Other suitable thiol skilled in the art will recognize which thiolester composition ester compositions will be apparent to those persons having comprises only thiol groups and which thiol ester composi ordinary skill in the art, can be used, and are to be considered tion comprises thiol groups and alcohol groups. In embodi within the scope of the present invention. ments, the functional group equivalent ratio (XH:NCO) can 0260 Generally, the isocyanate utilized to form the mix beat least 0.5. In some embodiments, the XH:NCO equiva ture can comprise, singly or in any combination, any isocy lent ratio can range from 0.50 to 1.3; or alternatively, from anate described herein. In an embodiment, the isocyanate 0.75 to 1.3. In some embodiments, the XH:NCO equivalent composition can comprise aliphatic isocyanates, ratio can range from 0.75 to 0.95; alternatively, from 0.95 to cycloaliphatic isocyanates, aromatic isocyanates, or mixtures 1.1; or alternatively, from 1.1 to 1.3. thereof. In some embodiments, the isocyanate composition 0263. In an aspect, the method of making the polythioure can comprise an aliphatic isocyanate; alternatively, a thane further comprises curing the mixture at a temperature cycloaliphatic isocyanate; or alternatively, an aromatic isocy ranging from 0°C. to 120° C. In embodiments; the mixture US 2009/0264669 A1 Oct. 22, 2009 39 may be cured at a temperature ranging from 10°C. to 30°C.; position) and the epoxide molecules (or epoxide composi alternatively, ranging from 50° C. to 80° C.; alternatively, at tion) are independent elements of the epoxy polymer. ambient temperature (room temperature); alternatively, at 65° Therefore, the epoxy polymer can be described as an epoxy C.; or alternatively, at 120° C. In some embodiments, the polymer produced from any combination of the thiol ester mixture may be cured at ambient temperature for a time molecules (or thiol ester compositions) described herein and ranging from one to 8 hours; alternatively, the mixture can be the epoxide molecules (or epoxide compositions) described cured at 65° C. for a time ranging from 10 to 18 hours; or herein. In aspects, the epoxy polymer can be linear. In other alternatively, the mixture may be cured at 120°C. for 3 hours. aspects, the epoxy polymer can be crosslinked. When the In other embodiments, the mixture may be cured at about ambient temperature for a time ranging from one to 8 hours epoxy polymer is crosslinked, either the thiol ester molecules and then cured at 65° C. for a time ranging from 10 to 18 have greater than 2 thiol groups per thiolester molecule or the hours; alternatively, the mixture may be cured at 65° C. for a epoxide molecules have greater than 2 epoxide groups per time ranging from 10 to 18 hours and then cured at 95°C. for epoxide molecule. Alternatively, when the epoxy polymer is 24 hours; or alternatively, the mixture may be cured at 120° C. crosslinked, the thiol ester molecules have greater than 2 thiol for 3 hours and then cured at 95°C. for 24 hours. groups per thiol ester molecule and the epoxide molecules 0264. In an aspect, the mixture further comprises a cata have greater than 2 epoxide groups per epoxide molecule. lyst. In embodiments, the catalyst may be contacted with the 0269 Generally, the thiol ester molecules have at least 2 mixture comprising the thiol ester composition and the iso thiol groups and the epoxide molecules have at least 2 cyanate composition. In other embodiments, the catalyst may epoxide groups. Additional embodiments regarding the num be combined with the thiol ester composition prior to con ber or average number of thiol groups present in the thiolester tacting the thiol ester composition with the isocyanate com molecules of the thiol ester composition are described herein position; or alternatively, may be combined with isocyanate and are generally applicable to the description of the epoxy composition prior to contacting the isocyanate composition polymeras a reaction product of a thiolester composition and with the thiol ester composition. an epoxide composition. Additional embodiments regarding 0265. In embodiments, the catalyst may be selected from the number or average number of epoxide groups present in the group consisting of a tertiary amine, an organotin com the epoxide molecules of the epoxide composition are pound, an amine initiated polypropylene glycol, and combi described herein and are generally applicable to the descrip nations thereof. In some embodiments the catalyst may be an tion of the epoxy polymeras a reaction product of a thiolester amine. In other embodiments, the catalyst may be an organo composition and an epoxide composition. tin compound. In some embodiment, the catalyst may be a 0270. In embodiments, the thiolester composition utilized mixture of an amine and an organotin compound. In some to produce the epoxy polymer composition can comprise a embodiments, the amine catalyst may be a primary amine; hydroxy thiol ester (hydroxy thiol ester composition); or alternatively, a secondary amine; or alternatively, a tertiary alternatively, a crosslinked thiol ester (crosslinked thiol ester amine. In other embodiments amine catalyst may be aliphatic composition). Additional aspects of the thiol ester molecules amine; or alternatively, an aromatic amine. In other embodi (e.g. average number of thiol groups per thiol ester molecule, ments, the amine catalyst may be a polyetheramine; alterna thiol sulfur content etc. . . . ) are described herein and can be tively, a polyalkylene amine; or alternatively, a tertiary amine utilized to further describe the thiol ester molecules of the polyol (e.g. JeffolR A-480). In yet other embodiments, the amine catalyst may be a polyamine comprising at least two thiolester compositions. Besides the thiolester compositions amine groups. In some amine catalyst embodiments, the cata described herein, other suitable thiol ester compositions will lyst may be 1,8-diazabicyclo[5.4.0]undec-7-ene DBU-CAS be apparent to those persons having ordinary skill in the art, #6674-22-2; alternatively, 1,4-diazabicyclo[2.2.2]octane can be used, and are to be considered within the scope of the DABCO-CAS #280-57-9); or alternatively, triethylamine. present invention. In an organotin compound catalyst embodiment, the organo 0271 Generally the epoxide composition can comprise, tin compound can be dibutyltin dilaurate. singly or in any combination, any epoxide described herein. In an embodiment, the epoxide is a polyol glycidyl ether. In 0266 Generally, the catalyst is utilized when the mixture Some embodiments, the polyol glycidyl ether may be an comprising the thiol ester composition and the isocyanate aliphatic polyol glycidyl ethers; alternatively, a does not cure under the desired conditions. In embodiments, cycloaliphatic polyol glycidyl ethers; alternatively, an aro the catalyst can comprise less than 10 weight percent of the matic glycidyl ethers; alternatively, a bisphenol glycidyl mixture. In other embodiments, the catalyst comprises from ethers; or alternatively, a novolak polyglycidyl ethers. In 0.01% to 9.0% by weight of the mixture; alternatively, from other embodiments, the epoxide may be a trimethylolethane 0.1% to 7.0% by weight of the mixture; or alternatively, from triglycidyl ether, alternatively, a pentaerythritol tetraglycidyl 0.5% to 3.0% by weight of the mixture. ether; alternatively, a dipentaerythritol tetraglycidyl ether; 0267 In aspects, the polythiourethane produced by the alternatively, a sorbitol tetraglycidyl ether; alternatively, a process described herein can be further described by the Sorbitol hexaglycidyl ether; alternatively, a bisphenol A dig properties of the polythiourethanes described herein. lycidyl ether; alternatively, a bisphenol F diglycidyl ether; alternatively, a formaldehyde-phenol novolak polyglycidyl Epoxy Polymer ether; alternatively, a formaldehyde-cresol novolak polygly 0268. In an aspect, the thiol ester molecules and thiolester cidyl ether; or alternatively, a formaldehyde-catechol novolak compositions described herein can be utilized to form an polyglycidyl ether. Other epoxide are described herein and epoxy polymer. The epoxy polymers can be described as a can generally be utilized to describe the epoxy polymers polymer produced from thiol ester molecules (or thiol ester produced from the thiol ester composition and the epoxide composition) and epoxide molecules (or epoxide composi composition. Additionally, other aspects of the epoxides (e.g. tion). Generally, the thiolester molecules (or thiolester com the number or average number of epoxide groups per epoxide US 2009/0264669 A1 Oct. 22, 2009 40 molecule, etc.) are described herein and can be utilized to hydroxyl group, the thiol ester composition and the epoxide further describe the epoxide composition. composition are contacted at a mercaptain plus hydroxyl to 0272 Generally, the thiol ester composition and the epoxide molar ratio ranging from 0.6 to 1.20; alternatively, epoxide composition are independent elements of the epoxy from 0.8 to 1.15; alternatively, from 0.9 to 1.10: or alterna polymer. Therefore, the epoxy polymer can be described as a tively, from 0.95 to 1.05. polymer produced from any combination of the thiol ester 0277. In embodiments, the epoxy polymer of the present composition described herein and the epoxide composition invention can be described as a epoxy polymer produced by described herein. any process described herein capable of producing the epoxy 0273. In embodiments, the epoxy polymer can be polymerand can be further described as being produced using described as a epoxy polymer produced by contacting any any embodiments of the processes described herein. thiolester composition comprising thiolester molecules hav 0278. The epoxy polymer has physical properties that are ing at least two thiol group described herein with any epoxide advantageous in many applications. For example, in embodi composition comprising epoxide molecules having at least ments, the epoxy polymer can have a glass transition tem two epoxide groups; or alternatively, a polyol glycidyl ether perature, Tg, ranging between -100° C. and 250°C. In some composition comprising a polyol glycidyl ether having at aspects, the glass transition temperature ranges from -50° C. least two epoxide groups. In some embodiments, the epoxy to 200° C.; alternatively, from 0°C. to 150° C.; alternatively, polymer can be described as a polymer produced by contact from 50° C. to 100° C.; or alternatively, from -50° C. to 50° ing the thiol ester composition with the epoxide composition C. In some aspects, the glass transition temperature ranges comprising a bisphenol diglycidyl ether, or alternatively, a from -50° C. to 0° C.; alternatively, from 0° C. to 50° C.: novolak polyglycidyl ether. In other embodiments, the poly alternatively, from 50° C. to 100° C.; alternatively, from 100° mercan be described as a polymer produced by contacting the C. to 150° C.; or alternatively, from 150° C. to 200° C. thiol ester composition with the epoxide composition com 0279 Besides the glass transition temperature, the epoxy prising a bisphenol A diglycidyl ether, a bisphenol F digly polymer of the present invention can have other desirable cidyl ether, a formaldehyde-phenol novolak polyglycidyl properties. For example, the epoxy polymer of the present ether, a formaldehyde-cresol novolak polyglycidyl ether, a invention can have desirable Young's modulus, tensile formaldehyde-catechol novolak polyglycidyl ether, or any strength, and elongations at break, which can be measured combination thereof. In yet other embodiments, the epoxy using ASTM D638-03. In embodiments, the epoxy polymer polymer can be described as a polymer produced by contact can have a stiffness (Young's modulus) greater than 10 psi; or ing the thiol ester composition with an epoxide composition alternatively, ranging from 10 psi to 1,000,000 psi. In some comprising a bisphenol A diglycidyl ether, alternatively, a embodiments, the epoxy polymer has a Young's modulus bisphenol F diglycidyl ether; alternatively, a formaldehyde ranging from 600 to 300,000 psi; alternatively, from 700 to phenol novolak polyglycidyl ether, alternatively, a formalde 20,000 psi; or alternatively, 20,000 to 200,000 psi. In an hyde-cresol novolak polyglycidyl ether; or alternatively, a aspect, the epoxy polymer can have a Young's modulus rang formaldehyde-catechol novolak polyglycidyl ether. ing from 10 psi to 4,000 psi. In some embodiments, the epoxy 0274. One skilled in the art will readily recognize other polymer has a Young's modulus ranging from 90,000 to 600, possible combinations of thiol ester compositions and 000 psi. In embodiments, the epoxy polymer can have a epoxide compositions based upon the present application. tensile strength (as measured using ASTM D638-03) greater 0275. In an aspect, the thiol ester composition and the than 10 psi; or alternatively, ranging from 10psi to 8,000 psi. epoxide composition are contacted at a mercaptan to epoxide In some embodiments, the epoxy polymer has a tensile molar ratio ranging from 0.8 to 1.15. In other embodiments, strength ranging from 300 to 6,000 psi; or alternatively, from the thiol ester composition and the epoxide composition are 300 to 1,000 psi. In some embodiments, the epoxy polymer contacted at a mercaptan to epoxide molar ratio ranging from can have a tensile strength ranging from 1,000 to 5,000 psi; or 0.9 to 1.10: or alternatively, from 0.95 to 1.05. In further alternatively, ranging from 4,000 to 7,500 psi. In an aspect, embodiments, the thiol ester composition and the epoxide the epoxy polymer can have an elongation at break (as mea composition are contacted at a mercaptan to epoxide molar sured using ASTM D638-03) less than 100 percent; or alter ratio of about 1. natively, greater than 100 percent. In embodiments, the epoxy 0276. When the thiolester molecules comprise a hydroxyl polymer can have an elongation at break less than 10 percent; group both the mercaptain group and the hydroxyl group can or alternatively, ranging from 10 percent to 100 percent. In react with the epoxide group. One of ordinary skill in the art embodiments, the epoxy polymer can have any combination realizes that, in this situation, both the mercaptain group and of the Young's modulus, tensile strength, and elongation at the hydroxyl group can react with the epoxide group, but break described herein. generally, recognizes that the thiol group is more reactive than 0280. The epoxy polymers described herein can be used in the hydroxyl group towards the epoxy group. Thus, the epoxy various applications. For example, the epoxy polymers can be polymer can be formed by contacting the thiol ester compo used as adhesives or as sealants. The physical properties of sition and the epoxide composition in a molar ratio based the epoxy polymers can be customized to Suit aparticular use. upon the mercaptan to epoxide molar ratio or based upon the As an example, if the desired application for the epoxy poly mercaptain plus hydroxyl to epoxide molar ratio (i.e. SH--OH: mers is as a sealant, the polymer composition can be prepared epoxide molar ratio or XH:epoxide molar ratio). In some so that the epoxy polymer has an elongation at break value in embodiments when the thiol ester composition further com a desired range that makes the epoxy polymer Suitable for use prises a hydroxyl group, the thiol ester composition and the as a sealant. epoxide composition are contacted at a mercaptan to epoxide Process of Making the Epoxy Polymer Composition molar ratio ranging from 0.8 to 1.15; alternatively, from 0.9 to 1.10: or alternatively, from 0.95 to 1.05. In other embodi 0281. In an aspect, a method of making epoxy polymer of ments when the thiol ester composition further comprises a the present invention comprises contacting a thiol ester com US 2009/0264669 A1 Oct. 22, 2009 position and an epoxide composition. In an embodiment, the epoxy polymer can be produced by forming a mixture com method of producing the epoxy comprises contacting the prising the thiol ester composition with the epoxide compo thiol ester composition and the epoxide composition to pro sition comprising bisphenol A diglycidyl ether, bisphenol F duce a mixture and curing the mixture to produce the epoxy diglycidyl ether, formaldehyde-phenol novolak polyglycidyl polymer. In some embodiments, the thiol ester composition ether, formaldehyde-cresol novolak polyglycidyl ether, form and/or the epoxide composition contain a solvent. In other aldehyde-catechol novolak polyglycidyl ether, or any combi embodiments, heat is needed to cure epoxy polymer produced nation thereof. In yet other embodiments, the epoxy polymer from the thiol ester composition and the epoxide composi can be produced by forming a mixture comprising the thiol tion. In an embodiment, including a solvent with the thiol ester composition with the epoxide composition comprising ester composition and/or the epoxide composition lowers the bisphenol A diglycidyl ether; alternatively, bisphenol F dig temperature needed to cure the epoxy polymer or can even lycidyl ether; alternatively, formaldehyde-phenol novolak allow the epoxy polymer to cure at ambient temperature. polyglycidyl ether; alternatively, formaldehyde-cresol 0282 Generally, the thiol ester composition utilized to novolak polyglycidyl ether; or alternatively, formaldehyde form the mixture can be anythiolester composition described catechol novolak polyglycidyl ether. herein. In embodiments, the thiol ester composition can be a 0286. In an aspect, the mixture further comprises a cata hydroxy thiol ester composition; or alternatively, a lyst. In embodiments, the catalyst may be contacted with the crosslinked thiol ester composition. Additional aspects of the mixture comprising the thiol ester composition and the thiol ester molecule (e.g. average number of thiol groups per epoxide composition. In other embodiments, the catalyst may thiol ester molecule, thiol Sulfur content, etc. . . . ) are be added to the thiolester composition prior to contacting the described herein and can be utilized to further describe the thiol ester composition with the epoxide composition. In yet thiol ester molecules. Other suitable thiol molecules will be other embodiments, the catalyst may be a component of the apparent to those persons having ordinary skill in the art, can thiol ester composition. be used, and are to be considered within the scope of the 0287. In some embodiments, the catalyst may be an present invention. amine. In some embodiments, the amine catalyst may be a 0283 Generally, the epoxide composition utilized to form primary amine; alternatively, a secondary amine; or alterna the mixture can comprise, singly or in any combination, any tively, a tertiary amine. In other embodiments the amine cata epoxide described herein. In an embodiment, the epoxide is a lyst may be aliphatic amine; or alternatively, an aromatic polyol glycidyl ether. In an aspect, the polyol glycidyl ether amine. In other embodiments, the amine catalyst may be a may be aliphatic polyol glycidyl ethers; alternatively, polyetheramine; or alternatively, a polyalkylene amine. In yet cycloaliphatic polyol glycidyl ethers; alternatively, aromatic other embodiments, the amine catalyst may be a polyamine glycidyl ethers; alternatively, bisphenol glycidyl ethers; or comprising at least two amine groups. In some amine catalyst alternatively, novolak glycidyl ethers. In embodiments, the embodiments, the catalyst can be 1,8-diazabicyclo[5.4.0]un epoxide may be a trimethylolethane triglycidyl ether; alter dec-7-ene DBU-CAS #6674-22-2; alternatively, 1,4-diaz natively, a pentaerythritol tetraglycidyl ether, alternatively, a abicyclo[2.2.2]octane DABCO-CAS #280-57-9); or alter dipentaerythritol tetraglycidyl ether; alternatively, a sorbitol natively, triethylamine. Alternatively, a phenolic catalyst can tetraglycidyl ether, alternatively, a Sorbitol hexaglycidyl be utilized. Generally, the class of phenolic catalysts com ether; alternatively, a bisphenol A diglycidyl ether; alterna prise materials having at least one hydroxy group attached to tively, a bisphenol F diglycidyl ether; alternatively, a formal a carbon atom of a benzene ring. Non-limiting examples of dehyde-phenol novolak polyglycidyl ether, alternatively, a phenolic catalysts, include phenol, resorcinol catechol, 1,4- formaldehyde-cresol novolak polyglycidyl ether; or alterna benzenediol, resorcinol monobenzoate, and their substituted tively, a formaldehyde-catechol novolak polyglycidyl ether. derivatives. Persons of ordinary skill in the art will readily Other epoxides are described herein and can generally be know other suitable phenolic catalysts that can be used in the utilized to describe the epoxy polymers produced from the present invention. thiol ester composition and the epoxide composition. Addi 0288. In some applications it can be advantageous cata tional aspects of the epoxides (e.g. number or average number lyze the formation of the epoxy polymer by the application of of epoxide groups per epoxide molecule, etc.) are described ultraviolet radiation (ultraviolet light). In an embodiment, the herein and can be utilized to further describe epoxides of the catalyst can be a compound that produces a Lewis acid when epoxide compositions. exposed to (irradiated with) ultraviolet radiation (light). Gen 0284 Generally, the thiol ester composition and the erally, these ultraviolet initiation catalysts comprise a cata epoxide composition are independent elements in the method lytic-effective amount of at least one ionic salt of an organo of making the epoxy polymers. Therefore, the epoxy polymer metallic complex cation selected from elements of Periodic can be made by forming a mixture comprising any combina Table Groups IVB, VB, VIIB, VIIB, and VIII. In an embodi tion of any thiol ester composition described herein and any ment, the ionic salts having the formula: epoxide composition described herein. (L)(L2)(L)M(L)(L)(L)M'L')(L2) 0285. In embodiments, the epoxy polymer can be pro (L3)MIL2)(L2)(L)M(L)(L)(L)"ex, duced by forming a mixture comprising the thiol ester com wherein M", M', M, and M represent metal atoms that can position with the epoxide composition comprising an epoxide be the same or different selected from the elements of peri having at least two epoxide groups; or alternatively, a polyol odic Groups IVB, VB, VIIB, VIIB, and VIII; L represents the glycidyl ether composition comprising a polyol glycidyl attendant ligands; e is an integer having a value of 1, 2, or 3. ether having at least two epoxide groups. In some embodi which is the residual electrical charge of the complex cation; ments, the epoxy polymer can be produced by forming a X is a halogen-containing complex anion of a metal or met mixture comprising the thiol ester composition with the alloid; f is an integer of 1 to 3 and represents the number of epoxide composition comprising bisphenol diglycidyl ether complex anions required to neutralize the charge e on the or novolak polyglycidyl ether. In other embodiments, the complex cation; and g, h, j, and kindependently are 0 or 1, US 2009/0264669 A1 Oct. 22, 2009 42 with at least one of them being equal to 1. The photoinitiator upon the mercaptain plus hydroxyl to epoxide molar ratio (i.e. can be a mononuclear, binuclear, trinuclear or tetranuclear SH--OH:epoxide molar ratio or XH:epoxide molar ratio). In complex compound comprising the metallic atoms and the some embodiments when the thiol ester composition further attendant ligands, L. The ligands can be any compound hav comprises a hydroxyl group, the thiol ester composition and ing an accessible unsaturated group, e.g., an ethylenic group. the epoxide composition are contacted at a mercaptan to anacetylenic group, oranaromatic group, which have L-elec epoxide molar ratio ranging from 0.8 to 1.15; alternatively, trons regardless of the total molecular weight of the com from 0.9 to 1.10: or alternatively, from 0.95 to 1.05. In other embodiments when the thiol ester composition further com pound. Applicable compounds are further described in U.S. prises a hydroxyl group, the thiol ester composition and the Pat. No. 5,089,536 (which is incorporated herein by refer epoxide composition are contacted at a mercaptain plus ence) and the references therein. Useful compounds include, hydroxyl to epoxide molar ratio ranging from 0.6 to 1.20; but are not limited to, cyclopentadienyl iron (II) hexafluoro alternatively, from 0.8 to 1.15; alternatively, from 0.9 to 1.10: antimonate, cyclopentadienyl iron (II) hexafluorophospho or alternatively, from 0.95 to 1.05. nate, cyclopentadienyl iron (II) hexafluoroarsenate, cumene 0293 Generally, the solvent is utilized when the mixture cyclopentadienyl iron(II) hexafluorophosphate, Xylene comprising the thiol ester composition and the epoxide does cyclopentadienyl iron(II)-tris(trifluoromethylsulfonyl) not cure under the desired conditions. In embodiments, the methide and the like. Other suitable types of catalysts useful Solvent has similar polarity and Viscosity properties to those in the present invention will be apparent to those of ordinary of the thiolester compositions. In an aspect, the solvents have skill in the art and are to be considered within the scope of the relatively low vapor pressures. In some embodiments, the present invention. Solvents have vapor pressures greater than 1 mm Hg at 20°C. 0289 Generally, the catalyst is utilized when the mixture In some embodiments, the solvent is selected from the group comprising the thiol ester composition and the epoxide does consisting of alcohols, esters, ethers, ketones, aromatic not cure under the desired conditions. In embodiments, the hydrocarbons, hydrocarbons, and combinations thereof. In an catalyst can comprise less than 10 weight percent of the embodiment the solvent is an alcohol; alternatively, an ester; mixture. In other embodiments, the catalyst comprises from 1 alternatively, an ether; alternatively, an aromatic hydrocar to 10 percent by weight of the mixture. Alternatively, when bon; or alternatively, a hydrocarbon. The alcohol solvent can the catalyst is combined with the thiolester composition prior be any alcohol having a vapor pressure greater than 1 mm Hg to contacting the thiol ester composition with the epoxide at 20° C. Such as methanol, ethanol. 1-propanol. 2-propanol composition, the catalyst can comprise less than 20 percent (isopropanol), 1-butanol, 2-butanol, 2-methyl-1-propanol by weight of the thiol ester composition. In other embodi (isobutyl alcohol), 2-methyl-2-proanol (tert-butanol), 1-pen ments, the catalyst can comprise from 1 to 20 percent by tanol, 2-pentanol, or combinations thereof. The ester Solvent weight of the thiol ester composition. The amount of the can be any ester having a vapor pressure greater than 1 mmHg ultraviolet initiation catalysts range generally from 0.05 to at 20° C. Such as methyl acetate, ethyl acetate, n-propyl 10.0 parts by weight; alternatively, from 0.075 to 7.0 parts by acetate, isopropyl acetate, n-butyl acetate, or combinations weight; alternatively, from 0.1 to 4.0 parts by weight; or thereof. The ether solvent can be any ether having a vapor alternatively, from 1.0 to 2.5 parts by weight. The amount of pressures greater than 1 mm Hg at 20° C. Such as dimethyl the ultraviolet initiation catalysts range is based upon 100 ether, methyl ethyl ether, diethyl ether, diisopropyl ether, parts by weight of the epoxy resin. dibutyl ether, or combinations thereof. The ketone solvent can 0290. In an aspect, the method of making the epoxy poly be any ketonehaving a vapor pressures greater than 1 mm Hg mer comprises curing the mixture at a temperature ranging at 20°C., such as acetone, 2-butanone (methyl ethyl ketone), from 0°C. to 100°C. In embodiments; the mixture is cured at 3-methyl-2-butanone, 2-pentanone, 3-pentanone, 4-methyl a temperature ranging from 5° C. to 80° C.; alternatively, 2-pentanone (methyl isobutyl ketone), or combinations ranging from 10°C. to 60° C.; or alternatively, ranging from thereof. The aromatic solvent can be any aromatic hydrocar 10° C. to 40° C. In some embodiments, the mixture can be bon having a vapor pressures greater than 1 mm Hg at 20°C., cured at about ambient temperature. Other suitable curing Such as toluene, Xylene (ortho, meta, para or mixtures thereof), or combinations thereof. The hydrocarbon solvent profiles are described in the Example section herein. can be any hydrocarbon having a vapor pressure greater than 0291. In an aspect, the thiol ester composition and the 1 mm Hg at 20° C. Such as pentane, hexane(s), cyclohexane, epoxide composition are contacted at a mercaptan to epoxide heptane(s), octane, or combinations thereof. In some embodi molar ratio ranging from 0.8 to 1.15. In other embodiments, ments, the solvent can contain two or more functional groups, the thiol ester composition and the epoxide composition are e.g. butoxyethanol, diacetone alcohol, or celloSolve acetate, contacted at a mercaptan to epoxide molar ratio ranging from among others. In an aspect, the solvent can be n-butanol, 0.9 to 1.10: or alternatively, from 0.95 to 1.05. In further butoxy ethanol, diacetone alcohol, or combinations thereof. embodiments, the thiol ester composition and the epoxide In some embodiments, the solvent is selected from the group composition are contacted at a mercaptan to epoxide molar consisting of n-butanol, n-butyl acetate, Xylene, MIBK (me ratio of about 1. thyl isobutyl ketone), acetone, n-butyl acetate, butoxyetha 0292. When the thiolester composition further comprises nol, diacetone alcohol, MIBK/toluene, cellosolve acetate, a hydroxyl group both the mercaptain group and the hydroxyl and combinations thereof. Other suitable solvents will be group can react with the epoxide group. One of ordinary skill apparent to those of skill in the art and are to be considered in the art realizes that, in this situation, both the mercaptain within the scope of the present invention. group and the hydroxyl group can react with the epoxide group, but generally, recognizes that the thiol group is more Feedstocks reactive than the hydroxyl group towards epoxides. Thus, the 0294 Unsaturated Ester Composition Comprising Unsat epoxy polymer can be formed by contacting the thiol ester urated Ester Having Internal Carbon-Carbon Double Bonds composition and the epoxide composition in a molar ratio 0295 The unsaturated ester molecules having internal car based upon the mercaptan to epoxide molar ratio or based bon-carbon double bonds may be described using a number US 2009/0264669 A1 Oct. 22, 2009

of different methods. For example, the unsaturated ester hav 0299 The unsaturated ester molecules having internal car ing internal carbon-carbon double bonds may be described by bon-carbon double bonds may be a mixture of unsaturated the number of estergroups and the number of internal carbon ester molecules having internal carbon-carbon double bonds. carbon double bonds that are in each unsaturated ester mol In this situation, the number of internal carbon-carbon double ecule. Suitable unsaturated esters having internal carbon bonds is best described as an average number of ester groups carbon double bonds may include at least one internal carbon per unsaturated ester molecule. In an embodiment, the unsat carbon double bond. However, the number of ester groups urated esters having internal carbon-carbon double bonds and internal carbon-carbon double bonds contained within may have an average of at least of at least 2 internal carbon the unsaturated esters are independent elements and may be varied independently of each other. Thus, the unsaturated carbon double bonds per unsaturated ester molecule; alterna esters having internal carbon-carbon double bonds may have tively, an average of at least 2.5 internal carbon-carbon double any combination of the number of ester groups and the num bonds per unsaturated ester molecule; or alternatively, an ber of internal carbon-carbon double bonds as described average of at least 3 internal carbon-carbon double bonds per separately herein. Suitable unsaturated esters may also con unsaturated ester molecule. In some embodiments, the unsat tain additional functional groups such as hydroxyl, aldehyde, urated esters having internal carbon-carbon double bonds ketone, epoxy, ether, aromatic groups, and combinations may have average of from 1.5 to 9 internal carbon-carbon thereof. For example, the castor oil has hydroxyl groups in double bonds perunsaturated ester molecule; alternatively, an addition to internal carbon-carbon double bonds and ester average of from 3 to 8 internal carbon-carbon double bonds groups. Alternatively, the unsaturated ester having internal per unsaturated ester molecule; alternatively, an average of carbon-carbon double bonds may be substantially devoid of from 2 to 4 internal carbon-carbon double bonds per unsat functional groups other than the ester groups and the internal urated ester molecule; or alternatively, an average of from 4 to carbon-carbon double bonds. Other suitable unsaturated 8 internal carbon-carbon double bonds per unsaturated ester esters will be apparent to those of skill in the art and are to be molecule. considered within the scope of the present techniques. 0300. In addition to the number of ester groups and the 0296. The unsaturated ester molecules having internal car number of non-terminal alkene groups present in the unsat bon-carbon double bonds may have more have at least 2 ester urated ester molecules, the disposition of the non-terminal groups, 3 ester groups or 4 ester groups. In some embodi alkene groups in unsaturated ester molecules having 2 or ments, Further, the unsaturated ester molecules may have more non-terminal alkenegroups may be a consideration. For from 2 to 8 ester groups, from 2 to 7 ester groups or from 3 to example, where the unsaturated ester molecules having inter 5 ester groups. In embodiments, the unsaturated ester may nal carbon-carbon double bonds have 2 or more internal car include from 3 to 4 ester groups. bon-carbon double bonds, the non-terminal alkene groups 0297. The unsaturated ester having internal carbon-carbon may be adjacent and, thus, conjugated. In another example, double bonds may be a mixture of unsaturated ester mol the internal carbon-carbon double bonds may be separated ecules having internal carbon-carbon double bonds. In this from each other by only one carbonatom. When two internal situation, the number of ester groups is best described as an carbon-carbon double bonds are separated by a carbon atom average number of ester groups per unsaturated ester mol having two hydrogen atoms attached to it, e.g. a methylene ecule. In an embodiment, the unsaturated esters having inter group, these internal carbon-carbon double bonds may be nal carbon-carbon double bonds may have an average of at termed as methylene interrupted double bonds. In other mol least 2 ester groups per unsaturated ester molecule; alterna ecules, the internal carbon-carbon double bonds alkene tively, an average of at least 2.5 ester groups per unsaturated groups may isolated, e.g. the internal carbon-carbon double ester molecule; or alternatively an average of at least 3 ester bonds are separated from each other by 2 or more carbon groups per unsaturated ester molecule. In some embodi atoms. Finally, the non-terminal alkene groups may be con ments, the unsaturated esters having internal carbon-carbon jugated with a carbonyl group. double bonds may have an average of from 1.5 to 8 ester 0301 Alternatively, the unsaturated ester molecules hav groups per unsaturated ester molecule; alternatively, an aver ing internal carbon-carbon double bonds of the unsaturated age of from 2 to 7 ester groups per unsaturated ester molecule ester composition may be described as having ester linkages alternatively, an average of from 2.5 to 5 ester groups per comprising a residue of a polyol and a carboxylic acid resi unsaturated ester molecule; or alternatively, an average of dues having an internal carbon-carbon double bond. Addi from 3 to 4 ester groups per unsaturated ester molecule. In tional features of the residue of the polyol and the carboxylic embodiments, the unsaturated esters having internal carbon acid residues having an internal carbon-carbon double bond carbon double bonds may have an average of about 3 ester are independently described herein and may be utilized in any groups per unsaturated ester molecule; or alternatively an combination to describe the unsaturated ester molecules hav average of about 4 ester groups per unsaturated ester mol ing ester linkages comprising a residue of a polyol and a ecule. carboxylic acid residues having an internal carbon-carbon 0298. The unsaturated esters having internal carbon-car double bond. bon double bonds have at least 2 internal carbon-carbon 0302. It will be appreciated that the unsaturated esters double bonds; alternatively, at least 3 internal carbon-carbon having ester linkages comprising a residue of a polyol and double bonds; or alternatively, at least 4 internal carbon carboxylic acid residues having an internal carbon-carbon carbon double bonds. Further, the unsaturated ester having double bond may be a mixture of many different compounds. internal carbon-carbon double bonds may have 2 to 9 internal Consequently, particular features of the unsaturated esters carbon-carbon double bonds; alternatively, 2 to 4 internal having ester linkages comprising a residue of a polyol and carbon-carbon double bonds; alternatively, 3 to 8 internal carboxylic acid residues having an internal carbon-carbon carbon-carbon double bonds; or alternatively, 4 to 8 internal double bond may be described as an average per unsaturated carbon-carbon double bonds. ester molecule. US 2009/0264669 A1 Oct. 22, 2009 44

0303. The residue of the polyol and the carboxylic acid double bond may have an average of at least 6 carbon atoms; residue having an internal carbon-carbon double bond are or alternatively, at least 8 carbon atoms; alternatively, alter independent elements of unsaturated ester molecules having natively, from 6 to 18 carbonatoms; alternatively, from 8 to 14 ester linkages comprising a residue of a polyol and carboxylic carbon atoms; alternatively, from 10 to 11 carbon atoms: acid residues having an internal carbon-carbon double bond. alternatively, about 10 carbon atoms; or alternatively, about Consequently, the features of the residue of the polyol and the 11 carbon atoms. carboxylic acid having an internal carbon-carbon double 0308 Infurther embodiments, the carboxylic acid residue bond are independently described herein and may be used in having an internal carbon-carbon double bond can further any combination to describe the unsaturated ester molecules comprise a hydroxyl group. In some embodiments, the car having ester linkages comprising a residue of a polyol and bon atom bearing the hydroxyl group is separated from the carboxylic acid residues having an internal carbon-carbon internal carbon-carbon double bond by a methylene group double bond. (—CH2—). In other embodiments, the carboxylic acid resi 0304. The carboxylic acid residue having an internal car due having at least one internal carbon-carbon double bond is bon-carbon double bond may be further described by its devoid of other functional groups. structural features. These structural features are indepen (0309 The residue of the polyol may be further described dently described herein and may be utilized in any combina by its structural features. These structural features are inde tion to describe the carboxylic acid residuehaving an internal pendently described herein and may be utilized in any com carbon-carbon double bond. bination to describe the residue of the polyol of the unsatur 0305. In an embodiment, the carboxylic acid residuehav ated ester molecules having ester linkages comprising, or ing an one carbon-carbon double bond may have one, two, consisting essentially of a residue of a polyol and carboxylic three, or more internal carbon-carbon double bonds; alterna acid residues having an one internal carbon-carbon double tively, only one internal carbon-carbon double bonds; alter bond. natively, only two internal carbon-carbon double bonds; or 0310. In an embodiment, residue of the polyol may have 2 alternatively, only three internal carbon-carbon double to 20 carbonatoms. In some embodiments, the residue of the bonds. In will be appreciated, that since the unsaturated ester polyol may have 2 to 12 carbon atoms; alternatively, 2 to 8 molecules comprise multiple carboxylic acid residues having carbon atoms; or alternatively, 2 to 5 carbon atoms. In other internal carbon-carbon double bonds, the unsaturated ester embodiments, the residue of the polyol may be a residue of a molecules having internal carbon-carbon double bonds may mixture of polyols. In Such an instance, the residue of the contain some of carboxylic acid residues having different polyol may have an average of 2 to 20 carbonatoms perpolyol number of internal carbon-carbon double bonds. For residue; alternatively, an average of 2 to 12 carbon atoms per example, an unsaturated ester composition comprising unsat polyol residue, alternatively, an average of 2 to 8 carbon urated ester molecules having ester linkages comprising a atoms per polyol residue, or alternatively, an average of 2 to 5 residue of a triol (e.g. glycerol or trimethylol propane) and carbon atoms per polyol residue. three carboxylic acid residues having an internal carbon 0311. In some embodiment, the residue of the polyol may carbon double bonds may have one carboxylic acid residue have had 2 to 8 hydroxyl group; alternatively, 3 to 6 hydroxyl having only one internal carbon-carbon double bonds, one groups; alternatively, 2 to 4 hydroxyl groups; alternatively, 4 carboxylic acid residue having only two internal carbon-car to 8 hydroxyl groups; alternatively, only 2 hydroxyl groups; bon double bonds, and one carboxylic acid residue having alternatively, only 3 hydroxyl groups; alternatively, only 4 only three internal carbon-carbon double bonds. hydroxyl groups; alternatively, only 5 hydroxyl groups; or 0306. In an embodiment, each internal carbon-carbon alternatively, only 6 hydroxyl groups. In other embodiments, double bond of the carboxylic acid residuehaving an internal the residue of the polyol may be a residue of a mixture of carbon-carbon double bond is a di-substituted internal car polyols. In Such an instance, the residue of the polyol may bon-carbon double bond. In some embodiments, the internal have an average of 2 to 20 carbonatoms per polyol molecule: carbon-carbon double bond closest to the carbonyl group of alternatively, an average of 2 to 12 carbon atoms per polyol the carboxylic acid residue having an internal carbon-carbon molecule; alternatively, an average of 2 to 8 carbonatoms per double bond is a di-substituted internal carbon-carbon double polyol molecule; or alternatively, an average of 2 to 5 carbon bond. In an embodiment, the carboxylic acid residue having atoms per polyol molecule. Further, the residues of the poly an internal carbon-carbon double bond is linear. In another ols may have had an average of at least 2.5 hydroxyl groups embodiment, the carboxylic acid residue having an internal per polyol molecule; alternatively, 2.5 to 8 hydroxyl groups carbon-carbon double bond is linear is branched. per polyol molecule; alternatively, an average of 2 to 6 0307. In an embodiment, the carboxylic acid residuehav hydroxyl groups per polyol molecule; alternatively, an aver ing an internal carbon-carbon double bond may have at least age of 2.5 to 5 hydroxyl groups per polyol molecule; alterna 4 carbon atoms; alternatively, at least 6 carbon atoms; or tively, an average of 2.5 to 4.5 hydroxyl group per polyol alternatively, at least 8 carbon atoms. In some embodiments, molecule; alternatively, an average of 2.5 to 3.5 hydroxyl the carboxylic acid residue having at least one internal car group per polyol molecule; alternatively, an average of 3 to 4 bon-carbon double bond may have from 4 to 20 carbonatoms: hydroxyl group perpolyol molecule; alternatively, an average alternatively, from 6 to 18 carbonatoms; alternatively, from 8 of about 3 hydroxyl groups perpolyol molecule; alternatively, to 14 carbonatoms; alternatively, from 10 to 11 carbonatoms: an average of about 4 hydroxyl groups per polyol molecule: alternatively, only 10 carbon atoms; or alternatively, only 11 alternatively, an average of about 5 hydroxyl groups per carbon atoms. In some embodiments, the carboxylic acid polyol molecule; or alternatively an average of about 6 equivalent having an internal carbon-carbon double bond hydroxy groups per polyol molecule. may be a mixture of carboxylic acid residues having an inter 0312. In an embodiment, the polyol or mixture of polyols nal carbon-carbon double bond. In such embodiments, the used to produce the unsaturated esters compositions compris carboxylic acid residues having an internal carbon-carbon ing or consisting essentially of unsaturated esters having a US 2009/0264669 A1 Oct. 22, 2009

terminal carbon-carbon double bonds has a molecular weight residues having an internal carbon-carbon double bond to or average molecular weight less than 300. In other embodi saturated carboxylic acid residues. In an embodiment, aver ments, the polyol or mixture of polyols have a molecular age ratio of carboxylic acid residues having an internal car weight or average molecular weight less than 250; alterna bon-carbon double bond to saturated carboxylic acid residues tively less than 200; alternatively, less than 150; or alterna may be greater than 5:1; alternatively, less than 7:1; or alter tively, less than 100. natively, less than 10:1. In other embodiments, the unsatur 0313. In an embodiment, the polyol that formed the resi ated ester molecules having ester linkages comprising any due of the polyol is a diol, triol, a tetraol, pentaol, hexaol, or residue of a polyol described herein and any carboxylic acid combination thereof; alternatively a diol, triol, tetraolor com residue having an internal carbon-carbon double bond bination thereof; or alternatively, a triol, tetraol or combina described herein may have an average of greater than 75, 80. tion thereof. In some embodiments, the polyol that formed the 85, or 90 percent of hydroxyl units of the polyol forming the residue of the polyol is a diol; alternatively, a triol; alterna residue of the polyol residue having an ester linkage with any tively, a tetraol; alternatively, a pentaol; or alternatively, a carboxylic acid having an internal carbon-carbon double hexaol. Suitable polyols that may form the residue of the bond described herein. polyol include ethane diol, propanediol, butanediol, pen 0316. In an embodiment, the unsaturated ester molecules, tanediol, hexanediol, cyclohexane diol, phenylethane diol. whether described as having particular functional groups or cyclohexanedimethanol, dimethyolpropane, benzene as unsaturated ester molecules having esterlinkages compris dimethanol, cyclohexanetriol, trihydroxybenzene, trim ing a residue of a polyol and a carboxylic acid residues having ethyolethane, trimethylolpropane, trimethylolbutane, glyc an internal carbon-carbon double bond, may have an average erol, pentaerythritol, sorbitol, or any combination thereof; ratio of carboxylic acid residues having an internal carbon alternatively, cyclohexane diol, trimethylol propane, glyc carbon double bond to ester groups in the thiol ester mol erol, pentaerythritol, or combinations thereof; alternatively, ecules less than 1.15:1; alternatively, less than 1.1:1; or alter glycerol, pentaerythritol, or combinations thereof. In some natively, less than 1.05:1. In some embodiments, the embodiments, the polyol that may form the residue of the unsaturated ester molecules, whether described as having polyol include 1.2-ethanediol. 1,3-propanediol, 1,4-butane particular functional groups oras unsaturated ester molecules diol. 1,5-pentanediol, 1.6-hexanediol, dimethylolpropane, having ester linkages comprising a residue of a polyol and a neopentylglycol, 2-propyl-2-ethyl-1,3-propanediol. 1,2-pro carboxylic acid residues having an internal carbon-carbon panediol. 1.2-butanediol. 1,3-butanediol, 1,4-butanediol, double bond, may have an average ratio carboxylic acid resi diethylene glycol, triethylene glycol, polyethylene glycol, dues having an internal carbon-carbon double bond to ester dipropylene glycol, tripropylene glycol, polypropylene gly groups in the thiol ester molecules ranges from 0.75:1 to col, 11-cyclohexanedimethanol, 1.2-cyclohexanedimetha 1.15:1; alternatively, ranges from 0.85:1 to 1.1:1; or alterna nol, 1.3-cyclohexanedimethanol, 1.4-cyclohexanedimetha tively, ranges from 0.90:1 to 1.05:1. In other embodiments, nol. 1,3-dioxane-5,5-dimethanol, 1-phenyl-1,2-ethanediol, the unsaturated ester molecules, whether described as having trimethylolpropane, trimethylolethane, trimethylolbutane, particular functional groups oras unsaturated ester molecules glycerol, 1,2,5-hexanetriol, pentaerythritol, ditrimethylol having ester linkages comprising a residue of a polyol and a propane, diglycerol, ditrimethylolethane, 1,3,5-trihydroxy carboxylic acid residues having an internal carbon-carbon benzene, 1,2-benzenedimethanol. 1,3-benzenedimethanol, double bond, may have an average ratio of carboxylic acid 1,4-benzenedimethanol, 1-phenyl-1,2-ethanediol, sorbitol, residues having an internal carbon-carbon double bond to or any combination thereof. In other embodiments, the polyol ester groups in the thiol ester molecules of about 1:1. that may be used as the polyol residue may be trimethylol propane, glycerol, pentaerythritol, or combinations thereof; Unsaturated Natural Source Oil alternatively, trimethylolpropane; alternatively, glycerol; 0317. In an aspect, the unsaturated ester having internal alternatively, pentaerythritol; or alternatively sorbitol. carbon-carbon double bonds may be an unsaturated natural 0314. It should be appreciated that not all of the hydroxyl Source oil. For example, the unsaturated natural Source oil groups of the polyol that form the residue of the polyol of the may be tallow, olive, peanut, castor bean, Sunflower, Sesame, thiol ester molecule having ester linkages must form ester poppy, seed, palm, almond seed, hazelnut, rapeseed, soybean, linkages. In some instances some of the hydroxyl groups may corn, safflower, canola, cottonseed, camelina, flaxseed, or not form ester linkages and may remain as hydroxyl group. In walnut oil. From these choices, any one or any combinations an embodiment, the thiol ester molecules having ester link ofunsaturated natural Source oils may be selected on the basis ages that may comprise a residue of a polyol and carboxylic of the desired properties, cost or Supply. For example, the acid residues having a thiol group are Substantially devoid of natural source oil may be selected from the group consisting hydroxy groups derived from the polyol. In other embodi of soybean, rapeseed, canola, or corn oil. Castor bean oil may ments, Substantially, all of the hydroxyl groups of the polyol be selected due to a large available Supply in some parts of the that forms the residue of a polyol form linkages with a car world. Soybean oil may be selected due to a low cost and/or boxylic acid having internal carbon-carbon double bonds. abundant Supply. Finally, other oils may be selected to pro 0315. It will be appreciated that not all of the ester linkages vide appropriate properties in the final composition. In some comprising the residue of the polyol may comprise carboxy embodiments, the unsaturated natural source oil may be Soy lic acid residues having an internal carbon-carbon double bean, corn, castor bean, safflower, canola, cottonseed, cam bond. For example, some of the ester linkages may comprise elina, flaxseed, or walnut oil. In other embodiments, the a residue of the polyol and Saturated carboxylic acid group. In unsaturated natural source oil may be, soybean oil, corn oil, Such an instance, the unsaturated ester molecules having ester canola oil, or castor bean oil. In further embodiments, the linkages comprising a residue of a polyol and carboxylic acid unsaturated natural source oil can be soybean oil; alterna residues having an internal carbon-carbon double bond may tively corn oil; alternatively castor bean oil; or alternatively, be further defined by the average ratio of carboxylic acid canola oil. For example, from the choices listed above, certain US 2009/0264669 A1 Oct. 22, 2009 46 unsaturated natural source oils may be selected to minimize ate, 2,4,4-trimethylhexamethylene diisocyanate, 1.6,11-un the number of methylene interrupted double bonds, which decane triisocyanate, 1.3.6-hexamethylene triisocyanate, or may result in greater amounts of undesirable side products. any combination thereof. In other embodiments, the aliphatic For, example some genetically modified Soybeans may com isocyanates of the isocyanate composition can comprise 1,4- prise triglycerides having reduced quantities of chain groups tetra-methylene diisocyanate, 1.6-hexamethylene, or any having methylene interrupted double bonds (e.g. a linoleic combination thereof. In yet other embodiments, the aliphatic group) and or Saturated chain groups. The unsaturated natural isocyanate of the isocyanate composition comprises 1.6- source oil may be a triglyceride derived from either naturally hexa-methylene. occurring or genetically modified nut, vegetable, plant, or 0321. In embodiments, the cycloaliphatic isocyanates of animal sources. the isocyanate composition can comprise 1-isocyanato-2-iso cyanatomethyl cyclopentane, 1.3-cyclohexane diisocyanate, Isocyanates and Isocyanate Compositions 1,4-cyclohexane diisocyanate, 2.4-methylcyclohexane diiso 0318 Generally, the isocyanate composition comprises an cyanate, 2.6-methylcyclohexane diisocyanate, 1,2-dimethyl isocyanate having at least one isocyanate group. In an cyclohexane diisocyanate, 1,4-dimethylcyclohexane diisocy embodiment, the isocyanate composition is comprised of iso anate, isophorone diisocyanate (IPDI), 1-isocyanato-1- cyanates having multiple isocyanate groups. In some embodi methyl-4(3)-isocyanatomethyl cyclohexane, 1,3-bis ments, the isocyanate has at least two isocyanate groups; (isocyanato-methyl) cyclohexane, 1,4-bis(isocyanato alternatively, at least three isocyanate groups; or alternatively, methyl)cyclohexane, 2,4'-dicyclohexylmethane at least 4 isocyanate groups. In other embodiments, the iso diisocyanate, 4,4'-dicyclohexylmethane diisocyanate (hydro cyanate has from 2 to 8 isocyanate groups; alternatively, from genated MDI, HMDI), 2,2'-dimethyldicyclohexylmethane 2 to 6; alternatively from 2 to 4 isocyanate groups. In yet other diisocyanate, 4,4'-bis(3-methylcyclohexyl)methane diisocy embodiments, the isocyanate has only 2 isocyanate groups; anate, or any combination thereof. In some embodiments, the alternatively, only 3 isocyanate groups; or alternatively, only cyclic aliphatic isocyanates of the isocyanate composition 4 isocyanate groups. In an aspect, the isocyanate composition can comprise 1.3-cyclohexane diisocyanate, 1,4-cyclohexane comprises a mixture of isocyanates. When the isocyanate diisocyanate, 2.4-methylcyclohexane diisocyanate, 2.6-me composition comprises a mixture of isocyanates, the isocy thylcyclohexane diisocyanate, 1,2-dimethylcyclohexane anates can have an average of at least 1.5 isocyanate groups diisocyanate, 1,4-dimethylcyclohexane diisocyanate, iso per isocyanate molecule; alternatively, an average of at least 2 phorone diisocyanate, 2,4'-dicyclohexylmethane diisocyan isocyanate groups per isocyanate molecule; alternatively, an ate, 4,4'-dicyclohexylmethane diisocyanate, or any combina average of at least 2.5 isocyanate groups per isocyanate mol tion thereof. In other embodiments, the cyclic aliphatic ecule; or alternatively, an average of at least 3 isocyanate isocyanate of the isocyanate composition comprises 1.3-cy groups per isocyanate molecule. In embodiments, the isocy clohexane diisocyanate; alternatively, 14-cyclohexane diiso anates can have an average of from 1.5 to 12 isocyanate cyanate; alternatively, 2.4-methylcyclohexane diisocyanate; groups per isocyanate molecule; alternatively, an average of alternatively, 2.6-methylcyclohexane diisocyanate; alterna from 1.5 to 9 isocyanate groups per isocyanate molecule: tively, isophorone diisocyanate; alternatively, 2,4'-dicyclo alternatively, an average of from 2 to 7 isocyanate groups per hexylmethane diisocyanate; or alternatively, 4,4'-dicyclo isocyanate molecule; alternatively, an average of from 2 to 5 hexylmethane diisocyanate. isocyanate groups per isocyanate molecule; or alternatively, 0322. In embodiments, the aromatic isocyanates of the an average of from 2 to 4 isocyanate groups per isocyanate isocyanate composition can comprise 1.3-phenylene diisocy molecule. anate, 1,4-phenylene diisocyanate, 2,4-tolylene diisocyanate 0319. In an embodiment, the isocyanate composition can (TDI), 2.5-toluene diisocyanate 2,6-tolylene diisocyanate, comprise aliphatic isocyanates, cycloaliphatic isocyanates, tolylene-C,4-diisocyante, 1.3-xylylene diisocyanate, 1,4-Xy aromatic isocyanates, or any combination thereof. In some lylene diisocyanate, diethylphenylene diisocyanate, diisopro embodiments, the isocyanate composition comprises ali pylphenylene diisocyanate, trimethylbenzene triisocyanate, phatic isocyanates; alternatively, cycloaliphatic isocyanates; C.C.C.'.C.'-tetramethyl-1,3-xylylene diisocyanate, C.C.C.'.C.'- or alternatively, aromatic isocyanates. tetramethyl-1,4-xylylene diisocyanate, mesitylene triisocy 0320 In an embodiment, the aliphatic isocyanates of the anate, benzene triisocyanate, 1.5-diisocyanato naphthalene, isocyanate composition can comprise ethylene diisocyanate, methylnaphthalene diisocyanate, bis(isocyanatomethyl) 1,3-trimethylene diisocyanate, 1,4-tetramethylene diisocyan naphthalene, biphenyl diisocyanate, 2,4'-diphenylmethane ate, 1.6-hexamethylene diisocyanate, 1.7-heptamethylene diisocyanate, 4,4'-diphenylmethane diisocyanate (MDI), isocyanate, 1.8-octamethylene diisocyanate, 1.9-nonameth polymeric 4,4'-diphenyl-methane diisocyanate (polymeric ylene diisocyanate, 1,10-decamethylene diisocyanate, 1,1- MDI, PMDI), 3,3'-dimethyl-diphenylmethane-4,4'-diisocy undecamethylene diisocyanate, 1,12-dodeca-methylene anate, bibenzyl-4,4'-diisocyanate, bis(isocyanatophenyl)eth diisocyanate, 2,2'-dimethylpentane diisocyanate, 2.2,4-trim ylene, triphenylmethane triisocyanate, bis(isocyanatoethyl) ethyl-1,6-hexamethylene diisocyanate, 2,4,4-trimethylhex benzene, bis-(isocyanatopropyl)benzene, bis amethylene diisocyanate, 1,6,11-undecane triisocyanate, 1.3, (isocyanatobutyl)benzene, naphthalene triisocyanate, 6-hexa-methylene triisocyanate, 1,8-diisocyanato-4- diphenylmethane-2,4,4-triisocyanate, 3-methyldiphenyl (isocyanatomethyl)octane, 2.5,7-trimethyl-1,8-diisocyanato methane-4,6,4'-triisocyanate, 4-methyldiphenyl-methane-3, 5-(isocyanatomethyl)octane, or any combination thereof. In 5.2',4',6'-pentaisocyanate, tetrahydronaphthylene diisocyan Some embodiments, the aliphatic isocyanates of the isocyan ate, or any combination thereof. In some embodiments, the ate composition can comprise ethylene diisocyanate, 1.3- aromatic isocyanates of the isocyanate composition can com trimethylene diisocyanate, 1,4-tetramethylene diisocyanate, prise 1.3-phenylene diisocyanate, 1,4-phenylene diisocyan 1.6-hexamethylene diisocyanate, 1,12-dodecamethylene ate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1.3- diisocyanate, 2,2,4-trimethyl-1,6-hexamethylene diisocyan Xylylene diisocyanate, 1,4-xylylene diisocyanate, US 2009/0264669 A1 Oct. 22, 2009 47 trimethylbenzene triisocyanate, benzene triisocyanate, group; or alternatively, Hora C to Cs hydrocarbyl group. In biphenyl diisocyanate, 2,4'-diphenylmethane diisocyanate, yet other embodiments, R', R, and Rare H, or R' and Rare 4,4'-diphenylmethane diisocyanate, polymeric 4,4'-diphenyl Hand R is a methyl group, or a combination thereof. In yet methane diisocyanate, 3,3'-dimethyl-diphenylmethane-4,4'- other embodiments, R', R, and Rare H; or alternatively, R' diisocyanate, bibenzyl-4,4'-diisocyanate, triphenylmethane and R are H and R is a methyl group. When an epoxide triisocyanate, polymeric MDI, naphthalene triisocyanate, or molecule comprises two or more E1 groups, the additional El any combination thereof. In other embodiments, the aliphatic isocyanates of the isocyanate composition comprises 1,3- can be located within R', R,R or the undesignated epoxide phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,4- Valency. In an embodiment when the epoxide molecule com tolylene diisocyanate, 2,6-tolylene diisocyanate, 1.3-Xy prises two or more E2 groups, R. R. and R can be any group lylene diisocyanate, 1,4-xylylene diisocyanate, 2,4'- described herein and the additional E2 group(s) are located in diphenylmethane diisocyanate, 4,4'-diphenylmethane the undesignated epoxide valency. diisocyanate, polymeric 4,4'-diphenylmethane diisocyanate, 0325 In embodiments, the epoxide composition com 3,3'-dimethyl-diphenylmethane-4,4'-diisocyanate, poly prises an epoxide having at least 2 epoxide groups having meric 4,4'-diphenylmethane diisocyanate, or any combina structure E1. In embodiments, the epoxide composition can tion thereof. In yet other embodiments, the aliphatic isocyan comprise an epoxide having at least 3 epoxide groups having ates of the isocyanate composition comprises 2,4-tolylene structure E1. In some embodiments, the epoxide composition diisocyanate; alternatively, 2,6-tolylene diisocyanate; alter comprises a mixture of epoxide molecules having structure natively, 2.4- and 2,6-tolylene diisocyanate; alternatively, E1. When the epoxide composition comprises a mixture of 4,4'-diphenylmethane diisocyanate; alternatively, polymeric epoxide molecules, the epoxide molecules can have an aver 4,4'-diphenylmethane diisocyanate; or alternatively, mixtures age of at least 1.5 epoxide groups having structure E1 per of 2,4'-diphenylmethane diisocyanate and 4,4'-diphenyl epoxide molecule; alternatively, an average of at least 2 methane diisocyanate. epoxide groups having structure E1 per epoxide molecule: alternatively, an average of at least 2.5 epoxide groups having Epoxide Compositions structure E1 per epoxide molecule; or alternatively, an aver 0323 Generally, the epoxide composition comprises an age of at least 3 epoxide groups having structure E1 per epoxide having at least 1 epoxide group. In an embodiment, epoxide molecule. In embodiments, the epoxide molecules the epoxide composition can comprise an epoxide having at can have an average of from 1.5 to 16 epoxide groups having least 2 epoxide groups; alternatively, at least three epoxide structure E1 per epoxide molecule; alternatively, an average groups. In some embodiments, the epoxide composition com of from 1.5 to 12 epoxide groups having structure E1 per prises a mixture of epoxide molecules. When the epoxide epoxide molecule; alternatively, an average of from 1.5 to 9 composition comprises a mixture of epoxide molecules, the epoxide groups having structure E1 per epoxide molecule: epoxide molecules can have an average of at least 1.5 epoxide alternatively, an average of from 2 to 7 epoxide groups having groups per epoxide molecule; alternatively, an average of at structure E1 per epoxide molecule; alternatively, an average least 2 epoxide groups per epoxide molecule; alternatively, an offrom 2 to 5 epoxide groups having structure E1 per epoxide average of at least 2.5 epoxide groups per epoxide molecule: molecule; or alternatively, an average of from 2 to 4 epoxide or alternatively, an average of at least 3 epoxide groups per groups having structure E1 per epoxide molecule. epoxide molecule. In other embodiments, the epoxide mol 0326. A class of epoxides that can be utilized in the ecules can have an average of from 1.5 to 16 epoxide groups epoxide composition is a polyol glycidylether. Generally, the per epoxide molecule; alternatively, an average of from 1.5 to polyol glycidylether composition may be comprised of mol 12 epoxide groups per epoxide molecule; alternatively, an ecules having multiple glycidylether groups having structure average of from 1.5 to 9 epoxide groups per epoxide mol E2: ecule; alternatively, an average of from 2 to 7 epoxide groups per epoxide molecule; alternatively, an average of from 2 to 5 epoxide groups per epoxide molecule; or alternatively, an E2 average of from 2 to 4 epoxide groups per epoxide molecule. Rs. R' 0324 Generally, the epoxide may be comprised of mol R6 O ecules having multiple groups having structure E1: o1 R5 R E1 where each R,R,R,R, and R can be H, an organyl group, or a hydrocarbyl group and the undesignated Valency repre sents the remainder of the structure of the polyol gly cidylether molecule. In embodiments, each R. R. R. R. and R can be Hora C, to Cao organyl group; alternatively, H where each R', R, and R can be H, an organyl group, or a or a C to Co organyl group; or alternatively, Hora C to Cs hydrocarbyl group and the undesignated Valency represents organyl group. In other embodiments, each R. R. R. R. the remainder of the structure of the epoxide molecule. In and R can be H or a C to Cao hydrocarbyl group; alterna embodiments, each R', R, and R can be H or a C to Co tively, Hora C to Cohydrocarbyl group; or alternatively, H organyl group; alternatively, H or a C to Co organyl group; or a C to Cs hydrocarbyl group. In yet other embodiments, or alternatively, H or a C to Cs organyl group. In other R. R. R. and Rare H and R is a methyl group; or alter embodiments, each R', R, and R can be H or a C to Co natively, R,R,R,R, and Rare H. In an embodiment when hydrocarbyl group; alternatively, Hora C to Cohydrocarbyl the epoxide molecule comprises two or more E2 groups, R. US 2009/0264669 A1 Oct. 22, 2009 48

R. R. R. and R can be any group described herein and the alcohol groups per alcohol molecule; or alternatively, an aver additional E2 group(s) are located in the undesignated age of from 2 to 4 alcohol groups per alcohol molecule. epoxide Valency. 0330. In an aspect, the polyol of the polyol glycidylether 0327. In embodiments, the epoxide composition com product can be an aliphatic polyol. In embodiments, the ali prises a glycidylethermolecule having at least 2 glycidylether phatic polyol of the polyol glycidylether product can com groups having structure E2. In embodiments, the gly prise ethylene glycol, diethylene glycol, triethylene glycol, cidylether composition can comprise a glycidylether having tetraethylene glycol, tripropylene glycol, polyethylene gly at least 3 glycidylether groups having structure E2. In some cols with a molecular weight of from 106 to 8500, polyeth ylene glycols with a molecular weight of from 400 to 2000, embodiments, the glycidylether composition comprises a 1.2-propanediol. 1,3-propanediol. 1.2-butanediol. 1,3-bu mixture of glycidylether molecules having structure E2. tanediol. 1,4-butanediol. 1.5-pentanediol, neopentylglycol, When the glycidylether composition comprises a mixture of 1.2-hexanediol, 1.6-hexanediol. 1.2-octanediol. 1.8-oc glycidylether molecules, the glycidylether molecules can tanediol. 1,2-decanediol. 1,10-decanediol, glycerol. 2.2-dim have an average of at least 1.5 glycidylether groups having ethylolpropane, trimethylolethane, trimethylolpropane, pen structure E2 per glycidylether molecule; alternatively, an taerythritol, dipentaerythritol, sorbitol, 1,2,4-butanetriol, 2.2, average of at least 2 glycidylether groups having structure E2 4-trimethyl-1,3-pentanediol, or combinations thereof. In per glycidylether molecule; alternatively, an average of at Some embodiments, the aliphatic polyol of the polyol gly least 2.5 glycidylether groups having structure E2 per gly cidylether product can comprise ethylene glycol, diethylene cidylether molecule; or alternatively, an average of at least 3 glycol, triethylene glycol, tetraethylene glycol; alternatively, glycidylether groups having structure E2 per glycidylether tripropylene glycol; alternatively, ethylene glycol, alterna molecule. In embodiments, the glycidylether molecules can tively, diethylene glycol, alternatively, triethylene glycol, have an average of from 1.5 to 16 glycidylether groups having alternatively, tetraethylene glycol, alternatively, polyethylene structure E2 per glycidylether molecule; alternatively, an glycols with a molecular weight of from 106 to 8500; alter average of from 1.5 to 12 glycidylether groups having struc natively, polyethylene glycols with a molecular weight of ture E2 per glycidylether molecule; alternatively, an average from 400 to 2000; alternatively, 1,2-propanediol. 1,3-pro of from 1.5 to 9 glycidylether groups having structure E2 per panediol, or mixtures thereof; alternatively, 1.2-butanediol, glycidylether molecule; alternatively, an average of from 2 to 1,3-butanediol, 1,4-butanediol, or mixtures thereof, alterna 7 glycidylether groups having structure E2 per glycidylether tively, 1.5-pentanediol, neopentyl glycol, or mixtures, molecule; alternatively, an average of from 2 to 5 gly thereof; alternatively, 1.2-hexanediol, or 1.6-hexanediol; cidylether groups having structure E2 per glycidylether mol alternatively, 1.2-octanediol, or 1.8-octanediol; alternatively, ecule; or alternatively, an average of from 2 to 4 glycidylether 1.2-decanediol, or 1,10-decanediol; alternatively, glycerol; groups having structure E2 per glycidylether molecule. alternatively, 2,2-dimethylolpropane; alternatively, trimethy 0328. In embodiments, the polyol glycidylether can be lolethane; alternatively, trimethylolpropane; alternatively, described as a glycidylether product of contacting a polyhy pentaerythritol; alternatively, dipentaerythritol; alternatively, dric alcohol (or polyol) with an epichlorohydrin (herein sorbitol; alternatively, 1,2,4-butanetriol; or alternatively, 2.2, referred to as “poly glycidylether product”). While this 4-trimethyl-1,3-pentanediol. In other embodiments, the ali description appears to imply that the polyol glycidylether is phatic polyol can comprise an ethoxylate, a propoxylate, or a prepared by contacting a polyol with an epichlorohydrin, this mixed ethoxylate/propoxylate of an aliphatic polyol or mix is not the intent of the description. The intent of the descrip ture of aliphatic polyols. In yet other embodiments, the polyol tion is to describe the polyol glycidylether. The polyol gly comprises a polyol ethoxylate product containing from 2 to cidylether product can be prepared using any method appar 400 mol of ethylene oxide per mole of polyol. ent to those persons having ordinary skill in the art. For 0331. In an aspect, the polyol of the polyol glycidylether example, the poly glycidylether product can be prepared by product can be a cyclic aliphatic polyol. In embodiments, the contacting a polyol with an epihalohydrin (chloro, bromo or cyclicaliphatic polyol of the polyol glycidylether product can iodo) or by contacting a metal salt of a polyol with an epiha comprise 1.2-cyclo-pentanediol, 1.3-cyclopentanediol. 1.2- lohydrin (chloro, bromo, or iodo) among other methods. The cyclohexanediol. 1.3-cyclohexanediol. 1,4-cyclohexanediol. polyol component can be any aliphatic, cycloaliphatic, or 1.2-cyclohexanedimethanol, 1.4-cyclohexanedimethanol, aromatic polyol. bis(4-hydroxycyclohexyl)methane, 2.2-bis(4-hydroxy-cy 0329. In embodiments, the polyol of the polyol gly clohexyl)propane, or any combination thereof. In some cidylether product comprises at least 2 alcohol groups (or embodiments, the cyclic polyol of the polyol glycidylether alternatively called hydroxy groups); alternatively, at least 3 product can comprise 1.2-cyclopentanediol, 1.3-cyclopen alcohol groups; or alternatively, at least 4 alcohol groups. In tanediol, or mixtures thereof; alternatively, 1.2-cyclohex Some embodiments, the polyol can comprise a mixture of anediol. 1.3-cyclohexanediol. 1.4-cyclohexanediol, or mix alcohols having an average of at least 1.5 alcohol groups per tures thereof; alternatively, 1.2-cyclopentanediol; alcohol molecule; alternatively, an average of at least 2 alco alternatively, 1.3-cyclopentanediol; alternatively, 1.2-cyclo hol groups per alcohol molecule; alternatively, an average of hexanediol; alternatively, 1.3-cyclohexanediol; alternatively, at least 2.5 alcohol groups per alcohol molecule; alternatively, 1,4-cyclohexanediol; alternatively, 1.2-cyclohexanedimetha an average of at least 3 alcohol groups per alcohol molecule: nol; or alternatively, 1.4-cyclohexanedimethanol; or alterna alternatively, an average of from 1.5 to 16 alcohol groups per tively, bis(4-hydroxycyclohexyl)methane; or alternatively, alcohol molecule; alternatively, an average of from 1.5 to 12 2.2-bis(4-hydroxy-cyclohexyl)propane. alcohol groups per alcohol molecule; alternatively, an aver 0332. In an aspect, the polyol of the polyol glycidylether age of from 1.5 to 9 alcohol groups per alcohol molecule: product can be an aromatic polyol. In embodiments, the aro alternatively, an average of from 2 to 7 alcohol groups per matic polyol of the polyol glycidylether product can comprise alcohol molecule; alternatively, an average of from 2 to 5 1-phenyl-1,2-ethanediol. 1.2-benzenediol (pyrocatechol), US 2009/0264669 A1 Oct. 22, 2009 49

1,3-benzenediol (resorcinol), 1,4-benzenediol, methyl cat alternatively, bisphenol M; alternatively, bisphenol P; alter echol, methyl resorcinol, 1,2,4-benzenetriol, 2-hydroxyben natively, bisphenol S; or alternatively, bisphenol Z. Zylalcohol, 3-hydroxybenzylalcohol, 4-hydroxybenzylalco 0336 Within the substituted phenolic compound portion hol. 3,5-dihydroxybenzylalcohol, 1,2-benzenedimethanol, of the novolak resin, the Substitute(s) can be any organyl 1,3-benzene-di-methanol, 1,4-benzene-dimethanol, 2-(2-hy group, a hydrocarbyl group, a halide atom, or any combina droxyphenyl)ethanol. 2-(3-hydroxy-phenyl)-ethanol, 2-(4- tion thereof. In some embodiments, the phenolic compound hydroxyphenyl)-ethanol. 2-phenyl-1,2-propanediol or mix Substituent(s) can be a C to Co organyl group, a C to Co tures thereof. In some embodiments, the aromatic polyol of hydrocarbyl group, a halide atom, or any combination the polyol glycidylether product can comprise 1-phenyl-1,2- thereof, alternatively, a C to Co organyl group, a C to Co ethanediol; alternatively, 1,2-benzenediol (catechol, pyrocat hydrocarbyl group, a halide atom, or any combination echol); alternatively, 1,3-benzenediol (resorcinol); alterna thereof, or alternatively, a C to Cs organyl group, a C to Cs tively, 1,4-benzenediol; alternatively, methyl catechol; hydrocarbyl group, a halide atom, or any combination alternatively, methyl resorcinol; alternatively, 1,2,4-benzen thereof. etriol; alternatively, 2-hydroxybenzylalcohol; alternatively, 0337 Generally, a particular novolak resin can be indi 3-hydroxybenzylalcohol; alternatively, 4-hydroxybenzylal cated by prefacing the novolak resin with the aldehyde and/or cohol; alternatively, 3,5-dihydroxybenzylalcohol; alterna phenolic compound utilized to produce the novolak resin. tively, 1,2-benzenedimethanol; alternatively, 1,3-benzene-di Thus, in embodiments, the novolak resin of the polyol gly methanol; alternatively, 1,4-benzenedimethanol: cidylether product can comprise a formaldehyde-phenol alternatively, 2-(2-hydroxyphenyl)ethanol; alternatively, novolak resin, a formaldehyde-substituted phenol novolak 2-(3-hydroxy-phenyl)ethanol; alternatively, 2-(4-hydrox resin, a formaldehyde-catechol novolak resin, a formalde yphenyl)ethanol; or alternatively, 2-phenyl-1,2-propanediol. hyde-substituted catechol novolak resin, a formaldehyde-re 0333. In an aspect, the aromatic polyol of the polyol gly Sorcinol novolak resin, a formaldehyde-substituted resorci cidylether product can be a bisphenol. In embodiments, the nol novolak resin, a formaldehyde-1,4-benzenediol novolak bisphenol can be bisphenol A (2,2-di(4-hydroxy-phenyl)pro resin, a formaldehyde-substituted 1,4-benzenediol novolak pane), bisphenol AP (4,4'-(1-phenyl-ethylidene)bisphenol), resin, a formaldehyde-1,2,4-benzenetriol novolak resin, a bisphenol F (bis(4-hydroxy-phenyl)methane), bisphenol M formaldehyde-bisphenol A novolak resin, a formaldehyde (4,4'-(1,3-phenylidene-diisopropylidene)bisphenol), bisphe bisphenol AP novolak resin, a formaldehyde-bisphenol F nol P (4,4'-(1,4-phenylidene-diisopropylidene)-bisphenol), novolak resin, a formaldehyde-bisphenol M novolak resin, a bisphenol S (4,4'-dihydroxydiphenylsulfone), bisphenol Z formaldehyde-bisphenol P novolak resin, a formaldehyde (4,4'-cyclohexylidene-bisphenol), or any combination bisphenol S novolak resin, a formaldehyde-bisphenol Z thereof. In some embodiments, the bisphenol can be bisphe novolak resin, or any combination thereof. In other embodi nol A; alternatively, bisphenol AP; alternatively, bisphenol F. ments, the novolak resin of the polyol glycidylether product alternatively, bisphenol M; alternatively, bisphenol P; alter can comprise a formaldehyde-phenol novolak resin; alterna natively, bisphenol S; or alternatively, bisphenol Z. tively, a formaldehyde-substituted phenol novolak resin; 0334. In an aspect, the aromatic polyol of the polyol gly alternatively, formaldehyde-catechol novolak resin; alterna cidylether product can be a novolak resin. Novolak resins are tively, a formaldehyde-substituted catechol novolak resin; a broad class of resins that are produced by the condensation alternatively, a formaldehyde-resorcinol novolak resin; alter reaction of a phenolic compound with an aldehyde. Novolak natively, a formaldehyde-substituted resorcinol novolak resins are manufactured using a wide range of phenolic com resin; alternatively, a formaldehyde-1,4-benzenediol novolak pounds and aldehyde combinations and can be produced in a resin; alternatively, a formaldehyde-substituted 1,4-benzene wide range of molecular weights. Within this specification, diol novolak resin; alternatively, a formaldehyde-1,2,4-ben the term “novolak resin' generally refers to the oligomerized Zenetriol novolak resin; alternatively, a formaldehyde or polymerized product of the aldehyde and phenolic com bisphenol A novolak resin; alternatively, a formaldehyde pound and does not connote any indication of the degree of bisphenol AP novolak resin; alternatively, a formaldehyde oligomerization, molecular weight, and/or the physical form bisphenol F novolak resin; alternatively, a formaldehyde (e.g. Solid, liquid etc. . . . ) of the novolak resin. bisphenol M novolak resin; alternatively, a formaldehyde 0335. In embodiments, the aldehyde used to produce the bisphenol P novolak resin; alternatively, a formaldehyde novolak resin can be formaldehyde. In embodiments, the bisphenol S novolak resin; or alternatively, a formaldehyde phenolic compound used to produce the novolak resin can be bisphenol Z novolak resin. any phenolic compound capable of undergoing a condensa 0338. In embodiments, aliphatic polyol glycidyl ethers tion reaction with an aldehyde. In some non-limiting embodi that can be utilized within the epoxide composition can ments, the phenolic compound can be phenol, a Substituted include, singly or in any combination thereof, ethylene glycol phenol, catechol (pyrocatechol), a Substituted catechol, resor diglycidyl ether, diethylene glycol diglycidyl ether, triethyl cinol, a Substituted resorcinol, 1,4-benzenediol, a Substituted ene glycol diglycidyl ether, tetraethylene glycol diglycidyl 1,4-benzene diol. 1,2,4-benzenetriol, bisphenol A, Bisphenol ether, tripropylene glycol diglycidyl ether, diglycidyl ethers AP, bisphenol F. bisphenol M, bisphenol P. bisphenol S. of polyethylene glycols with a molecular weight of from 106 bisphenol Z, or any combination thereof. In some embodi to 8500, diglycidyl ethers of polyethylene glycols with a ments, the phenolic compound can comprise phenol; alterna molecular weight of from 400 to 2000, 1,2-propanediol dig tively, a Substituted phenol; alternatively, catechol; alterna lycidyl ether, 1,3-propanediol diglycidyl ether, 1.2-butane tively, a substituted catechol; alternatively, resorcinol: diol diglycidyl ether, 1,3-butanediol diglycidyl ether, 1,4- alternatively, a substituted resorcinol; alternatively, 1,4-ben butanediol diglycidyl ether, 1,5-pentanediol diglycidyl ether, Zenediol; alternatively, a substituted 1,4-benzenediol; alter neopentylglycol diglycidyl ether, 1.2-hexanediol diglycidyl natively, 1,2,4-benzenetriol; alternatively, bisphenol A; alter ether, 1.6-hexanediol diglycidyl ether, 1.2-cyclohexanediol natively, Bisphenol AP; alternatively, bisphenol F. diglycidyl ether, 1.4-cyclohexanediol diglycidyl ether, 1.2- US 2009/0264669 A1 Oct. 22, 2009 50 octanediol diglycidyl ether, 1.8-Octanediol diglycidyl ether, alternatively, 1.2-cyclohexanediol diglycidyl ether, 1.3-cy 1,2-decanediol diglycidyl ether, 1,10-decanediol diglycidyl clohexanediol diglycidyl ether, 1.4-cyclohexanediol digly ether, glycerol triglycidyl ether, 2.2-dimethylolpropane dig cidyl ether, or mixtures thereof, alternatively, 1.2-cyclopen lycidyl ether, trimethylolethane triglycidyl ether, trimethylol tanediol diglycidyl ether, alternatively, 1.3-cyclopentanediol diglycidyl ether; alternatively, 1.2-cyclohexanediol digly propane diglycidyl ether, pentaerythritol tetraglycidyl ether, cidyl ether; alternatively, 1.3-cyclohexanediol diglycidyl dipentaerythritol tetraglycidyl ether, dipentaerythritol hexa ether; alternatively, 1,4-cyclohexanediol diglycidyl ether; glycidyl ether, sorbitol tetraglycidyl ether, sorbitol hexagly alternatively, 1.2-cyclohexanedimethanol diglycidyl ether; cidyl ether, 1,2,4-butanetriol triglycidyl ether, 2.2,4-trim alternatively, 1,4-cyclohexanedimethanol diglycidyl ether; ethyl-1,3-pentanediol triglycidyl ether, or combinations alternatively, bis(4-hydroxycyclohexyl)methane diglycidyl thereof. In some embodiments, aliphatic polyol glycidyl ether; or alternatively, 2.2-bis(4-hydroxy-cyclo-hexyl)-pro ethers that can be utilized within the epoxide composition can pane diglycidyl ether. comprise ethylene glycol diglycidyl ether, diethylene glycol 0340. In embodiments, aromatic polyol glycidyl ethers diglycidyl ether, triethylene glycol diglycidyl ether, tetraeth that can be utilized within the epoxide composition can ylene glycol diglycidyl ether, alternatively, tripropylene gly include, singly or in any combination thereof. 1-phenyl-1,2- col diglycidyl ether, alternatively, ethylene glycol diglycidyl ethanediol diglycidyl ether, 1,2-benzenediol diglycidyl ether ether; alternatively, diethylene glycol diglycidyl ether; alter (pyrocatechol diglycidyl ether), 1,3-benzenediol diglycidyl natively, triethylene glycol diglycidyl ether, alternatively, tet ether (resorcinol diglycidyl ether), 1,4-benzenediol digly raethylene glycol diglycidyl ether; alternatively, diglycidyl cidyl ether, methyl catechol diglycidyl ether, methyl resorci nol diglycidyl ether, 1,2,4-benzenetriol triglycidyl ether, ethers of polyethylene glycols with a molecular weight of 2-hydroxybenzylalcohol diglycidyl ether, 3-hydroxybenzy from 106 to 8500; alternatively, diglycidyl ethers of polyeth lalcohol diglycidyl ether, 4-hydroxybenzylalcohol diglycidyl ylene glycols with a molecular weight of from 400 to 2000; ether, 3,5-dihydroxybenzylalcohol diglycidyl ether, 1,2-ben alternatively, 1,2-propanediol diglycidyl ether, 1,3-pro Zenedimethanol diglycidyl ether, 1,3-benzene-dimethanol panediol diglycidyl ether, or mixtures thereof; alternatively, diglycidyl ether, 1,4-benzene-dimethanol diglycidyl ether, 1.2-butanediol diglycidyl ether, 1,3-butanediol diglycidyl 2-(2-hydroxyphenyl)ethanol diglycidyl ether, 2-(3-hydroxy ether, 1,4-butanediol diglycidyl ether, or mixtures thereof; phenyl)-ethanol diglycidyl ether, 2-(4-hydroxy-phenyl)etha alternatively, 1,5-pentanediol diglycidyl ether, neopentylgly nol diglycidyl ether, or 2-phenyl-1,2-propanediol diglycidyl col diglycidyl ether, or mixtures, thereof; alternatively, 1.2- ether. In embodiments, aromatic polyol glycidyl ethers that cyclohexanediol diglycidyl ether, 1.4-cyclohexanediol digly can be utilized within the epoxide composition can be 1-phe cidyl ether, or mixtures thereof, alternatively, 1.2-hexanediol nyl-1,2-ethanediol diglycidyl ether, alternatively, 1,2-ben diglycidyl ether or 1.6-hexanediol diglycidyl ether; alterna Zenediol diglycidyl ether; alternatively, 1,3-benzenediol dig tively, 1.2-octanediol diglycidyl ether or 1.8-octanediol dig lycidyl ether; alternatively, 1,4-benzenediol diglycidyl ether; lycidyl ether; alternatively, 1,2-decanediol diglycidyl ether or alternatively, methyl catechol diglycidyl ether; alternatively, 1,10-decanediol diglycidyl ether, alternatively, glycerol trig methyl resorcinol diglycidyl ether; alternatively, 1,2,4-ben lycidyl ether; alternatively, 2,2-dimethylolpropane diglycidyl Zenetriol triglycidyl ether; alternatively, 2-hydroxybenzylal ether; alternatively, trimethylolethane triglycidyl ether; alter cohol diglycidyl ether; alternatively, 3-hydroxybenzylalco natively, trimethylolpropane triglycidyl ether, alternatively, hol diglycidyl ether; alternatively, 4-hydroxybenzylalcohol pentaerythritol tetraglycidyl ether, alternatively, dipen diglycidyl ether; alternatively, 3,5-dihydroxybenzylalcohol taerythritol hexaglycidyl; alternatively, dipentaerythritol tet diglycidyl ether; alternatively, 1,2-benzenedimethanol digly cidyl ether; alternatively, 1,3-benzenedimethanol diglycidyl raglycidyl ether; alternatively, sorbitol tetraglycidyl ether; ether; alternatively, 1,4-benzenedimethanol diglycidyl ether; sorbitol hexaglycidyl ether; alternatively, 1,2,4-butanetriol alternatively, 2-(2-hydroxyphenyl)ethanol diglycidyl ether; triglycidyl ether; or alternatively, 2,2,4-trimethyl-1,3-pen alternatively, 2-(3-hydroxy-phenyl)ethanol diglycidyl ether; tanediol diglycidyl ether. In other embodiments, aliphatic alternatively, 2-(4-hydroxyphenyl)ethanol diglycidyl ether; polyol glycidyl ethers that can be utilized within the epoxide or alternatively, 2-phenyl-1,2-propanediol diglycidyl ether. composition can comprise a polyglycidyl ether of an ethoxy 0341. In embodiments, the glycidyl ether that can be uti late, a propoxylate, or a polyglycidyl ether of a mixed ethoxy lized within the epoxide composition can be a novolak polyg late/propoxylate of a polyol or mixture of a polyols. In yet lycidyl ether (a glycidylether product of a novolak resin). In other embodiments, aliphatic polyol glycidyl ethers that can embodiments, the novolak polyglycidyl ethers that can be be utilized within the epoxide composition can comprise a utilized within the epoxide composition can include a form polyglycidyl ether of a polyol ethoxylate product containing aldehyde-phenol novolak polyglycidyl ether, a formalde from 2 to 400 mol of ethylene oxide per mole of polyol. hyde-Substituted phenol novolak polyglycidyl ether, a form 0339. In embodiments, cyclic polyol glycidyl ethers that aldehyde-catechol novolak polyglycidyl ether, a can be utilized within the epoxide composition can include, formaldehyde-substituted catechol novolak polyglycidyl singly or in any combination thereof, 1.2-cyclopentanediol ether, a formaldehyde-resorcinol novolak polyglycidyl ether, diglycidyl ether, 1.3-cyclopentanediol diglycidyl ether, 1.2- a formaldehyde-substituted resorcinol novolak polyglycidyl cyclohexanediol diglycidyl ether, 1.3-cyclohexanediol digly ether, a formaldehyde-1,4-benzenediol novolak polyglycidyl cidyl ether, 1.4-cyclohexanediol diglycidyl ether, 1.2-cyclo ether, a formaldehyde-substituted 1,4-benzene diol novolak hexanedimethanol diglycidyl ether, 1,4- polyglycidyl ether, a formaldehyde-1,2,4-benzenetriol cyclohexanedimethanol diglycidyl ether, bis(4- novolak polyglycidyl ether, a formaldehyde-bisphenol A hydroxycyclohexyl)methane diglycidyl ether, 2.2-bis(4- novolak polyglycidyl ether, a formaldehyde-bisphenol AP hydroxy-cyclo-hexyl)-propane diglycidyl ether, or any novolak polyglycidyl ether, a formaldehyde-bisphenol F combination thereof. In some embodiments, aliphatic polyol novolak polyglycidyl ether, a formaldehyde-bisphenol M glycidyl ethers that can be utilized within the epoxide com novolak polyglycidyl ether, a formaldehyde-bisphenol P position can comprise 1.2-cyclopentanediol diglycidyl ether, novolak polyglycidyl ether, a formaldehyde-bisphenol S 1.3-cyclopentanediol diglycidyl ether, or mixtures thereof; novolak polyglycidyl ether, a formaldehyde-bisphenol Z US 2009/0264669 A1 Oct. 22, 2009

novolak polyglycidyl ether, or any combination thereof. In were charged to a 500-mL round-bottomed flask equipped other embodiments, the novolak polyglycidyl ether of the with a heating mantel, thermocouple, magnetic stirrer, and polyol glycidylether product can comprise a formaldehyde dean stark trap. The reaction mixture was heated to reflux phenol novolak polyglycidyl ether, alternatively, a formalde hyde-Substituted phenol novolak polyglycidyl ether, alterna (130° C.-192°C.). Reflux was continued for 5.5 hours. After tively, formaldehyde-catechol novolak polyglycidyl ether; this time period, the conversion of polyol alcohol groups to alternatively, a formaldehyde-substituted catechol novolak 10-decenoate esters as measured by GC peak area was 20%. polyglycidyl ether, alternatively, a formaldehyde-resorcinol The solution was cooled and sodium methoxide was added to novolak polyglycidyl ether, alternatively, a formaldehyde the round-bottomed flask and the reaction mixture heated to Substituted resorcinol novolak polyglycidyl ether, alterna reflux (140°C.-165° C.) for 2 hours. After this time period the tively, a formaldehyde-1,4-benzenediol novolak polygly GC area conversion had increased to 56%. cidyl ether; alternatively, a formaldehyde-substituted 1,4- benzene diol novolak polyglycidyl ether; alternatively, a Runs 2-4 formaldehyde-1,2,4-benzenetriol novolak polyglycidyl ether; alternatively, a formaldehyde-bisphenol A novolak 0346 Methyl 10-decenoate, the polyol, and dibuyltin polyglycidyl ether; alternatively, a formaldehyde-bisphenol oxide were charged to a 500 mL round-bottomed flask AP novolak polyglycidyl ether; alternatively, a formalde equipped with a heating mantle, thermocouple, magnetic stir hyde-bisphenol F novolak polyglycidyl ether; alternatively, a formaldehyde-bisphenol M novolak polyglycidyl ether; rer, and Dean-Stark trap. The reaction mixture was heated to alternatively, a formaldehyde-bisphenol P novolak polygly reflux and maintained at reflux to allow the reaction to pro cidyl ether; alternatively, a formaldehyde-bisphenol S ceed. Table 1 provides reaction information for Experiments novolak polyglycidyl ether, or alternatively, a formaldehyde 2-4. bisphenol Z novolak polyglycidyl ether. 0347 The reaction mixture was then vacuum-distilled to 0342. The following examples are included to demon remove most of the unreacted methyl 10-undecenoate. The strate specific embodiments of the invention. Those of skill in product was the subjected to wiped film evaporation (at <2 the art should appreciate that the techniques disclosed in the mmHg and 155° C. using a ~60 mL/min feed rate) to remove examples represent techniques discovered to function well in residual methyl 10-decenoate. Table 2 provides the distilla the practice of the invention. However, in light of the present tion information for Experiments 2-4. disclosure, those of skill in the art should will appreciate the 0348 All heating stages of the reaction and product isola changes that can be made in the specific disclosed embodi tion were conducted under a nitrogen atmosphere or under ments and still obtain similar results that do not depart from the spirit and scope of the invention vacuum (with the vacuum bleed valve attached to nitrogen). EXAMPLES Runs 5-9 0343 Runs 1-11 describe the production of esters having multiple terminal double bonds using various methods. Runs 0349 The polyol, 10-decenoic acid, and the catalyst oxide 1-4 describe the production of the esters having multiple were charged to a 500 mL round-bottomed flask equipped terminal double bonds via the esterification of polyols with with a heating mantle, thermocouple, magnetic stirrer, and carboxylic acids having terminal double bonds. Runs 5-9 Dean-Stark trap. The reaction mixture was heated to refluxing describe the production of the esters having multiple terminal and maintained at reflux to allow the reaction to proceed. double bonds via the transesterification with the mono-alco Table 3 provides reaction information for Experiments 5-9. hol esters of carboxylic acids having terminal double bonds 0350. The reaction mixture was then vacuum distilled to with polyols. Runs 10-11 describes the production of the remove most of the unreacted 10-undecenoic acid. The prod esters having multiple terminal double bonds via metathesis uct was subjected to wiped film evaporation (at <2 mmHg and of esters having internal double bonds with ethylene. 155° C. using a ~60 mL/min feed rate) to remove residual 0344 Runs 12-17 describe the production of esters having 10-decenoic acid. Table 4 provides the distillation informa multiple thiol groups from the ester having multiple terminal tion for Experiments 5-9. Within Tables 1, 2, 3 and 4. GC double bonds produced in Runs 5, 6, 7, and 8. conversion provides the percentage of polyol hydroxyl groups that were converted to 10-decenoate esters as deter Methyl 1-decenoate Transesterification with Polyols mined by GC area. Run 1 0351 All heating stages of the reaction and product isola 0345 Toluene (120 mL), methyl 10-decenoate (166.15g), tion were conducted under a nitrogen atmosphere or under trimethylolpropane (34.16 g), and Sodium acetate (0.418 g) vacuum (with the vacuum bleed valve attached to nitrogen).

TABLE 1. Reaction of Polyols with Methyl 10-Undecenoate

GC Polyol Ester/Polyol Temp. Range Time Conversion Run Ester (mass) (mass) Equiv. Ratio Catalyst (mass) (° C.) (hours) (Area %) 2 Methyl 10-undecenoate Trimethylolpropane 1.02 Dibutyltin oxide 198-259 10 80.3 (204.26 g) (45.38 g) (0.131 g) 3 Methyl 10-undecenoate Trimethylolpropane 1.25 Dibutyltin oxide 18O-249 5.5 90.5 (186.69 g) (33.81 g) (0.371 g) US 2009/0264669 A1 Oct. 22, 2009 52

TABLE 1-continued Reaction of Polyols with Methyl 10-Undecenoate GC Polyol Ester/Polyol Temp. Range Time Conversion Run Ester (mass) (mass) Equiv. Ratio Catalyst (mass) (° C.) (hours) (Area %) 4 Methyl 10-undecenoate Pentaerythritol 1.25 Dibutyltin oxide 186-2S2 4 92.9 (193.56 g) (26.58 g) (0.398 g)

TABLE 2 Distillation of Product Produced from the Reaction of Reaction of Polyols with Methyl 10-Undecenoate Vacuum Distillation Wiped Film Evaporation Temp. Range Pressure. Range Time GC Conversion GC Conversion Residual Methyl Run (° C.) (mm Hg) (hours) (Area %) (Area %) 10-Undecenoate 2: 179-189 47-9 8O.O 8O.O O-3621 3 108-138 11-O 3 90.6 910 O.O79 4 107-159 15-9 1 96.3 96.4 0.144 *Wiped Film Evaporation not performed on this experiment. Product yield, purity, and residual methyl unde cenoate values are those after vacuum distillation.

TABLE 3 Reaction of Polyols with 10-Undecenoic Acid GC Acid Polyol Temp. Range Time Conversion Run Ester (mass) Polyol (mass) Equiv. Ratio Catalyst (mass) (° C.) (hours) (Area %) 5 10-undecenoic Acid Trimethylolpropane 1.25 Dibutyltin oxide 160-215 5.5 96.6 (167.25 g) (32.51 g) (0.373 g) 6 10-undecenoic Acid Glycerol 122 Dibutyltin oxide 178-240 2.5 (178.39 g) (24.3 g) (0.398 g) 7 10-undecenoic Acid Unoxol TM diol 1.21 Dibutyltin oxide 152-238 4.5 98.1 (152.47 g) (49.51 g) (0.359 g) 8 10-undecenoic Acid Pentaerythritol 1.25 Dibutyltin oxide 162-220 3.0 98.6 (191.85g) (28.32 g) (0.415 g) 9 10-undecenoic Acid Pentaerythritol 1.24 CYCAT 151-175 4.0 98.1 (191.89 g) (28.49 g) (1.84.0 g)

TABLE 4 Distillation of Product Produced from the Reaction of Polyols with 10-Undecenoic Acid. Vacuum Distillation Wiped Film Evaporation

Temp. Range Pressure. Range Time GC Conversion GC Conversion Residual Run (° C.) (mm Hg) (hours) (Area %) (Area %) Undecenoic Acid Product M,

5 161-243 6-4 3.5 99.0 98.8 O.O874 632.96 6 222-240 2-1 3.5 99.5 99.6 O.1434 590.88 7 179-238 2 2.75 98.7 98.7 O.2922 476.74 8 160-220 3 3 99.7 99.7 O.8249 8O1.2 9 175-225 9-2 4 98.2 98.0 O US 2009/0264669 A1 Oct. 22, 2009

Production of Glycerol Tris(9-Decenoate) Via uct is then Subjected to wiped film evaporation to separate the Metathesis of Soy Bean Oil glycerol tris(9-decenoate) from the by-products. The product is obtained having greater than 70 percent yield. Methanoly Run 10 sis of the product is performed on the product. The product is 0352 Soybean oil is treated with alumina to reduce the found to contain greater than 90 percent 9-decenoate resi peroxide content to less than 10 milliequivalents peroxide per dues. kg of soybean oil. The soybean oil is then degassed by bub bling nitrogen through the alumina treated soybean oil for 30 Preparation of Terminal Thiols minutes. The treated soybean oil is then stored in container under a nitrogen atmosphere until it is used. Runs 12-17 General Procedure 0353 To a clean 500 ml stainless steel autoclave equipped with a magnetic stirring apparatus, heating apparatus, and a 0358. The esters having multiple terminal thiol groups gas inlet valve is added 250 mL of the alumina treated and were prepared by charging trimethylolpropane tris(10-unde degassed soybean oil. To the magnetic stirrer impeller is cenoate) produced in Run 5, pentaerythritol tetrakis(10-un attached a seal glass tube containing 35 milligrams of tricy decenoate) produced in Run 8, UnoxolTM bis(10-unde clohexylphosphine)benzylideneruthenium chloride dis cenoate) produced in Run 7, or glycerol tris(10-undecenoate) solved in 5 ml of toluene. The autoclave is closed, evacuated, produced in Run 6 to a clean 1.5 L stainless steel (316) reactor and placed under 60 psig nitrogen pressure for 1 minute. The via a /4 inch top port. Tributyl phosphite (TBP) was then autoclave is then evacuated, and placed under 80 psig nitro added to the stainless steel reactor by Syringe through a top gen for 1 minute two additional times. The autoclave is then port (to remove residual elemental sulfur in the subsequently evacuated and pressurized to 400 psig ethylene. The ethylene charged H2S). The stainless steal reactor was sealed and the supply is then left open for the reaction. Stirring is initiated to headspace pressured and de-pressured with dry N. (3 times) break the glass tube containing the tricyclohexylphosphine) to remove oxygen. Liquid H2S, was then added to the reactor benzylideneruthenium chloride. The autoclave is heated to by pressuring the desired weight of from a pressurized cylin 30°C., and maintained for 10 hours. der of HS placed on a balance. Once the HS charge was 0354. The autoclave is allowed to cool and the contents completed, the reactor mixture was warmed using heating/ passed through and alumina column to remove the tricyclo cooling coils attached to a circulating bath and stirred at 800 hexylphosphine)benzylideneruthenium chloride. The prod rpm utilizing a turbine-type mixer. Stirring was continued for uct is then subjected to wiped film evaporation to separate the one hour to allow the TBP to react with the elemental sulfur. glycerol tris(9-decenoate) from the by-products. The product 0359 The contents of the stainless steel reactor were then is obtained having greater than 70 percent yield. Methanoly heated to 40° C. using heating/cooling coils attached to a sis of the product is performed on the product. The product is circulating bath. Once the reaction temperature was attained, found to contain greater than 90 percent 9-decenoate resi the reaction was initiated by Supplying power to a low pres dues. sure (100 Watts) mercury-vapor UV light (inside a synthetic quartz lamp well) Submerged within the reaction mixture Production of Glycerol Tris(9-Decenoate) Via inside the stainless steel reactor. The reaction was continued Metathesis of Castor Bean Oil for two hours. The UV lamp was then turned off and the excess H2S is vented to a high pressure flare system. The Run 11 headspace is swept with N at 40 SCFH (standard cubic feet 0355 Castor bean oil is treated with alumina to reduce the per hour) for ~30 minutes to remove residual HS. peroxide content to less than 10 milliequivalents peroxide per 0360 Liquid products (those produced from trimethylol kg of castor bean oil. The castor bean oil is then degassed by propane tris(10-undecenoate) and glycerol tris(10-unde bubbling nitrogen through the alumina treated castor bean oil cenoate) were drained to a clean container and the tributyl for 30 minutes. The treated castor bean oil is then stored in phosphite was removed from the product by passing the prod container under a nitrogen atmosphere until it is used. uct through a wiped film evaporator at 135° C. and <2 mmHg. 0356. To a clean 500 ml stainless steel autoclave equipped 0361 Partially solid products (those produced from pen with a magnetic stirring apparatus, heating apparatus, and a taerythritol tetrakis(10-undecenoate) and UnoxolTM bis(10 gas inlet valve is added 250 mL of the alumina treated and undecenoate)), were removed from the stainless steel reactor degassed castor bean oil. To the magnetic stirrer impeller is by charging the reactor with 1.1 L of tetrahydrofuran and attached a seal glass tube containing 35 milligrams of 1,3- stirring to dissolve the product. The reactor contents were bis-(2,4,6-trimethylphenyl)-2-(imidazolidinylidene)(phe then discharged into a 1 L round bottomed flask. The tetrahy nylmethylene)dichloro(tricyclohexyl phosphine) ruthenium drofuran was removed from the product by rotary evaporation dissolved in 5 ml of toluene. The autoclave is closed, evacu (at 110 mmHg and 44° C.). The tributyl phosphite was then ated, and placed under 60 psig nitrogen pressure for 1 minute. removed from the product by passing the product through a The autoclave is then evacuated, and placed under 80 psig wiped film evaporator at 135° C. and <2 mmHg. nitrogen for 1 minute two additional times. The autoclave is 0362. The final products were characterized by metha then evacuated and pressurized to 400 psig ethylene. The nolysis/GC (to determine conversion of the double bonds), ethylene supply is then left open for the reaction. Stirring is FTIR (to observe the consumption of the olefinic peak), initiated to break the glass tube containing the tricyclohexy iodine titration (to determine the '% mercaptain sulfur value), lphosphine)benzylideneruthenium chloride. The autoclave is and "Hand 'C NMR analysis. heated to 30°C., and maintained for 10 hours. 0363 Table 5 provides the information regarding the 0357 The autoclave is allowed to cool and the contents charges to the stainless steel reactor for Runs 12-17. Table 6 passed through and alumina column to remove the tricyclo provides the results of the analytical tests performed on the hexylphosphine)benzylideneruthenium chloride. The prod products produced in Runs 12-17. US 2009/0264669 A1 Oct. 22, 2009 54

TABLE 5 Reaction of Unsaturated Esters having Multiple Carbon-Carbon Double Bonds with Hydrogen Sulfide. Tributyl-phosphite HS mass Olefin/HS Reaction Reaction Pressure Run Olefin of Run (mass in g) mass (g) (g) Molar Ratio Temperature (C.) (psig) 12 trimethylolpropane tris(10-undecenoate) 1.2 660 OO.7 34.3-35.9 420-434 of Run 5 (41.00) 13 pentaerythritol tetrakis(10-undecenoate) 1.4 760 O1.0 32.9-35.7 457-458 of Run 8, (44.35) 14 UnoxolTM bis(10-undecenoate) 1.4 760 O3.3 31.5-33.6 430-454 of Run 7 (52.10) 15 glycerol tris(10-undecenoate) 1.4 760 O2.3 32.3-32.9 433-446 of Run 6 (43.09) 16 UnoxolTM bis(10-undecenoate) 2.2 760 O16 37.O-374 426-433 of Run 7 (53.0)) 17 pentaerythritol tetrakis(10-undecenoate) 2.2 760 OO6 37.3 037.7 432-442 of Run 8 (44.50)

0367 The polythiourethanes were produced using a cata TABLE 6 lyst solution containing dibutyl tin dilaurate (DBTDL) and Addocat(R) PP in dried butyl acetate. The catalyst solution Yield and Properties of Thiol Esters Having Terminal Thiol Groups. utilized was never more than three days old. Generally, the Mercaptain Equivalent catalyst solution was prepared by weighing into a oven-dried Run Product Weight Conversion: Purity Sulfur Weight bottle placed on a 3-place balance, DBTDL, Addocat PP and 12 43.OO 98.7 95.79 11.55 250.5 the catalyst solvent (butyl acetate). The bottle was then 13 35.53 88.44 100 12.05 265.6 purged with nitrogen, capped with a rubber septum, and 14 47.70 65.1 94.1 423.4 Swirled to dissolve the catalyst. In one instance the catalyst 15 36.46 87.22 90.5 10.34 265.8 solution was prepared using 0.5833 grams DBTDL, 1.1667 16 47.22 97.87 90.1 10.60 281.6 grams Addocat PP catalyst, and 33.25 g of anhydrous butyl 17 39.35 99.2 90.8 12.42 236.8 acetate. Based upon Methanolysis. This value represent the percentage of unde cenoate units converted to thioundecanoate units. Runs 18-21—Polythiourethane Formulation Preparation— Based upon Methanolysis of product. General Procedure Calculated from the molecular weight of the starting terminal olefinic ester and the conversion 0368. An Erlenmeyer flask was placed on a 3- or 4-place balance. The polyhydric material was weighed into the flask Polythiourethane Production followed by the solvent, butyl acetate. The headspace of the 0364 Polythiourethanes were produced using pentaeryth flask was purged with nitrogen, sealed with a rubber septum, ritol tetrakis(11-mercapto undecanoate) (TMU) as the poly and swirled until complete dissolution had occurred. The hydric material and hexamethylene diisocyanate trimer (Ba flask was periodically opened to relieve built-up pressure. sonatr HI29OB). This polythiourethane was compared to the Once dissolution had occurred, the catalyst was added to the polythiourethanes produced from mercaptanized epoxidized flask using a pipette. The solution was then Swirled to mix the soybean oil (MHSO) produced according to the methods Solution. The flask was then purged with nitrogen and sealed disclosed in U.S. patent application Ser. No. 1 1/060.675 filed with a rubber septum. Table 7 provides the formulation data on Feb. 17, 2005, which is entitled “Thiol Ester Compositions for the polythiourethane formulations. and Processes for Making and Using Same and Basonatr HI 290B, mercaptanized castor oil (MCO) produced according Runs 18-21—Polythiourethane Coating Formation and Test to the methods disclosed in U.S. patent application Ser. No. ing General Procedure 11/060,675 filed on Feb. 17, 2005, which is entitled “Thiol 0369. Once the polythiourethane formulation solution Ester Compositions and Processes for Making and Using was well mixed, test panels were prepared by pipetting ali Same' and Basonat(R) HI 290B, and castor oil and BasonatR) quots of the formulation mixture onto a test panels and draw HI 29OB. ing down the formulation with a 5 mill WFT drawdown bar. 0365. The polyhydric materials pentaerythritol tetrakis(1'- Once drawn down the test panels were placed in a vented mercapto undecanoate), mercaptanized epoxidized soybean drying cabinet. oil, mercaptanized castor oil, and castor oil, along with the 0370 A Byk dry time panel was prepared on a glass panel polyisocyanate (Basonatr HI 290B hexamethylene diiso and the Byk dry time recorder started immediately after the cyanate trimer) and solvent (butyl acetate) were dried using formulation solution was drawn down. The Byk dry time was standard procedures to a moisture level of less than 500 ppm. determined by ASTM Method D 5895-03, “Standard Test Methods for Evaluating Drying or Curing During Film For Runs 18-21—General Preparations mation of Organic Coatings Using Mechanical Recorders.” 0366 Glassware and syringes utilized to prepare the poly Test Method A Straight Line Drying Time. thiourethanes were pre-dried in an oven at >110° C. for at 0371. Additional test panels were prepared by pipetting least 2 hours and then allowed to cool under a dry nitrogen aliquots of the formulation mixture onto a test panels and purge just before use. drawing down the formulation with a 5 mill WFT drawdown US 2009/0264669 A1 Oct. 22, 2009

bar. These test panels were allowed to cure at ambient tem Runs 22-27 General Preparations perature for ten minutes and then placed in a 130° C. oven for 0375 Glassware utilized to prepare the thiol-ene coatings 3 hours. The test panels were then allowed to cool overnight were pre-dried in an oven at > 110°C. for at least 2 hours and before testing. then allowed to cool under a dry nitrogen purge just before 0372 MEK resistance was tested by wetting a small area use. The Bonderite 1000-treated CRS test panels were used as on the coated test panel with methyl ethyl ketone. A cotton received. swab was rubbed, back and forth, across the methyl ethyl 0376. A nitrogen atmosphere was maintained over the ketone wetted area of the coating by holding the Swab tip materials place into the sample preparation bottle by purging firmly but lightly against the coating. Each back and forth the headspace of the bottle with nitrogen after the addition of stroke is called a double rub. The number of strokes was each component. counted until resistance was felt during the rub (due to solvent Runs 22-27. Thiol Ene Formulation Preparation—General softening or removal of the coating), or until 50 double rubs Procedure was reached (whichever comes first). The rubbing was then 0377. A bottle was place on a 3-place or 4-place balance. stopped and the methyl ethyl ketone removed from the coated Into the bottle was weighed the polymercaptain and the pho test panel by gently rubbing with a Kimwipe R. The test area toinitiator. The photoinitiator was charged using a lab area was then visually inspected to determine if any visible equipped with red light, to avoid exposing the photoinitiators changes (physical damage, whitening, and/or softening) had to harmful ambient lighting conditions before passing occurred to the coating and noted. If the coating was damaged through the UV cure line. After the photoinitiator was added in under 50 strokes, another fresh test was prepared using into the bottle, the solution was swirled or stirred using a fewer strokes to get a more accurate number of strokes the Small magnetic stir bar to mix the components. Into the solu coating could withstand before Sustaining visible damage. If tion, was weighed the polyene, 1,3,5-triallyl-1,3,5-triazine no visible changes were observed the procedure was repeated 2.4.6(1H.3H,5H)-trione. The solution was then swirled to for an additional 50 double rubs or until the coating appeared create a single phase solution and the headspace of the bottle to be affected. The procedure was repeated until the coating was then purged with nitrogen. The bottle was then stored in was affected or 200 double rubs (in total). The highest number a dark place when not used to prepare the coating panels. of double rubs the coating is able to withstand before suffer Runs 22-27. Thiol Ene Coated Test Panel Preparation and ing visible damage is reported Testing General Procedure 0373 Table 7 provides the polythiourethane coating test 0378 Coating test panels were prepared by pipetting ali data. quots of the formulation mixture onto a test panels and draw

TABLE 7 Polythiourethane Formulation and Coating Test Data Polythiourethane Formulation Data Thiol, grams TMU, 25.46 MHSO, 32.05 MCO, 24.86 Basonat (R) HI 29OB, grams 29.62 4.1.8 36.46 Butyl Acetate 9.78 65.82 20.72 Dibutyltin Diluarate, mL O.O16 O.O16 O.O16 Addocat PP (20% solution in Butyl Acetate), mL O140 O.200 O. 160 Polythiourethane Coating Test data

Cure Temperature, C. 150 150 150 Cure Time, minutes 18O 18O 18O Set to Touch, minutes 6 5 90 Tack-Free Time, minutes 10 15 175 Dry-Through Time, minutes 65 >18O >18O MEK Resistance, if Double Rubs >2OO >2OO >2OO Peroz Hardness, post cure Swings 264 311 227 Peroz Harness, 24 hours, Swings 286 314 3O4 20 degree gloss, 96 92.6 86.9 86.4 60 degree gloss, 96 99.7 98.7 99.1 85 degree gloss, % 97.7 97.1 97.7 Forward Impact, inch-lb >188 >188 >188 Reverse Impact, in-lb >188 100 >188 Crosshatch Rating 5 5 Pencil Hardness Rating SH F Nandrel Bend, Inches

Thiol Ene Coating Formulations ing down the formulation with a 2 mill WFT drawdown bar. 0374. A thiol-ene coating formulation was produced using The cure speed was then tested by passing the test panel the trimethylolpropane tris(11-mercapto undecanoate) of through a Fusion UV Cure line at ambient temperature. Run 12 and compared to thiol-ene coating formulation pro 0379 A test panel was passed through the Fusion UV cure duced without trimethylolpropane tris(11-mercapto unde line ten times at a line speed of 53 feet per minute and the canoate). The coating formulations were coated on Bonder MEK resistance was tested. The UV radiation incident on the ite-treated CRS test panels and evaluated for their chemical test panels, per pass, was determined by passing a portable resistance. UV measuring device through the Fusion UV cure line at a 53 US 2009/0264669 A1 Oct. 22, 2009 56 fpm cure line speed. The measured incident radiation perpass Epoxy Resin Production was approximately 154 m/cm (average of three indepen dent values. 0384 An epoxy resin was produced using pentaerythritol 0380. The initial cure of the coatings was measured by tetrakis(11-mercapto undecanoate) of Run 17 and D.E.RTM development of resistance to MEK using the following pro 331 TM Liquid Epoxy Resin (an epoxy resin reaction product cedure. formed from epichlorohydrin and Bisphenol A). 0381. A small area on the coated test panel was wetted Runs 28 Epoxy Resin Preparation and Testing with methyl ethyl ketone. A cotton swab was rubbed, back and forth, across the methyl ethyl ketone wetted area of the 0385. The pentaerythritol tetrakis(11-mercapto unde coating by holding the Swab tip firmly but lightly against the canoate) of Run 17 was liquefied by warming the bottle with coating. Each back and forth stroke is called a double rub. The hot tap water. The pentaerythritol tetrakis(11-mercapto unde number of strokes was counted until resistance was felt dur canoate), 30.04 grams was transferred to a plastic cup. To the ing the rub (due to solvent softening or removal of the coat plastic cup was added Versamine(R, EH 30 0.844 grams. The ing), or until 50 double rubs was reached (whichever comes pentaerythritol tetrakis(11-mercapto undecanoate) and Ver first). The rubbing was then stopped and the methyl ethyl samine(REH 30 were then mixed together using a flatwooded ketone removed from the coated test panel by gently rubbing stick. To the plastic cup was added D.E.RTM 331TM Liquid with a Kimwipe(R). The test area was then visually inspected Epoxy Resin, 28.47 grams. The contents of the cup were then to determine if any visible changes (physical damage, whit mixed using a flat wooden Stick for 3 minutes. ening, and/or softening) had occurred to the coating and 0386 A portion of the cup contents were poured into a noted. If the coating was damaged in under 50 strokes, Teflon-lined tensile bar mold. The mold was then placed in an another fresh test was prepared using fewer strokes to get a oven set at 120° C. for three hours, removed from the oven, more accurate number of strokes the coating could withstand allowed to cool, and the cured epoxy resin bar remove from before Sustaining visible damage. If no visible changes were the mold. The epoxy resin bar was then tested for Shore observed the procedure was repeated for an additional 50 Hardness according to ASTM Method D2240-05 “Standard double rubs or until the coating appeared to be affected. The Test Method for Rubber Property Durometer Hardness.” procedure was repeated until the coating was affected or 200 The epoxy resin had a Shore A Hardness of 58. Dynamic double rubs (in total). The highest number of double rubs the Scanning Calorimetry over a range of -60 to 120° C. with a coating is able to withstand before Suffering visible damage is ramp rate of 10°C/min showed a well-defined glass transi reported. tion temperature at 8.70° C. (inflection point). 0382 Table 8 provides the formulation data and test data 0387 To the remainder of the cup mixture was added for the thiol-ene coating compositions. additional Versamine R. EH 30, 0.291 grams. The gel time at

TABLE 8 Preparation and testing of Thiol-Ene Coating Test Panels

Materials 22 23 24 25 26 27 Trimethylolpropane 9.00 9.OO 18.01 7.28 tris(2-mercaptoacetate), grams Mercaptainized Soybean Oil 18.00 18.00 9.00 9.OO (grams) Trimethylolpropane 8.84 tris(11-mercaptOundecanoate) (grams) 1,3,5-triallyl-1,3,5-triazine- 4.49 4.49 8.24 8.24 1266 7.89 2,4,6(1H,3H,5H)-trione (grams) Darocur 1173 (grams) O.3369 0.3957 O46SO O.3364 Darocur 4265 (grams) O.6840 O.7983 O.1519 Calc’d Initiator level (wt %) 1.5% 3.0% 1.5% 3.0% 1.5% 2.0% Surface Feel (after 10 passes at tacky tacky sl tacky sl tacky cured cured 54 fpm) MEK double Rubs 16 18 30 40 >2OO 2OO Curing was performed at 22-25° C. and at ambient relative humidity.

0383. This example shows that the trimethylolpropane tris ambient temperature (approx. 24°C.) was then determined (11-mercaptoundecanoate) of the invention provides a more using a Bykgel timer, which automatically records the time at a point where free rotation of a sample clip in the gelling effective cure than Mercaptanized Soybean Oil in a blend mixture stops due to the mixture becoming no longer liquid. with trimethylolpropane tris(mercaptoacetate), even when The epoxy resin had an ambient temperature gel time of the new trimethylolpropane tris(11-mercaptoundecanoate) is approximately 5 hours and the cured cup sample was trans more than half by weight of the resin blend (i.e. with the parent and homogeneous inappearance with a tough, rubbery acetate). The blend is required for miscibility purposes since character. phase separation prevented cure in the case of the pure trim What is claimed is: ethylolpropane tris(11-mercaptoundecanoate). The ratios 1. A thiol ester composition comprising thiol ester mol were calculated to provide a 1.0 to 1.05 ratio of the mercaptain ecules, the thiol ester molecules having ester linkages com over the triester (ene) reactant on an equivalent basis. prising: US 2009/0264669 A1 Oct. 22, 2009 57

a) a residue of a polyol; and 16. The thiol ester composition of claim 11, wherein the b) carboxylic acid residues having; carboxylic acid residues having the thiol group located on the i) at least 4 carbon atoms; and terminal carbon atom or the carbon atom adjacent to the ii) a thiol group located on a terminal carbon atom or a terminal carbon atom have only 10 carbon atoms. carbon atom adjacent to the terminal carbon atom; 17. The thiol ester composition of claim 11, wherein the and thiolester molecules have an average thiol sulfur content of 9 wherein the average ratio of carboxylic acid residues hav to 16 weight percent. ing a thiol group located on a terminal carbon atom or a 18. The thiol ester composition of claim 11, wherein the carbon atom adjacent to the terminal carbon atom to polyol of the residue of polyol was cyclohexane diol, trim hydroxyl groups of the polyol of the residue of the polyol ethylol propane, glycerol, pentaerythritol, or combinations is greater than 0.70:1. thereof, the carboxylic acid residues having a terminal C-hy 2. The thiol ester composition of claim 1, wherein the droxy thiol group have from 10 to 11 carbon atoms, and the carboxylic acid residues are substantially devoid of hydroxyl thiolester molecules have an average thiol sulfur content of 9 groups. to 16 weight%. 3. The thiol ester composition of claim 2, wherein the 19. A method of producing the composition of claim 2, the polyol of the residue of polyol was a diol, triol, or a tetraol. method comprising: 4. The thiol ester composition of claim 2, wherein the a) contacting ethylene and natural Source oil with a met polyol of the residue of polyol was cyclohexane diol, trim athesis catalyst composition; ethylol propane, glycerol, pentaerythritol, or combinations b) forming unsaturated ester molecules having terminal thereof. carbon-carbon double bonds at metathesis conditions 5. The thiol ester composition of claim 2, wherein the capable of forming the unsaturated ester molecules hav polyol of the residue of the polyol was glycerol. ing terminal carbon-carbon double bonds; 6. The thiol ester composition of claim 2, wherein the c) contacting the unsaturated ester molecules having ter carboxylic acid residues having a thiol group located on a minal carbon-carbon double bonds and hydrogen Sul terminal carbon atom or a carbon atom adjacent to the termi fide; and nal carbon atom have from 10 to 11 carbon atoms. d) forming the thiol ester composition comprising thiol 7. The thiol ester composition of claim 2, wherein the ester molecules having the thiol group located on the carboxylic acid residues having the thiol group located on the terminal carbon atom at conditions capable of forming terminal carbon atom or the carbon atom adjacent to the thiol ester molecules having the thiol group located on terminal carbon atom have only 10 carbon atoms. the terminal carbon. 8. The thiolester composition of claim 2, wherein the thiol 20. The method of claim 19, wherein the metathesis cata ester molecules have an average thiol sulfur content of 9 to 16 lyst composition comprises ruthenium carbene metathesis weight%. catalyst or a molybdenum carbene metathesis catalyst. 9. The thiolester composition of claim 2, wherein an aver 21. The method of claim 19, wherein the metathesis cata age ratio of thiol groups located on a terminal carbon atom to lyst comprises dichloro(phenylmethylene)bis(tricyclohexy thiol groups located on the carbon atom adjacent to the ter lphosphine)ruthenium or 1,3-bis-(2,4,6-trimethylphenyl)-2- minal carbon atom is greater than 5:1. (imidazolidinylidene)(phenylmethylene)dichloro 10. The thiol ester composition of claim 2, wherein the (tricyclohexylphosphine)ruthenium. polyol of the residue of the polyol was cyclohexane diol, trimethylol propane, glycerol, pentaerythritol, or combina 22. The method of claim 19, wherein the metathesis con tions thereof, the carboxylic acid residues having a thiol ditions include a ethylene partial pressure ranging from 50 to group located on a terminal carbon atom or a carbon atom 3000 psig and a temperature ranging from 5°C. to 100° C. adjacent to the terminal carbon atom have from 10 to 111 23. The method of claim 19, wherein the natural source oil carbon atoms, an average ratio of thiol groups located on a comprises a tallow oil, an olive oil, a peanut oil, a castor bean terminal carbon atom to thiol groups located on the carbon oil, a Sunflower oil, a sesame oil, a poppy seed oil, a palm oil, atom adjacent to the terminal carbon atom is greater than 5:1, an almond seed oil, a hazelnut oil, a rapeseed oil, a canola oil, and wherein the thiol ester molecules have an average thiol a Soybean oil, a corn oil, a safflower oil, a cottonseed oil, a sulfur content of 9 to 16 weight%. camelina oil, a flaxseed oil, or a walnut oil, or any combina 11. The thiol ester composition of claim 1, wherein the tion thereof. carboxylic acid residue having the thiol group located on the 24. The method of claim 19, wherein the natural source oil terminal carbon atom or the carbon atom adjacent to the is soybean oil, corn oil, canola oil, or castor bean oil. terminal carbon atom is a carboxylic acid residue having a 25. The method of claim 19, wherein the natural source oil terminal C-hydroxy thiol group. is soybean oil. 12. The thiol ester composition of claim 11, wherein the 26. A method of producing the thiol ester composition of polyol of the residue of polyol was a diol, triol, or a tetraol. claim 11, the method comprising: 13. The thiol ester composition of claim 11, wherein the a) contacting ethylene and natural Source oil with a met polyol of the residue of polyol was cyclohexane diol, trim athesis catalyst composition; ethylol propane, glycerol, pentaerythritol, or combinations b) forming unsaturated esters molecules having terminal thereof. carbon-carbon double bonds at metathesis conditions 14. The thiol ester composition of claim 11, wherein the capable of forming the unsaturated ester molecules hav polyol of the residue of the polyol was glycerol. ing terminal carbon-carbon double bonds; 15. The thiol ester composition of claim 11, wherein the c) contacting the unsaturated ester molecules having ter having a terminal C-hydroxy thiol group have from 10 to 11 minal carbon-carbon double bonds and an oxygen con carbon atoms. taining compound; US 2009/0264669 A1 Oct. 22, 2009

d) forming epoxide ester molecules having terminal lphosphine)ruthenium or 1,3-bis-(2,4,6-trimethylphenyl)-2- epoxide groups at conditions capable of forming (imidazolidinylidene)(phenylmethylene)dichloro epoxide ester molecules having terminal epoxide (tricyclohexylphosphine)ruthenium. groups: 29. The method of claim 26, wherein the metathesis con e) contacting the epoxide ester composition and hydrogen ditions include a ethylene partial pressure ranging from 50 to sulfide; and 3000 psig and a temperature ranging from 5°C. to 100° C. f) forming the thiol ester composition comprising thiol 30. The method of claim 26, wherein the natural source oil ester molecules at conditions capable of forming thiol comprises a tallow oil, an olive oil, a peanut oil, a castor bean ester molecules, the thiol ester molecules having ester oil, a Sunflower oil, a sesame oil, a poppy seed oil, a palm oil, linkages comprising: an almond seed oil, a hazelnut oil, a rapeseed oil, a canola oil, a Soybean oil, a corn oil, a safflower oil, a cottonseed oil, a i) a residue of a polyol; and camelina oil, a flaxseed oil, or a walnut oil, or any combina ii) carboxylic acid residues having a terminal C-hydroxy tion thereof. thiol group. 31. The method of claim 26, wherein the natural source oil 27. The method of claim 26, wherein the metathesis cata is soybean oil, corn oil, canola oil, or castor bean oil. lyst composition comprises ruthenium carbene metathesis 32. The method of claim 26, wherein the natural source oil catalyst or a molybdenum carbene metathesis catalyst. is soybean oil. 28. The method of claim 26, wherein the metathesis cata lyst comprises dichloro(phenylmethylene)bis(tricyclohexy