US 2009001 8300A1 (19) United States (12) Patent Application Publication (10) Pub. No.: US 2009/0018300 A1 Bloom et al. (43) Pub. Date: Jan. 15, 2009

(54) MONOMERS AND POLYMERS FROM Related U.S. Application Data BODERVED CARBON (60) Provisional application No. 60/949,091, filed on Jul. (75) Inventors: Paul D. Bloom, Decatur, IL (US); 11, 2007. Padmesh Venkitasubramanian, Publication Classification Decatur, IL (US) (51) Int. Cl. Correspondence Address: COSH 5/00 (2006.01) K&L GATES LLP (52) U.S. Cl...... 52.7/102 HENRY W. OLVER BUILDING 535 SMITHFIELD STREET (57) ABSTRACT PITTSBURGH, PA 15222 (US) The present disclosure provides compositions including bio based monomers derived from biological sources for the Syn (73) Assignee: Archer-Daniels-Midland thesis of polymers from bioderived carbon. The monomers Company, Decatur, IL (US) and resulting polymers are comparable to petroleum derived monomers and polymers, but have a carbon isotope ratio (21) Appl. No.: 12/169,248 characteristic of bioderived materials. Methods for synthesiz ing polymers having 100% biobased materials are also dis (22) Filed: Jul. 8, 2008 closed.

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MONOMERS AND POLYMERS FROM 0007 FRISA has established certification requirements BODERVED CARBON for determining biobased content. These methods require the measurement of variations in isotopic abundance between CROSS REFERENCE TO RELATED biobased products and petroleum derived products, for APPLICATIONS example, by liquid Scintillation counting, accelerator mass 0001. The application claims the priority benefit of U.S. spectrometry, or high precision isotope ratio mass spectrom Provisional Patent Application 60/949,091, filed Jul. 11, etry. Isotopic ratios of the isotopes of carbon, such as the 2007, the disclosure of the entirety of which is incorporated 'C/°C carbon isotopic ratio or the ''C/°C carbon isotopic by this reference. ratio, can be determined using isotope ratio mass spectrom etry with a high degree of precision. Studies have shown that TECHNICAL FIELD isotopic fractionation due to physiological processes, such as, 0002 The present disclosure provides compositions com for example, CO transport within plants during photosynthe prising biobased monomers derived from biological sources sis, leads to specific isotopic ratios characteristic of natural or for the synthesis of polymers from bioderived carbon. The bioderived compounds. Petroleum and petroleum derived monomers and resulting polymers may be comparable to products have a different carbon isotopic ratio than bio petroleum derived monomers and polymers, but have a car derived products, for example, due to different chemical pro bon isotope ratio characteristic of bioderived materials. cesses and isotopic fractionation during the generation of Methods for synthesizing polymers having up to 100% bio petroleum. In addition, radioactive decay of the unstable ''C based materials are also disclosed. carbon radioisotope leads to different isotope ratios in bio based products compared to petroleum products. Biobased BACKGROUND content of a product may be verified by ASTM International 0003 Acrylate esters may be produced commercially Radioisotope Standard Method D6866. ASTM International from petrochemical sources. For example, in industry, acrylic Radioisotope Standard Method D6866 determines biobased acid is typically synthesized from acrolein through the cata content of a material based on the amount of biobased carbon lytic oxidation of the petroleum derived propylene. Alterna in the material or product as a percent of the weight (mass) of tively, acrylic acid may be industrially synthesized from pet the total organic carbon in the material or product. Both rochemically derived ethylene, carbon monoxide, and water. bioderived and biobased products will have carbon isotope These processes are industrially feasible due to the relatively ratios characteristic of a biologically derived composition, low price of the propylene and ethylene feedstock. Both pro whereas petroleum derived products will have carbon isotope pylene and ethylene are industrial by-products of gasoline ratios characteristic of compositions derived from petro manufacturing, for example, as by-products of fluid cracking chemical sources. of gas oils or steam cracking of hydrocarbons. 0008. The olefin metathesis reaction has become a power 0004. The world's supply of petroleum is being depleted at ful weapon for the coupling of carbon-carbon double bonds. an increasing rate. Eventually, demand for petrochemical Drs. Grubbs, Schrock, and Chauvin shared the 2005 Nobel derived products may outstrip the Supply of available petro Prize in Chemistry for the development of the olefin metathe leum. When this occurs, the market price of petroleum and, consequently, petroleum derived products will likely sis reaction. The generally accepted mechanism for the olefin increase, making products derived from petroleum more metathesis reaction involves a metal carbene acting as a cata expensive and less desirable. As the available supply of petro lyst to metathesize two alkenes into a new alkene through a leum decreases, alternative sources and, in particular, renew metallocyclobutane intermediate. The newly synthesized alk able sources of comparable products will necessarily have to ene contains one methylene carbon from each of the two be developed. starting alkenes. Olefin metathesis catalysts developed by 0005. In an effort to diminish dependence on petroleum Schrock, Grubbs, and others are commercially available, products the United States government enacted the Farm making the olefin metathesis reaction a viable and useful Security and Rural Investment Act of 2002, section 9002 (7 strategy in organic chemistry. Examples of commercially U.S.C. S8102), hereinafter “FRISA', which requires federal available olefin metathesis catalysts include the “Schrock agencies to purchase biobased products for all items costing catalyst” (i.e., |Mo(=CHMe, Ph)(=N-Ar)(OCMe(CF).) over S10,000. In response, the United States Department of , the “1st generation Grubb’s catalyst” (i.e., Ru(=CHPh) Agriculture (“USDA) has developed Guidelines for Desig Cl(PCy), and the "2nd generation Grubb's catalyst” (i.e. nating Biobased Products for Federal Procurement (7 C.F.R. Ru(=CHPh)ClPCys(N,N'-diaryl-2-imidazolidinyl) S2902) to implement FRISA, including the labeling of bio (Me-methyl, Ph phenyl, Ar-aryl, and Cy-cyclohexyl). based products with a “U.S.D.A. Certified Biobased Product” 0009 Olefins, for example, acrylate esters, may be used label. for the synthesis of polymers, for example, by free radical 0006. As used herein, the term “bioderived' means chain polymerization or by ring-opening metathesis polymer derived from or synthesized by a renewable biological feed ization (“ROMP) of cyclic olefins with diacrylates. For stock, Such as, for example, an agricultural, forestry, plant, example, ring-opening metathesis polymerization of cyclic bacterial, or animal feedstock. As used herein, the term “bio olefins with diacrylates for the synthesis of A.B-alternating based means a product that is composed, in whole or in co-polymers are generally described in U.S. Patent Applica significant part, of biological products or renewable agricul tion Publication Nos. 2003/02363.67 and 2003/0236377; and tural materials (including plant, animal and marine materials) Choi et al., in Angewandte Chemie, International Edition, or forestry materials. As used herein, the term “petroleum 2002, 41, 3839-3841, the disclosures of which are incorpo derived means a product derived from or synthesized from rated by reference herein in their entirety. However in these petroleum or a petrochemical feedstock. references, since the diacrylate and cyclic olefin co-mono US 2009/001 8300 A1 Jan. 15, 2009 mers are derived from petrochemical sources, the resulting monomer unit via a Baylis-Hillman type reaction to form a polymers will have the isotopic ratios of petroleum derived polymer are also disclosed, wherein the monomer unit com products. prises an electrophilic reactive group and a nucleophilic reac 0010 Biology offers an attractive alternative for industrial tive group. Suitable electrophilic groups may be selected manufacturers looking to reduce or replace their reliance on from the group consisting of an aldehyde, an aldimine, an petrochemicals and petroleum derived products. The replace C.f3-unsaturated carbonyl, and an O.f3-unsaturated nitrile and ment of petrochemicals and petroleum derived products or the nucleophilic reactive group is selected from the group building blocks with products and/or feedstocks derived from consisting of an O.f3-unsaturated ester, C.B-unsaturated biological Sources (i.e., bioderived products) may offer many amide, C. B-unsaturated aldehyde, an O.f3-unsaturated ketone, advantages. For example, products and feedstocks from bio an C.f3-unsaturated Sulfone, an O.B-unsaturated Sulfonate, logical Sources are typically a renewable resource. As the C.f3-unsaturated nitrile, and an O.f3-unsaturated phosphate. Supply of easily extracted petrochemicals continue to be 0017 Still other embodiments include AB alternating depleted, the economics of petrochemical production will condensation polymer compositions comprising a first mono likely force the cost of the petrochemicals and petroleum mer unit and a second monomer unit, wherein the first mono derived products to higher prices. In addition, companies may mer unit reacts with the second monomer unit via a Baylis benefit from the marketing advantages associated with bio Hillman type reaction to form a polymer. Methods of forming derived products from renewable resources in the view of a an AB alternating condensation polymer composition com public becoming more concerned with the Supply of petro prising polymerizing a first monomer unit and a second chemicals. monomer unit via a Baylis-Hillman type reaction to form the AB alternating condensation polymer are also disclosed. The SUMMARY first monomer unit comprises a first electrophilic reactive 0011 Certain embodiments of the present disclosure group and a second electrophilic reactive group, wherein the relate to polymer and monomer compositions that are 100% first electrophilic reactive group and the second electrophilic biobased as determined by ASTM International Radioisotope reactive group are each independently selected from the Method D 6866. Other embodiments relate to methods for group consisting of an aldehyde, an aldimine, an O.B-unsat producing polymers that are 100% biobased as determined by urated carbonyl, and an O.f3-unsaturated nitrile. The second ASTM International Radioisotope Method D 6866. monomer unit comprises a first nucleophilic reactive group 0012. An embodiment includes a polymer composition and a second nucleophilic reactive group, wherein the first that is 100% biobased as determined by ASTM International nucleophilic reactive group and the second nucleophilic reac Radioisotope Method D 6866. The polymer comprises a tive group are each independently selected from the group product from a metathesis polymerization reaction of a bio consisting of an O.B-unsaturated ester, an O.B-unsaturated derived olefin and an acrylate ester of a bioderived alcohol. amide, an O.f3-unsaturated aldehyde, an O.B-unsaturated The acrylate ester is produced by reacting the bioderived ketone, an O.f3-unsaturated Sulfone, an O.B-unsaturated Sul alcohol with at least one equivalent of acrylic acid produced fonate, an O.B-unsaturated nitrile, and an O.B-unsaturated from bioderived glycerol. phosphate. 0013. Other embodiments include a polymer composition 0018. In another embodiment, a method of forming a poly that is 100% biobased as determined by ASTM International mer is presented, the method comprising polymerizing a Radioisotope Method D 6866. The polymer comprises a monomer unit via a Baylis-Hillman type reaction to form a product of an acyclic diene metathesis polymerization reac polymer, wherein the monomer unit comprises an electro tion of a bioderived acyclic diene. The bioderived acyclic philic reactive group and a nucleophilic reactive group, diene is made from a bioderived fatty acid. wherein the electrophilic reactive group is selected from the 0014 Still other embodiments include a monomer com group consisting of an aldehyde, an aldimine, an O.B-unsat position for a polymerization reaction. The monomer com urated carbonyl, and an O.f3-unsaturated nitrile and the prises a diacrylate ester that is 100% biobased as determined nucleophilic reactive group is selected from the group con by ASTM International Radioisotope Method D 6866. The sisting of an O.f3-unsaturated ester, an O.B-unsaturated amide, diacrylate ester is produced by reacting a bioderived diol with an O.B-unsaturated aldehyde, an O.B-unsaturated ketone, an at least two equivalents of acrylic acid produced from bio C.f3-unsaturated Sulfone, an O.f3-unsaturated Sulfonate, an derived glycerol. C.f3-unsaturated nitrile, and an O.f3-unsaturated phosphate. 0015. Further embodiments include methods for produc 0019. In another embodiment, a method of forming an AB ing a bioderived polymer that is 100% biobased as deter alternating condensation polymer is presented, the method mined by ASTM International Radioisotope Method D6866. comprising polymerizing a first monomer unit and a second The method comprises reacting one of a bioderived diol, a monomer unit via a Baylis-Hillman type reaction to form an bioderived amino alcohol, and a bioderived diamine with at AB alternating condensation polymer, wherein the first least two equivalents of acrylic acid to yield a diacryl mono monomer unit comprises a first electrophilic reactive group mer product and reacting the diacryl monomer product with a and a second electrophilic reactive group, wherein the first bioderived olefin in a metathesis polymerization reaction to electrophilic reactive group and the second electrophilic reac form the bioderived polymer. The acrylic acid is produced tive group are each independently selected from the group from bioderived glycerol. consisting of an aldehyde, an aldimine, an O.B-unsaturated 0016 Other embodiments include polymer compositions carbonyl, and an O.B-unsaturated nitrile; and the second comprising a monomer unit having an electrophilic reactive monomer unit comprises a first nucleophilic reactive group group and a nucleophilic reactive group, wherein the nucleo and a second nucleophilic reactive group, wherein the first philic reactive group reacts with the electrophilic reactive nucleophilic reactive group and the second nucleophilic reac group via a Baylis-Hillman type reaction to form a polymer. tive group are each independently selected from the group Methods of forming a polymer comprising polymerizing a consisting of an O.B-unsaturated ester, an O.B-unsaturated US 2009/001 8300 A1 Jan. 15, 2009

amide, an O.f3-unsaturated aldehyde, an O.B-unsaturated materials. As used herein, the term “petroleum derived ketone, an O.f3-unsaturated Sulfone, an O.B-unsaturated Sul means a product derived from or synthesized from petroleum fonate, an O.f3-unsaturated nitrile, and an O.B-unsaturated or a petrochemical feedstock. phosphate. 0034. As used in this specification and the appended claims, the articles “a”, “an, and “the include plural refer BRIEF DESCRIPTION OF DRAWINGS ents unless expressly and unequivocally limited to one refer ent. 0020. The various embodiments of the present disclosure 0035. Other than in the operating examples, or where oth will be better understood when read in conjunction with the erwise indicated, all numbers expressing quantities of ingre following figures. dients, reaction conditions and the like used in the specifica 0021 FIG. 1 illustrates one non-limiting strategy for the tion and claims are to be understood as being modified in all conversion of glycerol to industrial useful chemical feed instances by the term “about'. Accordingly, unless indicated stocks. to the contrary, the numerical parameters set forth in the 0022 FIGS. 2A, 2B, and 3 illustrate non-limiting strate following specification and attached claims are approxima gies for synthesizing biobased diols from Saturated or unsat tions that may vary depending upon the desired properties urated fatty acids. sought to be obtained. At the very least, and not as an attempt 0023 FIGS. 4 and 5 illustrate NMR spectra of butoxym to limit the application of the doctrine of equivalents to the ethylfurfuryl acrylate product. Scope of the claims, each numerical parameter should at least 0024 FIGS. 6 and 7 illustrate NMR spectra of 5-hy be construed in light of the number of reported significant droxymethylfurfuryl acrylate product. digits and by applying ordinary rounding techniques. 0025 FIGS. 8 and 9 illustrate NMR spectra of 5-hy 0036 Notwithstanding that the numerical ranges and droxymethylfurfuryl acrylate ester product. parameters setting forth the broad scope of the invention are 0026 FIGS. 10 and 11 illustrate NMR spectra of isosor approximations, the numerical values set forth in the specific bide diacrylate product. examples are reported as precisely as possible. Any numerical 0027 FIGS. 12 and 13 illustrate NMR spectra of triallyl values, however, inherently contain certain errors necessarily citrate product. resulting from the standard deviation found in their respective 0028 FIG. 14. illustrates the NMR spectrum of epoxi testing measurements. dized triallyl citrate. 0037 Also, it should be understood that any numerical 0029 FIGS. 15 and 16 illustrate NMR spectra of 5-bu range recited herein is intended to include all sub-ranges toxymethylfurfuryl acrylate (Baylis-Hillman adduct). subsumed therein. For example, a range of “1 to 10” is 0030 FIGS. 17 and 18 illustrate NMR spectra of 5-hy intended to include all Sub-ranges between (and including) droxymethylfurfuryl acrylate (Baylis-Hillman adduct). the recited minimum value of 1 and the recited maximum 0031 FIG. 19 illustrates an NMR spectrum of a polymer value of 10, that is, having a minimum value equal to or formed from HMF acrylate. greater than 1 and a maximum value of equal to or less than 0032 FIG. 20 illustrates a gel permeation chromatogram 10. of a polymer formed from HMF acrylate. 0038 Any patent, publication, or other disclosure mate rial, in whole or in part, that is said to be incorporated by reference herein is incorporated herein only to the extent that DETAILED DESCRIPTION the incorporated material does not conflict with existing defi 0033. Various embodiments of the present disclosure nitions, statements, or other disclosure material set forth in relate to a biobased monomer units derived from glycerol. In this disclosure. As such, and to the extent necessary, the particular, glycerol from biological Sources may be converted disclosure as set forth herein Supersedes any conflicting mate to acrylic acid and corresponding acrylate derivatives. Such rial incorporated herein by reference. Any material, orportion as, for example, diacrylate esters, by condensation with a thereof, that is said to be incorporated by reference herein, but bioderived diol. The resulting diacrylate monomers may be which conflicts with existing definitions, statements, or other used in the synthesis of polymers having up to a 100% bio disclosure material set forth herein will only be incorporated based carbon isotoperatio, for example, via olefin metathesis to the extent that no conflict arises between that incorporated polymerization reactions or free radical polymerization reac material and the existing disclosure material. tions. The resulting polymers may be differentiated from 0039. The present disclosure describes several different polymers derived from petroleum feedstocks, for example by features and aspects of the invention with reference to various the carbon isotopic ratio using ASTM International Radio exemplary non-limiting embodiments. It is understood, how isotope Standard Method D6866 (ASTM Method D6866'). ever, that the invention embraces numerous alternative As used herein, the term “100% biobased carbon isotope embodiments, which may be accomplished by combining any ratio” means a composition or component of a composition of the different features, aspects, and embodiments described having a carbon isotope ratio that is indicative of a composi herein in any combination that one of ordinary skill in the art tion that is produced by a biological source (i.e., bioderived), would find useful. Such as, for example, a botanical or plant source. As used 0040 Acrylic acid having a 100% biobased carbon iso herein, the term “bioderived means derived from or synthe tope ratio may be produced from bioderived glycerol, lactic sized by a renewable biological feedstock, such as, for acid, and/or lactate esters. For example, FIG. 1 illustrates one example, an agricultural, forestry, plant, bacterial, or animal non-limiting strategy for the conversion of bioderived glyc feedstock. As used herein, the term “biobased' means a prod erol to industrial useful chemical feedstocks, such as, acrylic uct that is composed, in whole or in significant part, of bio acid (2-propenoic acid), allyl alcohol (2-propen-1-ol), and logical products or renewable agricultural materials (includ 1,3-propanediol, having a 100% biobased carbon isotope ing plant, algal, animal and marine materials) or forestry ratio. Referring now to FIG. 1, bioderived glycerol may be US 2009/001 8300 A1 Jan. 15, 2009

dehydrated (reaction A) to give acrolein (2-propenal). The 0043 Suitable bioderived olefins include, but are not lim acrolein may be oxidized to afford acrylic acid (2-propenoic ited to monoacrylates, diacrylates, and allyl esters. acid) via pathway D. Alternatively, acrolein may be reduced 0044 Alternatively, bioderived glycerol may be produced to give allyl alcohol (2-propen-1-ol) via pathway B. Suitable as a co-product of biodiesel production. Glycerol produced methods for the conversion of acrolein to allyl alcohol by these methods will have a carbon isotope ratio consistent include, but are not limited to, reactions catalyzed by a silver with a 100% biobased product and will provide a renewable indium catalyst as described by Lucas et al. in Chemie Ing Source of acrolein and acrylic acid that may be used as a enieur Technik, 2005, 77, 110-113, the disclosure of which is feedstock for the biobased monomers and polymers of the incorporated by reference herein in its entirety. Further, present disclosure. Non-limiting examples of methods and acrolein may be converted to 1,3-propanediol by pathway C. processes for producing biodiesel may be found in U.S. Pat. One suitable method for the conversion of acrolein to 1,3- No. 5,354,878; U.S. Patent Application Publication Nos. propanediol includes hydration followed by hydrogenation as 2005.0245405A1; 2007-0181504; and 20070158270A1; Pro described in U.S. Pat. No. 5,171,898, the disclosure of which visional Patent Application Ser. No. 60/851.575, the disclo is incorporated by reference herein in its entirety. The indus sures of which are incorporated in their entirety by reference trial/chemical feedstocks produced from glycerol, via herein. acrolein, as set forth herein, will have a carbon isotope ratio 0045. The monomers and polymers, as set forth herein, that can be identified as being derived from biomass (i.e., may have up to 100% biobased carbon isotope ratio as deter biobased). mined by ASTM Method D6866. The monomers and poly 0041 Alternatively, biobased acrylic acid or acrylate mers may be differentiated from, for example, similar mono esters may be synthesized from biobased lactic acid or lactate mers and polymers comprising petroleum derived esters. Biobased lactic acid derivatives may be bio-synthe components by comparison of the carbon isotope ratios, for sized, for example, by fermentation of a carbohydrate mate example, the ''C/°C or the 'C/°C carbon isotoperatios, of rial. Conversion of lactic acid and lactate esters into acrylic the materials. As described herein, isotopic ratios may be acid and acrylate esters, respectively, may be accomplished determined, for example, by liquid Scintillation counting, by dehydration of the alcohol group of the lactate moiety. accelerator mass spectrometry, or high precision isotopic Suitable methods for the conversion of lactic acid and lactate ratio mass spectrometry. esters, for example, lactic acid/lactate esters from the fermen 0046 Biobased acrylic acid (or acrylate esters), for tation of carbohydrate material in the presence of ammonia, example acrylic acid and esters synthesized by any of the into an acrylate ester or acrylic acid are disclosed in U.S. Pat. embodiments described herein, may be esterified (or transes Nos. 5,071,754 and 5,252,473, the disclosures of which are terified) with other bioderived alcohols, diols, or polyols. incorporated by reference herein in their entirety. Non-limiting suitable bioderived alcohols and diols include, 0042. As discussed herein, the present disclosure relates to for example, methanol; ethanol; n-butanol, for example from biobased monomers that may be used for the synthesis of an acetone/butanol fermentation; fusel oil alcohols (n-pro polymers having up to a 100% biobased carbon isotoperatio. panol, isobutyl alcohol, isoamyl alcohol, and/or furfural); and According to certain embodiments, the present disclosure alcohol and diol derivatives derived from carbohydrates or provides for biobased monomers that may be used for the their derivatives. synthesis of polymers having from 1% to 99.9% biobased 0047. Non-limiting examples of carbohydrate derived carbon. According to other embodiments, the present disclo diols include hydroxymethylfurfuryl, 2.5-bis(hydroxym sure provides for biobased monomers that may be used for the ethyl)furan, 2.5-bis(hydroxymethyl)tetrahydrofuran, and synthesis of polymers having from 50% to 99.9% biobased isosorbide (dianhydrohexitol), isomannide, mannitol, Xylitol, carbon. Thus, the glycerol and carbohydrate starting materi maltitol, maltitol syrup, lactitol, erythritol, isomalt, isoidide als described herein will necessarily be derived from biologi (the dianhydrohexitol of iditol), structure A, or ethoxylated or cal sources. For example, bioderived glycerol containing propoxylated derivatives of these, 100% biobased carbon, as determined by ASTM Method D 6866, may be derived from triglycerides (triacylglycerols) from biological sources, for example, a vegetable oil or an animal fat, by splitting the triglyceride into the corresponding fatty acids and glycerol. Triglycerides may be converted into the corresponding fatty acids and glycerol by acidic hydroly sis, basic hydrolysis (Saponification) or by a catalytic de esterification. Suitable triglycerides for use in the formation of bioderived glycerol include, but are not limited to, corn oil, soybean oil, canola oil, vegetable oil, safflower oil, sunflower oil, nasturtium seed oil, mustard seed oil, olive oil, Sesame oil, peanut oil, cottonseed oil, rice bran oil, babassu nut oil, castor oil, palm oil, palm kernel oil, rapeseed oil, low erucic acid rapeseed oil, lupin oil, jatropha oil, coconut oil, flaxseed oil, Non-limiting representative structures of diacrylate esters of evening primrose oil, jojoba oil, tallow, beef tallow, butter, certain carbohydrate derived alcohols are presented in chicken fat, lard, dairy butterfat, shea butter, biodiesel, used Scheme I. The diacrylate esters produced from carbohydrate frying oil, oil miscella, used cooking oil, yellow trap grease, derived diols may act as monomers or co-monomers having hydrogenated oils, derivatives of these oils, fractions of these 100% biobased carbons, as determined by ASTM Method D oils, conjugated derivatives of these oils, and mixtures of any 6866, for the synthesis of polymers having up to 100% bio thereof. based carbon. US 2009/001 8300 A1 Jan. 15, 2009

(2003), 69(10), 5983-5991 and/or U.S. Pat. No. 6,569,670 to Anderson et al., the disclosures of which are incorporated in Scheme I their entirety by reference herein. Other C.O)-dicarboxylic O O acids from biobased sources, such as, for example, maleic acid, fumaric acid, oxalic acid, malonic acid, adipic acid, N- O -- Succinic acid, and glutaric acid, adipic acid, pimelic acid, Suberic acid, azelaic acid, and sebacic acid may also be used 2,5-bishydroxymethyl(tetrahydrofuran)diacrylate according to various embodiments of the present disclosure. According to certain embodiments, the O.co-dicarboxylic acid may be an unsaturated C.()-dicarboxylic acid or a satu rated C.co-dicarboxylic acid. Reduction of the carbonyls of n----- the O.co-dicarboxylic acids provides a biobased diol which 2,5-bishydroxymethyl(furan) diacrylate may then be esterified or transesterified with acrylic acid oran acrylate ester, as produced herein, to form a biobased diacry O O s late monomer. One non-limiting embodiment of this approach is illustrated in FIG. 3. 0051. According to other embodiments, bioderived dia -- O O crylamide derivatives may serve as monomers for the poly merization reactions described herein. For example, accord isosorbide diacrylate ing to certain embodiments, the diol component in the formation of the diacrylate esters described herein, may be 0.048. Other embodiments of biobased diols suitable for chemically converted to a biobased diamine, for example, by producing diacrylate esters having 100% biobased carbon a double Mitsunobu-type reaction. Non-limiting examples of may be produced from fatty acids, such as, for example, resulting biobased diamines may include, for example, bis unsaturated fatty acids. For example, hydroformylation of amino isosorbide, 2,5-bisaminomethyltetrahydrofuran, 2.5- unsaturated fatty acids and their derivatives to produce fatty acid derivatives having a hydroxymethylene group is bisaminomethylfuran. Alternatively, naturally occurring bio described in U.S. Pat. No. 3,210,325 to De Witt et al., the derived diamines, such as, for example, 1,4-diaminobutane, disclosure of which is incorporated in its entirety by reference 1.5-diaminopentane, or other alkyldiamines or diamine con herein. Reduction of the carbonyl of the fatty acid derivative, taining alkaloid derivatives, may be replace the diol reactant for example, by hydrogenation, produces a biobased diol in the reaction with the bioderived acrylate derivative to form suitable for esterification or transesterification with acrylic a diacryl amide compound. Further, it is also contemplated acid or an acrylate ester, as produced herein, to form a bio that bioderived amino alcohols may replace the diol compo based diacrylate monomer. One non-limiting embodiment of nent in the formation of the biobased monomers. According this approach is illustrated in FIG. 2A. to these embodiments, the bioderived amino alcohols may be 0049 According to another embodiment, biobased diols reacted with the bioderived acrylic acidor bioderived acrylate suitable for producing diacrylate esters having 100% bio esters to form a bioderived monomer possessing both an based carbon may be produced by epoxidation of at least one acrylate ester and an acrylamide functionality. Non-limiting of the double bonds of an unsaturated fatty acid/ester or unsaturated fatty alcohol. One non-limiting example of the examples of several potential biobased diacrylamides or epoxidation procedure is described by Rao et al., Journal of monomers derived from amino alcohols that may be suitable the American Oil Chemists Society, (1968), 45(5), 408, the for use in various embodiments of the present disclosure are disclosure of which is incorporated in its entirety by reference illustrated in Scheme II and Scheme III. herein. The epoxidation may be followed by reduction, for example, by hydrogenation, to open the epoxide to the alco hol, which may also include reduction of the carbonyl of the fatty acid/ester to the alcohol. Any biobased diol may then be Scheme II esterified or transesterified with acrylic acid or an acrylate ester, as produced herein, to form a diacrylate monomer hav O O ing 100% biobased carbon. One non-limiting embodiment of this approach is illustrated in FIG. 2B. 0050. According to still another embodiment, diols suit able for producing diacrylate esters having 100% biobased carbon may be produced by reduction of C.O)-dicarboxylic acids. As used herein, the term C,c)-dicarboxylic acid includes organic molecules comprising a carbon chain of at least 1 carbon atom and two carboxylic acid functional groups, each of which is positioned at opposite ends of the carbon chain. For example, C.O)-dicarboxylic acids may be produced by a fermentation process involving biobased fatty acids, such as, by a fermentation process as described in Craft, et al., Applied and Environmental Microbiology, US 2009/001 8300 A1 Jan. 15, 2009

reaction may react a bioderived diacryl derivative with a bioderived cyclic olefin to produce a polymer that is up to Scheme III 100% biobased as determined by ASTM Method D 6866. H Bioderived cyclic olefins may be prepared, for example, from palmitoleic acid, oleic acid, erucic acid, linoleic acid, lino O l lenic acid, arachidonic acid, eicosapentaenoic acid, docosa O SUS O hexaenoic acid, and other unsaturated fatty acids. N O 0054 According to certain embodiments of the polymer -- H comprising a product from a ROMP reaction of a bioderived cyclic olefin and a diacryl derivative, as described herein, the polymer may be an A.B-alternating polymer (also called an O o AB alternating condensation polymer or -(AB), ). As used SCS O herein, the terms A.B-alternating polymer or “AB alternat N O ing condensation polymer include regioregular polymers -- H having a polymeric backbone wherein the co-polymer is composed of the two monomeric units (i.e., monomeric unit 0052 Bioderived diacryl derivatives, such as the diacry A and monomeric unit B) connected in a regularly alternating late esters, diacrylamides, and acrylate? acrylamide mono arrangement (i.e., ... ABABABAB . . . ) along the backbone. mers, according to various embodiments of the present dis Examples of ROMP procedures suitable for use in various closure, may serve as monomers or co-monomers in a embodiments of the present disclosure are set forth, for polymerization reaction to produce a biobased polymer. For example, in Choi et al., Angewandte Chemie, International example, according to certain embodiments, an olefin met Edition, (2002), 41 (20),3839-3841, and U.S. Pat. Nos. 6,987, athesis polymerization reaction may be used to produce the 154 and 7,034,096 to Choi et al., the disclosures of which are biobased polymer. As used herein, the term “metathesis poly incorporated in their entirety by reference herein. merization' includes an olefin metathesis reaction involving a 0055. The bioderived cyclic olefin may be, for example, metal carbene acting as a catalyst to metathesize alkene the product from an anodic coupling of a bioderived monoun monomers or co-monomers into a polyunsaturated polymer saturated long chain C.O)-dicarboxylic acid. For example, through a metallocyclobutane intermediate. Thus, certain bioderived monounsaturated long chain C.O)-dicarboxylic embodiments of the present disclosure provide for a polymer acids, which may be synthesized as described herein, may be comprising a product from an olefin metathesis polymeriza cyclized to a cyclic olefin via an intramolecular cyclic anodic tion reaction of a bioderived olefin and a diacrylate ester of a coupling process. For example, one non-limiting method for bioderived diol, wherein the diacrylate ester is produced by synthesizing cyclic olefins from dicarbonyl compounds using reacting a bioderived diol with at least two equivalents of TiCl, with a Zn Cu couple is described in McMurry et al., acrylic acid or an acrylate ester derived from a bioderived Journal of Organic Chemistry, (1977), 42(15), 2655-2656, glycerol. The olefin metathesis polymerization reaction may the disclosure of which is incorporated in its entirety by be catalyzed by an olefin metathesis catalyst, such as a metal reference herein. Cyclic olefins having a ring size containing carbene catalyst, for example, metal carbenes of molybde 4-20 ring carbons may be synthesized using this approach. num or ruthenium. Commercially available olefin metathesis According to other embodiments, bioderived cyclic olefins catalysts suitable for use in the polymerization reactions of having from 10-20 ring carbons may be synthesized by the present disclosure include, but are not limited to, the anodic coupling of monounsaturated long chain C,c)-dicar “Schrock catalyst” (i.e., |Mo(=CHMePh)(=N-Ar) boxylic acids derived from biobased fatty acids. According to (OCMe(CF))), the “1st generation Grubb's catalyst” (i.e., still other embodiments, the bioderived cyclic olefin may be Ru(=CHPh)Cl(PCy)), and the "2nd generation Grubb's derived from oleic acid and have 18 ring carbons (cycloocta catalyst” (i.e., Ru(=CHPh)Cl·PCy(N,N'-diaryl-2-imidazo decene). According to other embodiments, the bioderived lidinyl)) (Me-methyl, Ph phenyl, Ar-aryl, and cyclic olefins having from 10-20 ring carbons may be synthe Cy-cyclohexyl). Other olefin metathesis catalysts that may sized by anodic coupling of monounsaturated long chain be suitable for use in various embodiments of the present C.co-dicarboxylic acids derived from biobased unsaturated disclosure include those catalysts set forth in U.S. Pat. 7,034, fatty acids including palmitoleic acid, oleic acid, erucic acid, 096 to Choi et al. at column 12, line 27 to column 19, line 2, linoleic acid, linolenic acid, arachidonic acid, eicosapen the disclosure of which is incorporated in its entirety by taenoic acid, docosahexaenoic acid, and other unsaturated reference herein. It should be noted that the polymers and fatty acids. polymerization process claimed in the present disclosure are 0056. According to other embodiments, certain bio not limited to a particular olefin metathesis catalyst(s) and derived olefin components of the metathesis polymerization that any olefin metathesis catalyst, either currently available may be a bioderived acyclic diene, wherein the metathesis or designed in the future, may be suitable for use in various polymerization reaction is an acyclic diene metathesis (AD embodiments of the present disclosure. MET) polymerization reaction. As used herein, the term 0053 According to certain embodiments, the bioderived “acyclic diene metathesis polymerization reaction' includes olefin component of the metathesis polymerization may be a a reaction between a diacrylate ester of a bioderived diol with bioderived cyclic olefin, wherein the metathesis polymeriza at least one bioderived acyclic diene. Bioderived acyclic tion reaction is a ring opening metathesis polymerization dienes suitable for use in ADMET polymerization reactions (“ROMP) reaction. As used herein, the term “ring opening according to various embodiments herein may be synthe metathesis polymerization reaction' includes olefin metathe sized, for example, from bioderived fatty acids. For example, sis polymerization reactions wherein at least one of the mono bioderived dienes may be synthesized from C,c)-dicarboxylic mer alkene units comprises a cyclic olefin. Thus, the ROMP acids (or their ester or amide derivatives, which may be syn US 2009/001 8300 A1 Jan. 15, 2009

thesized, for example, from fatty acids as described herein) by reduction of both carbonyl functionalities to hydroxyl groups followed by a bis-dehydration of both hydroxyl groups to form the terminal diene. One non-limiting example of a reduction/dehydration strategy for forming bioderived dienes is represented in Scheme IV.

Scheme IV

1) Reduction "r-n-n-n-n-n-n-r" He2) Dehydration O O from icosanoic acid or oleic acid 21\-1N1\-1N 1\-1N1 S-1s

The resulting bioderived diene may be used as a co-monomer with at least one diacrylate ester of a bioderived diol co monomer in an ADMET polymerization reaction, for example, to form an AB-alternating polymer. Alternatively, the bioderived diene may be used directly as a monomer in an ADMET reaction as represented in Scheme V.

Scheme V ADMET 2N-1N1,N121 N 1-1N1,N1SN -(CHFCH)polymerization efn-1\-1N1\ 1 N-1 n-1\-1N

0057 Alternatively, according to other embodiments, bio ADMET polymerization reactions, such as those reactions derived acyclic dienes suitable for use in ADMET type poly described herein, to form 100% biobased polymers.

Scheme VI HO 2 ~~~~-n-n-n-n O anodic coupling -2 CO 1N1 N1-1N-1N1,N1,N1 N1 n-1N1,N-1\-1N1N1 N. ADMET polymerization clichel-ch 1N1 S-1N1\ 1 N-1N-1N1 N-1N1\-1N) 1\-1N1,N-1\ merization reactions, either as a monomer or a co-monomer, 0.058 Other embodiments of the present disclosure pro may be synthesized from biobased unsaturated fatty acids via vide for a biobased polymer comprising a product of an an anodic coupling process. For example, according to one ADMET polymerization reaction of a bioderived acyclic embodiment, an unsaturated fatty acid, such as, but not lim diene, wherein the bioderived acyclic diene is made from a ited to, oleic acid, may be anodically coupled to yield a Ca bioderived fatty acid and the polymer is 100% biobased as internal alkyldiene having a 100% biobased carbon content, determined by ASTM international Radioisotope Method D as represented in Scheme VI. The alkyldienes produced by 6866. Scheme VI illustrates one non-limiting approach for this process may be used as monomers or co-monomers in using a biobased alkyldiene as a monomer in an ADMET US 2009/001 8300 A1 Jan. 15, 2009

polymerization reaction to produce a biobased polymer prod mer, Such as, the bioderived polymers disclosed herein. uct. According to certain embodiments where the biobased According to one embodiment, the method may comprise alkyldiene is used directly as a monomer in an ADMET reacting a reactant comprising a bioderived diol, a bioderived polymerization, the product of the polymerization reaction amino alcohol, or a bioderived diamine, wherein the com may be a polymer having an average molecular weight in the pounds may be synthesized as described herein, with at least range of 3,000 g/mol to 60,000 g/mol. For example, accord two equivalents of acrylic acid oran acrylate derivative (such ing to one non-limiting embodiment, the polymer product of as, an ester, anhydride, acylhalide, oramide) to yield a diacryl the coupling product of oleic acid may have an average product and reacting the diacryl product with a bioderived molecular weight of approximately 40,000 g/mol. Further olefin in a metathesis polymerization reaction to form the according to other embodiments, the ADMET polymeriza bioderived polymer, wherein the bioderived polymer is 100% tion products from the direct polymerization of biobased biobased as determined by ASTM Method D6866. Accord alkyldiene monomers may have a polydispersity index ing to various embodiments, the acrylic acid or acrylate (“PDI) within the range of 1 to 3. As used herein, the poly derivative may be produced by a bioderived glycerol. Accord dispersity index is a measure of the distribution of molecular ing to other embodiments, the bioderived olefin may be any of weights in a given polymer sample. The PDI may be calcu the bioderived olefins disclosed herein, such as, for example, lated as the weight average molecular weight divided by the a bioderived cyclic olefin, a bioderived acyclic diene, or com number average molecular weight. binations thereof. 0059. The ADMET polymerization products of biobased 0062 According to certain embodiments of the methods, alkyldiene monomers may be useful, for example, by further the bioderived diol may be selected from the group consisting functionalization to synthesize intermediates, plasticizers, of 2.5-bis(hydroxymethyl)tetrahydrofuran, 2.5-bis(hy coatings, polyurethanes, foams, and the like. For example droxymethyl)furan, hydroxymethylfurfural, isosorbide (di according to certain embodiments, ADMET polymerization anhydrohexitol), isomannide, mannitol. Xylitol, maltitol, products of biobased alkyldiene monomers may be further maltitol syrup, lactitol, erythritol, isomalt, isoidide, structure functionalized by hydroformylation, hydroxylation (includ A, ethoxylated or propoxylated derivatives of these, a diol ing both monohydroxylation and dihydroxylation of at least produced from the hydrogenation of a hydroformylated fatty one of the alkene moieties), epoxidation, hydrogenation, or acid, a diol produced from the hydrogenation of an epoxi other reactions of the alkene functionality. Hydroformylation dized fatty acid ester, a diol produced from the reduction of an may be carried out according to the procedures described in C.()-dicarboxylic acid, and mixtures of any thereof. Accord U.S. Pat. No. 3,210,325 to DeWitt et al. Hydroxylation may ing to other embodiments of the methods, the bioderived be carried out as described by Frank D. Gunstone in “10. diamine may be selected from the group consisting of bis Chemical Properties; 10.4.2 Hydroxylation, in The Lipid amino isosorbide, 2,5-bisaminomethyltetrahydrofuran, 2.5- Handbook, Second Edition (Frank D. Gunstone, John L. Har bisaminomethylfuran, and mixtures of any thereof. Non-lim wood & Fred D. Padley, eds.), Chapman & Hall, London, iting examples of the bioderived diols, bioderived diamines, 1994 and references therein. Epoxidation may be carried out and methods of synthesis thereofare disclosed herein. as described by Frank D. Gunstone in “10. Chemical Proper 0063. According to various embodiments of the methods, ties; 10.4.1 Epoxidation', in The Lipid Handbook, Second the bioderived olefin may be a cyclic olefinand the metathesis Edition (Frank D. Gunstone, John L. Harwood & Fred D. polymerization reaction may be a ROMP reaction. According Padley, eds.), Chapman & Hall, London, 1994 and references to certain embodiments, the resulting bioderived polymer therein. Heat-bodying (polymerization) may be carried out as may be a bioderived A.B-alternating polymer. According to described by Fred L. Fox in “Unit Three: Oils for Organic certain embodiments, the bioderived cyclic olefin may be Coatings, in Federation Series on Coatings Technology produced, for example, from the anodic coupling of a (Wayne R. Fuller, Ed.), Federation of Societies for Paint monounsaturated C. ()-dicarboxylic acid derived from a bio Technology (Philadelphia) 1965 and references therein. derived fatty acid. According to still other embodiments of the Hydrogenation may be carried out as described by Frank D. methods, the bioderived olefin may be an acyclic diene Gunstone in “10. Chemical Properties; 10.1.1 Catalytic derived from a bioderived fatty acid, as described herein. Hydrogenation', in The Lipid Handbook, Second Edition According to certain embodiments, wherein the bioderived (Frank D. Gunstone, John L. Harwood & Fred D. Padley, olefin is an acyclic diene, the metathesis polymerization reac eds.), Chapman & Hall, London, 1994 and references therein. tion may be an ADMET polymerization reaction. The disclosures of each of these references are hereby incor 0064. According to various embodiments of the methods porated in their entirety by reference herein. herein, the bioderived glycerol may be produced from a tria 0060. Other non-limiting embodiments of reactions and/ cylglycerols (triglyceride) from biological Sources, for or further functionalizations of long chain polyunsaturated example, a vegetable oil or an animal fat, by splitting the hydrocarbons are set forth in greater detail in U.S. Patent triglyceride into the corresponding fatty acids and glycerol. Application Publication No. 20060149085A1, the disclosure Triglycerides may be converted into the corresponding fatty of which is specifically incorporated in its entirety by refer acids and glycerol by heat and/or pressure, acidic hydrolysis, ence herein. According to still other embodiments, the basic hydrolysis (Saponification), or by a catalytic de-esteri ADMET polymerization products of biobased alkyldiene fication. Suitable triglycerides for use in the formation of monomers may be further functionalized by heat bodied bioderived glycerol include, but are not limited to, corn oil, polymerization, for example, as described in U.S. Patent soybean oil, canola oil, vegetable oil, safflower oil, sunflower Application Publication Nos. 20040030056A1 and oil, nasturtium seed oil, mustard seed oil, olive oil, Sesame oil, 20070151480A1, the disclosures of which are specifically peanut oil, cottonseed oil, rice bran oil, babassu nut oil, castor incorporated in their entirety by reference herein. oil, palm oil, palm kernel oil, rapeseed oil, low erucic acid 0061 According to other embodiments, the present dis rapeseed oil, lupin oil, jatropha oil, coconut oil, flaxseed oil, closure provides for methods of producing a bioderived poly evening primrose oil, jojoba oil, tallow, beef tallow, butter, US 2009/001 8300 A1 Jan. 15, 2009

chicken fat, lard, dairy butterfat, shea butter, biodiesel, used frying oil, oil miscella, used cooking oil, yellow trap grease, hydrogenated oils, derivatives of these oils, fractions of these Scheme VII oils, conjugated derivatives of these oils, and mixtures of any OH thereof. According to various embodiments of the methods O O herein, the bioderived glycerol may be produced from dia -- cylglycerols (diglycerides) and/or monoacylglycerols OH OH HO O (monoglycerides). OH 0065 According to other embodiments, the present dis O O closure provides for a monomer for a polymerization reac tion. The monomer may comprise a diacrylate ester that is O O 100% biobased as determined by ASTM Method D 6866, O O wherein the diacrylate ester is produced by reacting a bio derived diol with at least two equivalents of acrylic acid C D produced from bioderived glycerol or an acrylate derivative produced from bioderived glycerol. Various non-limiting methods of producing the monomer for the polymerization acetylation/ Nosition reaction are described herein. According to certain embodi OAc OH ments, the bioderived diol may be selected from the group O O O O consisting of 2,5-bis(hydroxymethyl)tetrahydrofuran, 2.5- bis(hydroxymethyl)furan, hydroxymethylfurfuryl, isosor O O O O bide (dianhydrohexitol), isomannide, mannitol. Xylitol, O O O O maltitol, maltitol syrup, lactitol, erythritol, isomalt, isoidide, O structure A, ethoxlated or propoxylated derivatives of these, a N 2 diol produced from the hydrogenation of a hydroformylated fatty acid, a diol produced from the hydrogenation of an epoxidized fatty acid ester, a diol produced from the reduction of an C. ()-dicarboxylic acid, and mixtures of any thereof. 0067. According to other embodiments, Baylis-Hillman According to other embodiments, the monomer may com type adducts may be formed between a bioderived electro prise a diacryl amide as described herein. philic reactive group and a bioderived compound having an C.f3-unsaturated electron-withdrawing group Such as acrylic 0066. As described herein, the biobased glycerol may be acid, and catalyzed by a tertiary amine. Such as, for example, converted to alcohol derivatives, such as, for example, allyl 1,4-diazabicyclo[2.2.2]octane (DABCO) to give polymers, alcohol (2-propen-1-ol, see FIG. 1, reactions A and B). Vari for example, as described in Baylis, A. B. Hillman, M. E. D. ous embodiments of further biobased materials that may be German Patent 2155113 (1972), the disclosure of which is derived from biobased glycerol and its derivatives, such as, incorporated in its entirety by reference herein. Alternatively, allyl alcohol, may include reaction products of allyl alcohol bioderived adducts may be formed between a bioderived with bioderived carboxylic acids and/or esters. For example, electrophilic group and a bioderived compound having an according to certain embodiments, citric acid is a bioderived C.f3-unsaturated electron-withdrawing group Such as acrylic tri-carboxylic acid. The carboxylic acid moieties of citric acid acid, and catalyzed by an organophosphine, Such as described or other biobased carboxylic acids may be esterified with by Rauhut and Currier in U.S. Pat. No. 3,074,999, the disclo glycerol to form allyl esters. One example of this process is sure of which is incorporated in its entirety by reference illustrated in Scheme VII. The allyl ester products may be herein. used as industrial chemicals having 100% biobased content, 0068 For example, according to one embodiment, a poly as determined by ASTM Method D 6866. According to cer mer may be formed from at least one bioderived monomer tain embodiments, the allyl esters may be incorporated into a unit wherein the polymer composition comprises a monomer variety of applications, such as, for example, alkyd coatings unit having an electrophilic reactive group and a nucleophilic reactive group, wherein the nucleophilic reactive group reacts as reactive diluents to help reduce emissions of volatile with a electrophilic reactive group via a Baylis-Hillman type organic compounds. Alternatively, the double bond(s) of the reaction to form the polymer. As used herein, the term “Bay allyl esters, such as the allyl citrate esters, may be further lis-Hillman type reaction' includes reactions such as the derivatized, such as, for example, by epoxidation or derivati "Bayliss-Hillman reaction' and the “Rauhut-Currier reac zation of the free hydroxyl group (as shown in Scheme VII). tion’. While not intending to be limited by any particular Other biobased carboxylic acids and poly-carboxylic acids mechanism, such reactions may characterized by activation may be derivatized in a similar manner. For example the ofan C. B-unsaturated moiety by a Michael-type addition of a biobased C,c)-dicarboxylic acids may be converted to the nucleophile, such as a tertiary amine oran organophosphine, bis-allyl ester product. It is further contemplated that the to form an enolate which may then react with an electrophilic double bonds of the allyl esters may react as monomers or reactive group (Such as a carbonyl or B-carbon of an O.f3 co-monomers in olefin metathesis polymerization reactions, unsaturated carbonyl) to form a carbon-carbon bond, fol such as the ROMP and/or ADMET polymerization reactions lowed by elimination of the nucleophile. One example of such disclosed herein. a mechanism is presented in Mechanism A. US 2009/001 8300 A1 Jan. 15, 2009 10

mine, an O.B-unsaturated carbonyl, and an O.B-unsaturated nitrile. The second monomer unit comprises a first nucleo philic reactive group and a second nucleophilic reactive group, wherein the first nucleophilic reactive group and the second nucleophilic reactive group are each independently selected from the group consisting of an O.B-unsaturated ester, an O.f3-unsaturated amide, an O.B-unsaturated alde R hyde, an O.B-unsaturated ketone, an O.f3-unsaturated Sulfone, an O.B-unsaturated Sulfonate, an O.B-unsaturated nitrile, and an C.B-unsaturated phosphate. Nu 0071. The present disclosure also contemplates methods O O O O for forming an -(AB), type alternating condensation poly R" mer comprising polymerizing a first monomer unit and a R 21 R 41 y R second monomer unit via a Baylis-Hillman type reaction to O form the AB alternating condensation polymer. The first Nu Nu monomer unit comprises a first electrophilic reactive group O O O O and a second reactive electrophilic group, which may be the R" same or different, and the second monomer unit comprises a first nucleophilic reactive group and a second nucleophilic R 21 or R R" reactive group, which may be the same or different. Suitable electrophilic reactive groups and nucleophilic reactive groups Baylis-Hillman adduct Rauhut-Currier adduct are set forth in detail herein. 0072 The monomer units of the various embodiments of the Baylis-Hillman type polymerization reactions may be derived, at least in part, from biobased materials. For As used herein, the term “electrophilic reactive group' example, acrylic acid made from glycerol according to the includes a functional group that accepts electrons or electron various methods disclosed herein, may be used to form acry density during a bond forming process. As used herein, the lamines, acrylonitrile, acrolein, and various acrylates which term “nucleophilic reactive group” includes a functional may be used as biobased monomers. Alternatively, or in addi group that donates electrons or electron density during a bond tion, biobased monomer units, such as, but not limited to, forming process. Suitable electrophilic reactive groups isosorbide diacrylate, hydroxymethylfuran, the acrylate (and include, for example, an aldehyde, an aldimine, an C. B-un other derivatives) of hydroxymethyl furfural, or diformylfu saturated nitrile, or an O.B-unsaturated carbonyl containing ran may be prepared from biologically derived carbohy compound, such as, an O.B-unsaturated aldehyde, and C. B drates. unsaturated ketone, an O.f3-unsaturated ester, or an O.f3-un 0073. In other embodiments, bioderived polyfunctional saturated amide. Suitable nucleophilic reactive groups carboxylic acids, such as citric acid, may be subjected to include, for example, an O.B-unsaturated ester, C.f3-unsatur formation of esters with bioderived allyl alcohol to form ated amide, C.B-unsaturated aldehyde, an O.B-unsaturated materials suitable for bioderived thermoset polymers. In still ketone, an O.f3-unsaturated Sulfone, an O.B-unsaturated Sul other embodiments, the olefin groups of allyl esters may be fonate, C.B-unsaturated nitrile, and an O.B-unsaturated phos subjected to oxidation to form epoxides suitable for use as phate. bioderived epoxy resins. 0069. The present disclosure also contemplates methods 0074 The following examples illustrate various non-lim for forming a polymer comprising polymerizing a monomer iting embodiments of the compositions within the present unit via a Baylis-Hillman type reaction to form the polymer, disclosure and are not restrictive of the invention as otherwise wherein the monomerunit comprises an electrophilic reactive described or claimed herein. group and a nucleophilic reactive group as set forth herein. According to certain embodiments, a polymerization reaction EXAMPLES occurs by the repeated reaction of an electrophilic reactive Example 1 group on one monomer unit with the nucleophilic reactive group on another monomer unit to form the polymer. Copoly 0075 Acrylic acid (which may be biobased) is esterified mers in which the different monomer units each contain an with bioderived alcohols, such as those disclosed in U.S. electrophilic reactive group and a nucleophilic reactive group Patent Application Ser. Nos. 1 1/614,349, 60/913,572, (as described herein) are also contemplated. 60/854.987, and 60/853,574 (the disclosures of which are 0070 According to other embodiments, the present dis incorporated in their entirety by reference herein); glycerol, closure also provides for an -(AB), type alternating con ethanol, n-butanol, (from Acetone/Butanol fermentation), densation polymer comprising a first monomer unit and a fusel oil alcohols (n-propanol, isobutyl alcohol, isoamyl alco second monomer unit covalently bonded in an alternating hol), and derivatives of HMF. pattern, wherein the first monomer unit reacts with the second (0076 Synthesis of 5-butoxymethylfurfuryl acrylate monomer unit via a Baylis-Hillman type reaction to form the (Scheme VIII): Immobilized Candida antarctica Lipase B polymer. The first monomer unit comprises a first electro (Novozymes 435, 50 mg) was added to a stirred solution of philic reactive group and a second electrophilic reactive 5-butoxymethyl furfuryl alcohol (2 g, 10.8 mmol) in 5 mL group, wherein the first electrophilic reactive group and the methyl acrylate at 60° C. The mixture was stirred at 60° C. second electrophilic reactive group are each independently overnight. The lipase was removed from the mixture by fil selected from the group consisting of an aldehyde, an aldi tration and excess methyl acrylate was removed in vacuo. The US 2009/001 8300 A1 Jan. 15, 2009 yellow colored residue was purified by passing through a Example 2 silica gel column and eluting with 0-10% ethyl acetate/hex 0078. In this example, the diacrylate of bioderived furan anes to give a colorless liquid. NMR analysis was performed dimethanol (2B) was produced. on a Bruker 400 NMR instrument yielding the NMR spectra shown in FIGS. 4 and 5.

Scheme VIII: The reaction of BMFalcohol with methyl acrylate catalyzed by Novozyme 435 N----

Novozyme 435 n----- 2C Her OMe --- --~~~~ --" 0077 Synthesis of 5-hydroxymethylfurfuryl acrylate O (Scheme IX): Triethylamine (2.5 mL, 15.9 mmol) was added to a solution of 5-hydroxymethylfurfural (2g, 15.9 mmol) in (0079. Synthesis of 5-hydroxymethylfurfuryl diacrylate tetrahydrofuran (THF, 40 mL) at 0°C. under N. The reaction ester (Scheme X): Triethylamine (5.5 mL, 37.5 mmol) was mixture was stirred at 0°C. for 5 min and acryloyl chloride added to a solution of 5-hydroxymethylfurfuryl alcohol (2 g, 15 mmol) in THF (40 mL) at 0°C. under N. The mixture was was added dropwise to this mixture. A white precipitate stirred at 0°C. for 5 min and acryloyl chloride (3.16 mL, 37.5 formed concomitantly with the addition of acryloyl chloride. mmol) was added. The reaction mixture was stirred at 0°C. After the addition was complete, the reaction temperature and monitored by TLC (20% ethyl acetate/hexanes). The was increased to room temperature and the progress of the reaction was quenched after 0.5 hr with methanol and the complete reaction mixture was concentrated in vacuo. The reaction was monitored by TLC (hexanes/ethyl acetate 2:8 remaining pale yellow solid was taken up in ethyl acetate and v:v). The reaction was quenched using methanol after 0.5 hr. water was added to dissolve the Solids. The aqueous layer was The reaction mixture was concentrated by removal of metha extracted twice with ethyl acetate. The combined organic nol in vacuo. The resulting pale yellow solid was taken up in layer was washed with brine, dried over NaSO and concen trated in vacuo to give a yellow oil. The oil was purified on a ethyl acetate, and water was added to dissolve the solids. The silica gel column (0-50% ethyl acetate/hexanes). H NMR aqueous layer was extracted twice with ethyl acetate. The analysis was performed on an EFT NMR instrument (CDC1, combined organic layer was washed with brine, dried over 90 MHz) to give NMR spectra shown in FIGS. 8 and 9. Na2SO and concentrated in vacuo to give a yellow oil. The oil was purified on a silica gel column (0-50% ethyl acetate/ hexanes). NMR analysis was performed on a Bruker 400 NMR instrument to give the NMR spectra shown in FIGS. 6 O and 7. or O rol -- N-- TirooEtN c. Scheme IX: Esterification of HMF O O with acryloyl chloride atroom termperature

O HO O No s wo n------rCr rail. Example 3 O 0080. In this example, the diacrylate of bioderived isosor bide (2C) was produced. A 250 mL 3-neck flask was charged N- O 'N-1s with 60% wt sodium hydride (1.35 g, 34.2 mmol), 5 mL hexanes and 30 mL dry THF at 0°C. under nitrogen atmo rar sphere. The mixture was stirred for 5 min at 0°C. A solution of bioderived isosorbide (2g, 13.6 mmol) in 20 mL dry THF was added dropwise into this solution. The mixture was US 2009/001 8300 A1 Jan. 15, 2009

stirred for 10 min at 0°C. Acryloyl chloride (2.75 mL, 34.2 evaporator to yield the diacrylamide of 2,5-bisaminomethyl mmol) was added dropwise into the above reaction mixture. furan (4A). Structures 4B, 4C, and 4D may be synthesized by The temperature of the reaction mixture was slowly increased a similar process, using other reductive amination reactions. to room temperature and progress of the reaction was moni The products can be further purified by chromatography, tored by TLC. After 8 hours, the reaction mixture was cooled distillation, or recrystallization techniques. to 0°C. and 30 mL of water was added dropwise to quench the reaction. The organic layer was separated and the aqueous Amide Derivatives: phase was extracted twice with ethyl acetate. The combined 0084 organic layer was dried over NaSO and concentrated in vacuo to give a colorless oil. The oil was purified on a silica gel column (0-50% EtOAc/Hexanes) to give a colorless oil 4B (1.1 g, 29% yield (mol/mol)) that polymerized to form a gel O O upon complete removal of solvents in vacuo. "HNMR analy O sis was performed on an EFT NMR instrument (CDC13, 90 MHz) to give the NMR spectra shown in FIGS. 10 and 11. N- Hre-r H--- 0081. In a prophetic example, the bioderived diacrylate of 4A 2.5-bishydroxymethyl (tetrahydrofuran) (2A) can be pro O O duced in a similar manner. O Example 4 0082 In a prophetic example, bioderived diacrylate can undergo ring-opening metathesis with cyclic olefins to pro 4C duce olefin macrocycles by ring expansion to make repeating O A.B-alternating olefin polymers (biomass-derived diacry lates of butanediol can be polymerized with cyclooctene). O O--- Cyclooctene, the bioderived diacrylate (e.g. butanediol dia crylate ester) and the material produced in example 2 are charged in a round bottom flask under an inert atmosphere. A ring-opening metathesis polymerization catalyst as described in PCT Published No. WO2003/070779 (the disclosure of -" O which is incorporated in its entirety by reference herein) is O added into the reaction mixture and the degassed mixture is 4D heated at 80° C. until polymerization occurs. Methanol is O added to precipitate the polymer. The polymer is character ized by H NMR and GPC. --- O HN Example 5 0083. In a prophetic example, the diacrylamide of 2.5- bisaminomethylfuran is prepared. 2.5-Bishydroxymethylfu ran is prepared by selective hydrogenation of bioderived hydroxymethylfurfural substantially as described in U.S. Pat. 1. NH O No. 3,040,062 (the disclosure of which is incorporated in its entirety by reference herein). 2.5-Bishydroxymethylfuran is O converted to the corresponding diacrylamide using a method similar to that described by Parris in Organic Syntheses, Coll. Example 6 Vol. 5, 1973, p.73 and Vol. 42, 1962, p. 16 (the disclosures of I0085. In a prophetic example, dicarboxylic acids are pre which are incorporated in their entirety by reference herein). pared as described in U.S. Pat. No. 5.254.466 (the disclosure Acrylonitrile (401.1 g, 7.56 moles) is added to a two liter, of which is incorporated in its entirety by reference herein). 3-necked, round-bottomed flask equipped with mechanical About 3.0 to about 4.0 mmol of a C18 monounsaturated agitation, a dropping funnel, and athermocouple. The flaskis diacid (1,18-octadecen-9E-dioic acid) is dissolved in metha cooled in an ice-water bath and 100 mL of concentrated nol, followed by neutralization with about 0.3 to about 0.6 mL sulfuric acid is added dropwise over about 1.5 hours while the of 1 M sodium methoxide. The solution is placed in an anodic temperature in maintained below 5°C. 2.5-Bishydroxymeth coupling cell equipped with platinum electrodes (1.5 cmx1.5 ylfuran (128 g, 1 mol) is then added dropwise over two hours cm and 2.5 cmx1.0 cm, spaced <0.5 cm apart). A potentiostat/ while maintaining the temperature between 0-5°C. The tem galvanostat with a 100-V maximum compliance Voltage perature of the resulting mixture is held below 5° C. for 5 (Princeton Applied Research Model 173) is applied to main hours and then the temperature is increased slowly to room tain a constant current between the platinum electrodes in the temperature and stirred for 2 days. The reaction mixture is anodic coupling cell. The anodic coupling is performed in a poured over 2 liters of crushed ice and extracted with 1 liter of water-jacketed cell to maintain a constant temperature, which ethyl acetate split into 4x250 mL volumes. The aqueous is generally set at a temperature between about 40° C. and phase is separated and the ethyl acetate phase is washed with about 60°C. A magnetic stir bar is used to agitate the reaction a saturated solution of sodium chloride followed by neutral mixture. The electrolysis is stopped, when an electrical ization using a saturated Solution of sodium bicarbonate to charge equivalent to 1.3 Faradays per mole of the starting acid yield a neutralized ethyl acetate extract. The ethyl acetate at the specified current density (generally between about 0.05 extract is dried over anhydrous magnesium sulfate, filtered and 0.12 A cm', or about 0.18-0.63 A) passes through the and the solvent is removed under reduced pressure on a rotary reaction mixture. The reaction mixture is acidified with a few US 2009/001 8300 A1 Jan. 15, 2009

drops of concentrated HCl, which converts methoxide to Example 8 methanol and protonates the carboxylate ions. Following evaporation of methanol, the crude product is dissolved in 50 I0087. In a prophetic example, bioderived dienes are pro mL of hexanes, transferred to a 125 mL separatory funnel, duced. The diolofan C,c)-dicarboxylic acid is produced as set and washed with three 75 mL portions of water at 60° C. A forth in Example 11 by the reduction of the carboxylic acid mixture of the desired cyclic product, linear coupled polymer/ moieties of the diacid and the diol is heated with 1% Amber oligomer and disproportionated compounds is obtained lite 35 at 130° C. under vacuum. The reaction is cooled to (Scheme XI). This mixture can be separated by chromatog room temperature and the catalyst removed by filtration. The raphy, distillation, or recrystallization and any combination catalyst is washed with hexanes and the combined filtrate is of these techniques. concentrated in vacuo to give the diene (Scheme XIV).

S XI. F ion of CVcli ing of

HO OH Anodic Coupling ~~~~-n-n-n-r He-2CO O O

Example 7 0.086. In a prophetic example, ring-opening metathesis (Scheme XII) using ring-opening metathesis polymerization catalyst such as those described in PCT Publication No. WO2003/070779 (the disclosure of which is incorporated in its entirety by reference herein) is performed. Isosorbide dia crylate as produced in Example 3 is coupled with cyclic olefins produced from anodic coupling of C18:1 diacid as described in Example 6. The product is precipitated in metha nol and characterized by H NMR and GPC.

Ru cat. US 2009/001 8300 A1 Jan. 15, 2009 14

s XIV. C ion of C.(I)-di

1) Reduction "--- ~~~~ He2) Dehydration O O or methyl ester

Example 9 Solvent, under inert atmosphere, and the mixture is stirred at 0088. In a prophetic example, polymers from bioderived room temperature. Vacuum is applied to remove the evolving dienes, such as, the dienes produced by the process in ethylene and the mixture is stirred until the solution become Example 8, are produced by an ADMET-type polymerization viscous. The mixture is warmed to 50-55° C. and stirring is (Scheme XV). In a prophetic example, the bioderived diene continued until stirring is no longer possible. Polymerization produced in Example 8 is added under an inert atmosphere to is quenched by exposure to air. The Viscous solution is dis a flame dried flask equipped with a vacuum valve. An solved in THF and the product analyzed by "H NMR and gel ADMET-type polymerization catalyst is then added without permeation chromatography.

s XV. ADMET- ization of bioderi ADMET wiR olefin metathesis 4\-1N1\-1n 1\-1N1\-1s -ethylenecatalyst 4N1a1a1a 1-1-1-1N

I0089. In another prophetic example, a bioderived long chain polyunsaturated hydrocarbon (C-Cso) produced by anodic coupling for bioderived unsaturated fatty acids, Such as described in U.S. Patent Application Publication No. 2006/ 014.9085 A1 (the disclosure of which is incorporated in its entirety by reference herein) is coupled using an ADMET type polymerization catalyst to give a polymer of high molecular weight (Scheme XVI).

C18:1, C18:1 N-11-1-1 DMT Polymerization

N-N-N-1-1 (N-N-N-N-N-N-N-1 nu-n-n-n- US 2009/001 8300 A1 Jan. 15, 2009

0090 The polymers are expected to range in molecular 1 mM MgSO4. A trace element solution consisting of 2.7% weight from the C18:1-C18:1 coupling product to about (w/v) FeC1.6HO, 0.2% (w/v), ZnC14HO, 0.2% (w/v) 40,000 g/mol., with a polydispersity index of from about 1 to CoCl2.6H2O, 0.2% (w/v) Na MoO2HO, 0.1% (w/v) about 3. These polymers will make valuable feedstocks for CaCl2HO, 0.1% (w/v) CuCl, 0.1% (w/v) MnC14H2O, further functionalization to make intermediates, plasticizers, 10% (v/v) conc. HCl is provided. A single colony of BL21 coating, polyurethanes and foam. This will produce bio (DE3) RP/pPV2.83 is used to inoculate 5 mL of M9 medium derived displaced terminal alkenes. and incubated at 37°C. for 12 h to form an overnight culture. Example 10 The overnight culture (1%) is transferred to 100 mL of M9 medium in a shake flaskand incubated at 37°C. with shaking 0091. In a prophetic example, bioderived polymers are at 250 rpm. Dicarboxylic acid, prepared as described in U.S. prepared Substantially according to Example 9 (Scheme Pat. No. 5,254,466, is added to the shake flask after 4 h of XVI), are subjected to one or more of hydroformylation, incubation. After incubating in the shake flask for 24 hours, hydroxylation, epoxidization, heat-bodying/polymerization, the reduced diol is recovered from the fermentation broth by or hydrogenation (Scheme XVII). extraction with hexanes. The diol is purified on a silica gel

N-1-1-1-1 (S-1-1-1-1-1-1-1 Y-1-1-1-1

/ / N N Hydrogenated Hydroformylated Hydroxylated Epoxidized Heat-Bodied (Polymerized)

Example 11 column (ethyl acetate/hexanes, 0-40% V/v). The diacrylate of 0092. In a prophetic example, the C18:1 diacid prepared in the recovered diol is synthesized substantially as in Example Example 6 (prepared as described in U.S. Pat. No. 5.254.466, 1. The recovered diol is mixed with excess methyl acrylate the disclosure of which is incorporated in its entirety by and immobilized lipase (Novozymes 435) is added to the reference herein) may be reduced to diol, and esterified to solution. The mixture is stirred at 60° C. for 12 h and the form a biomass-derived diacrylate, which may be used as a progress of the reaction is monitored by thin layer chroma co-monomer in an olefin metathesis polymerization with a tography (TLC) (ethyl acetate/hexanes, 4/6 V/v). The immo cyclic olefin using a Ruthenium olefin metathesis catalyst. bilized lipase is removed by filtration, excess methyl acrylate 0093. Synthesis of bioderived diacrylate (Scheme XVIII). is removed under vacuum, and the diacrylate ester of the fatty E. coli BL21 (DE3) RP/pPV2.83 expressing the Carboxylic diol is purified on a silica gel column (ethyl acetate/hexanes, Acid Reductase (car) gene is cultivated in M9 glucose 0-40% V/v). Other suitable diacids including polyunsaturated medium. The M9 medium (1 L) consists of 6 g Na HPO, 3 g diacids, such as those prepared from linoleic acid, linolenic KHPO, 0.5g NaCl, 1 g NHCl, 0.1% yeast extract, 0.4% acid, arachidonic acid, eicosapentaenoic acid, docosa glucose, 20 mg of D-Pantothenic acid hemi-calcium salt, 40 hexaenoic acid and others, as well as monoacrylate esters mg L-cysteine, 3 mL trace elements, 40 g/mL amplicillinand may be prepared by similar methods.

S XVIII. S is of bi rari

HO OH 1) Reduction o 2) Acrylic Acid esterification O O or methyl ester --" Srs O O

O

HO 1) Reduction OH - 2) Acrylic Acid - esterification US 2009/001 8300 A1 Jan. 15, 2009

-continued 1. O ---

Example 12 Example 13 0094. In a prophetic example, bioderived fatty acids can be 0095. In a prophetic example, bioderived epoxidized fatty hydroformylated/hydrogenated (as described in U.S. Pat. No. alcohols or fatty acid esters selectively hydrogenated are 3.210,325, the disclosure of which is incorporated in its esterified with bioderived acrylic acid to yield bioderived entirety by reference herein) and esterified with bioderived branched diacrylates (Scheme XX). acrylic acid to form bioderived diacrylates (Scheme XIX). 0096 Bioderived epoxidized fatty acid are used as sub Bioderived fatty acids are hydroformylated substantially as strates for reduction with E. coli BL21 (DE3) RP/pPV2.83 described in Example 10. The hydroformylated fatty acid is substantially as described in Example 11 to give epoxidized used as a substrate for reduction with E. coli BL21 (DE3) fatty alcohol. The epoxidized fatty alcohol is hydrogenated RP/pPV2.83 substantially as described in Example 11 to give according to the procedure described by Rao et. al (JAOCS, a branched diol. The branched diols are esterified with methyl 1965, 45(5), 408, the disclosure of which is incorporated in its acrylate and Novozymes 435 as catalyst as described in entirety by reference herein) to produce a diol. The diol is Example 1 to form the diacrylates. Other suitable bioderived esterified with bioderived methyl acrylate and Novozymes fatty acids including polyunsaturated diacids, such as those 435 as catalyst, substantially as described in Example 1 to prepared from linoleic acid, linolenic acid, arachidonic acid, form a bioderived branched diacrylate. Other suitable bio eicosapentaenoic acid, docosahexaenoic acid and others, as derived fatty acids include monounsaturated fatty acids. Such well as monoacrylate esters may be prepared by similar meth as palmitoleic acid, oleic acid, and erucic acid, and polyun ods. saturated diacids, such as those prepared from linoleic acid,

Scheme XIX. Bioderived diacrylates formed from hydroxyformylated fatty acids HCO

r-o-OH

Hydrogenation

HO

OH

Esterification or transesterification w acrylic acid

Srs US 2009/001 8300 A1 Jan. 15, 2009 linolenic acid, arachidonic acid, eicosapentaenoic acid, 50% HO was stirred at room temperature. The progress of docosahexaenoic acid and others. Bioderived branched acry the reaction was monitored by TLC (Ethyl acetate: Hexanes, lates may be formed at all possible hydroxyl groups, or free 6:4 v/v). H NMR analysis was carried out on an EFT NMR hydroxyl groups may remain, so that mono-, di-, tri-, etc instrument (CDC1, 90 MHz) to yield the spectra shown in acrylate esters may be prepared. FIG. 14, indicating oxirane formation.

| st genation N----~~~~ OH Esterification or transesterification w acrylic acid

Example 14 0097. Synthesis of triallylcitrate (Scheme XXI): A 50 mL round bottom flask fitted with a Dean-Stark trap and con Scheme XXII: Synthesis of epoxidized triallyl citrate esters denser was charged with citric acid (5g, 26 mmol), Amberlyst 35 (0.5 g) and allyl alcohol (15 mL). The slurry was stirred OH and heated to 105° C. and the progress of the reaction was O O H2O2 monitored by TLC (Ethyl acetate:Hexanes: Acetic acid, 4:6: Her 0.1 V/v/v). After 12 h, the reaction mixture was cooled to room O O HCO2H temperature. The catalyst was filtered and excessallyl alcohol O O was evaporated in vacuo. The residue was purified by chro matography on a silica gel column (Ethyl acetate/Hexanes, 0-50%) to afford a dark yellow oil (2.2g, 27% yield (mol/ mol)). H NMR analysis was carried out on an EFT NMR instrument (CDC1, 90 MHz) to yield the spectra shown in FIG. 12 and FIG. 13. OH O O

Scheme XXI: Synthesis of triallyl citrate O O HO O O O O --

OH OH O O HO O O OH

OH Amberlyst 35 Example 16 21\-1 Her 1050 C. (0099 Synthesis of the Baylis-Hillman adduct of 5-bu toxymethylfurfural with methyl acrylate (Scheme XXIII). 5-Butoxymethylfurfural (BMF, 2 g, 10.9 mmol) in methanol (10.9 mL, 1 M) was stirred, and 45% (w/v) aqueous trimethyl amine (0.805 g, 13.6 mmol) was added. The solution was Example 15 stirred at room temperature for 2 min. To this solution, methyl 0098 Synthesis of citrate esters of propylene oxide acrylate (2.83 g, 32.7 mmol) was added slowly and the result (Scheme XXII). A mixture of allyl citrate (1 g, 3.2 mmol ing Solution was stirred at room temperature for 1 day. The prepared as in Example 14), 0.5 mL formic acid, and 1 mL progress of the reaction was monitored by Thin Layer Chro US 2009/001 8300 A1 Jan. 15, 2009 matography (TLC) (Hexanes: Ethyl acetate, 6:4 v:v). The Baylis-Hillman adduct of 5-hydroxymethyl furfural with color of the reaction mixture turned from pale to dark yellow methyl acrylate. during the course of the reaction. The reaction was quenched by adding 20 mL of ethyl acetate and 5 mL H.O.The organic layer was separated and the aqueous layer was extracted twice Scheme XXIV: The reaction of HMF with methyl acrylate at room with ethyl acetate. The combined organic layer was dried over temperature Sodium sulfate and concentrated in vacuo. The product was O purified on a silica gel column (Ethyl acetate/Hexanes, 0-30%) to afford a yellow oil (2 g. 68% yield). "H NMR O analysis was carried out on a Bruker 400 NMR instrument HO \ f H + (CDC1,400MHz) to yield the spectra shown in FIGS. 15 and 16, indicating the presence of pure Baylis-Hillman adduct of O 5-butoxymethyl furfural with methyl acrylate. Aq MeN (45% w/v) o1 CH3OH, rt Scheme XXIII: The reaction of BMF with methyl acrylate OH O O O 1N1N O O \ f H + HO \ f O O Aq MeN (45% w/v) o1 CH3OH, rt Example 18

OH O 0101 Polymers from HMF acrylate: 5-Hydroxymethyl O furfuryl acrylate synthesized in Example 1 was self con densed to give a Baylis-Hillman adduct using the procedure ~~~~ substantially as described in Example 16. Crude "H NMR showed disappearance of starting material and production of Baylis-Hillman adduct (FIG. 19) and the reaction product had Example 17 a polydispersity index of 1.4. TLC (Ethyl acetate/Hexane, 40% V/v) showed disappearance of the starting material and 0100. The Baylis-Hillman adduct of 5-hydroxymethyl development of a polar compound of Rf O.2 indicating devel furfural (HMF) with methyl acrylate was synthesized opment of product of high polarity (Scheme XXV). Gel per (Scheme XXIV) essentially using the procedure described in meation chromatography showed a polymer having an aver Example 16, except that 5-hydroxymethylfurfural (2 g, 10.9 age molecular weight of 63414 g/mol (FIG. 20).

Scheme XXV: Synthesis of polymer from HMF acrylate O Nulls O Me3N irr H2O:MeOHrt

mmol) was used instead of 5-butoxymethyl furfural. The Example 19 progress of the reaction was monitored by TLC (Hexane: Ethyl acetate, 2:8 v:v). The reaction turned from pale to dark 0102 Polymers from condensation of diformylfuran yellow in color during the course of the reaction. The reaction (DFF) and the diacrylate of 2,5-dihydroxymethylfuran: In a was quenched, separated, and dried as with the BMF adduct prophetic example, DFF is synthesized from HMF according (Example 16). The product was purified on a silica gel column to the procedure described in PCT Publication No. WO2006/ (Ethyl acetate/Hexanes, 0-70%) to afford a yellow oil (2 g, 063287, the disclosure of which is specifically incorporated 68% yield). "HNMR analysis was carried out on a Bruker 400 in its entirety by reference herein. Condensation of DFF with NMR instrument (CDC1, 400 MHz) to yield the spectra the diacrylate of 2,5-dihydroxymethylfuran or diacrylamides shown in FIG. 17 and FIG. 18, indicating the presence of pure as produced in Examples 2 and 5, respectively, according to US 2009/001 8300 A1 Jan. 15, 2009 the Baylis-Hillman procedure described in Example 16 give an A.B-alternating condensation polymer Such as that depicted in Scheme XXVI.

Scheme XXVI: Polymer formed by condensation of diformylfuran and the diacrylate of 2,5-hydroxymethylfuran. O O O O O -- O MeN -- Sry-ry MeOH, H2O

Example 20 (0103 Polymer from condensation of diformylfuran (DFF) -continued and isosorbide diacrylate: In a prophetic example, DFF is condensed with isosorbide diacrylate (produced as described in Example 3) according to the Baylis-Hillman procedure described in Example 16 to give A.B-alternating condensa tion polymer such as those depicted in Scheme XXVII. OH OH O O ... O O O Scheme XXVII: Polymer formed by condensation of DFF and isosorbide \ / O / ÖH diacrylate. O O 21 \ f n O t

O Example 21 N-- 0104 Polymer from condensation of diformylfuran (DFF) O Me3N and diacrylamide of 2.5-bisaminomethylfuran. In a prophetic Her H2O:MeOH example, DFF is condensed with the diacrylamide of 2.5- O bisaminomethylfuran (produced according to Example 5) or with the diacrylamide of 2.5-bisaminomethyl tetrahydrofu r ran according to the Baylis-Hillman procedure described in O Example 16 to yield A.B-alternating condensation polymer such as those depicted in Scheme XXVIII.

Scheme XXVIII: Example polymers formed by condensation of DFF and diacrylamide of 2,5-bisaminomethylfuran or with diacrylamide of 2,5-bisaminomethyl tetrahydrofuran O O O O O He N f 1. MeOH, H2O CryOH OH O rary O O O O Me3N rry-rN N 1. \ f MeOH, H2O US 2009/001 8300 A1 Jan. 15, 2009 20

-continued O OH OH O O O O O N N N H \ / rars

Example 22 Example 23 0105 Polymer from condensation of diformylfuran (DFF) 0106 Polymer from condensation of diacrylate of 2.5- and diacrylamide of isosorbide: In a prophetic example, DFF bishydroxymethylfuran: In a prophetic example, the diacry is condensed with the diacrylamide ofisosorbide according to late of 2,5-bisaminomethylfuran undergoes self-condensa the Baylis-Hillman procedure described in Example 16 to tion according to the procedure described in example 16 to yield an A.B-alternating polymeric compound Such as that give a polymeric compound Such as that depicted in Scheme depicted in Scheme XXIX. XXX.

Scheme XXX: Polymer that can be formed by condensation of diacrylate of 2,5-bishydroxymethylfuran O O MeN Her MeOH, H2O

O ---, O Cr-r)

0107 Although the foregoing description has necessarily presented a limited number of exemplary embodiments of the Scheme XXIX: Polymer formed by condensation of DFF and diacrylamide invention, those of ordinary skill in the relevant art will appre of isosorbide ciate that various changes in the components, details, mate rials, and process parameters of the examples that have been herein described and illustrated in order to explain the nature \ . of the invention may be made by those skilled in the art, and NH all such modifications will remain within the principle and O O Scope of the invention as expressed herein in the appended O O MeN claims. It will also be appreciated by those skilled in the art that changes could be made to the embodiments described \ f -- O MeOH:HO above without departing from the broad inventive concept thereof. It is understood, therefore, that this invention is not HN limited to the particular embodiments disclosed, but it is intended to cover modifications that are within the principle and scope of the invention, as defined by the claims. \ 1-27. (canceled) 28. A polymer comprising: a product from a metathesis polymerization reaction of a OH O bioderived olefin and an acrylate ester of a bioderived alcohol, wherein the acrylate ester is produced by reacting the bio derived alcohol with at least one equivalent of acrylic acid produced from bioderived glycerol, wherein the polymer is 100% biobased as determined by ASTM International Radioisotope Method D 6866. 29. The polymer of claim 28, wherein the bioderived diol is selected from the group consisting of isosorbide, 2.5-bishy droxymethyltetrahydrofuran, 2.5-bishydroxymethylfuran, a diol produced from the hydrogenation of a hydroformylated fatty acid, a diol produced from the hydrogenation of an US 2009/001 8300 A1 Jan. 15, 2009 epoxidized fatty acid ester or fatty acid alcohol, a diol pro isosorbide, 2.5-bisaminomethyltetrahydrofuran, 2.5-bisami duced from the reduction of an a.o)-dicarboxylic acid, and nomethylfuran, and mixtures thereof. mixtures thereof. 41. The method of claim 38, wherein the bioderived olefin 30. The polymer of claim 28, wherein the bioderived olefin is a cyclic olefin and the metathesis polymerization reaction is is a bioderived cyclic olefin and the metathesis polymeriza a ring opening metathesis polymerization reaction. tion reaction is a ring opening metathesis polymerization 42. The method of claim 41, wherein the polymer is an AB reaction. alternating polymer. 31. The polymer of claim30, wherein the polymer is an AB 43. The method of claim 41, wherein the cyclic olefin is alternating polymer. produced from an anodic coupling of a monounsaturated long chain dicarboxylic acid derived from a bioderived fatty acid. 32. The polymer of claim 28, wherein the product is from 44. The method of claim 38, wherein the bioderived olefin an acyclic diene metathesis polymerization reaction and is an acyclic diene derived from a bioderived fatty acid and wherein the bioderived olefinis an acyclic diene derived from wherein the metathesis polymerization reaction is an acyclic a bioderived fatty acid. diene metathesis polymerization reaction. 33. The polymer of claim 28, wherein the bioderived glyc 45. The method of claim 38, wherein the bioderived glyc erol is produced from a triacylglycerol selected from the erol is produced from a triacylglycerol selected from the group consisting of corn oil, soybean oil, canola oil, vegetable group consisting of corn oil, Soybean oil, canola oil, vegetable oil, safflower oil, Sunflower oil, nasturtium seed oil, mustard oil, safflower oil, Sunflower oil, nasturtium seed oil, mustard seed oil, olive oil, Sesame oil, peanut oil, cottonseed oil, rice seed oil, olive oil, Sesame oil, peanut oil, cottonseed oil, rice bran oil, babassu nut oil, castor oil, palm oil, palm kernel oil, bran oil, babassu nut oil, castor oil, palm oil, palm kernel oil, rapeseed oil, low erucic acid rapeseed oil, lupin oil, jatropha rapeseed oil, low erucic acid rapeseed oil, lupin oil, jatropha oil, coconut oil, flaxseed oil, evening primrose oil, jojoba oil, oil, coconut oil, flaxseed oil, evening primrose oil, jojoba oil, tallow, beef tallow, butter, chicken fat, lard, dairy butterfat, tallow, beef tallow, butter, chicken fat, lard, dairy butterfat, shea butter, biodiesel, used frying oil, oil miscella, used cook shea butter, biodiesel, used frying oil, oil miscella, used cook ing oil, yellow trap grease, hydrogenated oils, derivatives of ing oil, yellow trap grease, hydrogenated oils, derivatives of these oils, fractions of these oils, conjugated derivatives of these oils, fractions of these oils, conjugated derivatives of these oils, and mixtures of any thereof. these oils, and mixtures of any thereof. 34. The polymer of claim 28, wherein the bioderived olefin 46. A polymer composition comprising: is selected from the group consisting of monoacrylates, dia a monomer unit having an electrophilic reactive group and crylates, and allyl esters. a nucleophilic reactive group, wherein the electrophilic 35. A polymer comprising: reactive group is selected from the group consisting of a product of an acyclic diene metathesis polymerization an aldehyde, an aldimine, an O.B-unsaturated carbonyl, reaction of a bioderived acyclic diene, wherein the bio and an O.f3-unsaturated nitrile and the nucleophilic reac derived acyclic diene is made from a bioderived fatty tive group is selected from the group consisting of an acid and the polymer is 100% biobased as determined by C.B-unsaturated ester, C.f3-unsaturated amide, C.f3-un ASTM international Radioisotope Method D 6866. Saturated aldehyde, an O.B-unsaturated ketone, an O. B 36. The polymer of claim 35, wherein the polymer has a unsaturated Sulfone, an O.f3-unsaturated Sulfonate, C. B polydispersity index from 1 to 3. unsaturated nitrile, and an O.B-unsaturated phosphate, 37. The polymer of claim 35, wherein the polymer is fur wherein the nucleophilic reactive group reacts with the ther functionalized in a reaction selected from the group electrophilic reactive group via a Baylis-Hillman type consisting of hydroformylation, hydroxylation, epoxidation, reaction to form a polymer. hydrogenation, and heat-bodied polymerization. 47. An AB alternating condensation polymer comprising: 38. A method for producing a bioderived polymer, the a first monomer unit comprising a first electrophilic reac method comprising: tive group and a second electrophilic reactive group, reacting a compound selected from the group consisting of wherein the first electrophilic reactive group and the bioderived diols, bioderived amino alcohols, bioderived second electrophilic reactive group are each indepen diamines, and combinations of any thereof with at least dently selected from the group consisting of an alde two equivalents of acrylic acid to yield a diacryl mono hyde, an aldimine, an O.B-unsaturated carbonyl, and an mer product, wherein the acrylic acid is produced from C.B-unsaturated nitrile; and bioderived glycerol; and a second monomer unit comprising a first nucleophilic reacting the diacryl monomer product with a bioderived reactive group and a second nucleophilic reactive group, olefin in a metathesis polymerization reaction to form a wherein the first nucleophilic reactive group and the bioderived polymer, wherein the bioderived polymer is second nucleophilic reactive group are each indepen 100% biobased as determined by ASTM Method Inter dently selected from the group consisting of an O. B national Radioisotope Method D 6866. unsaturated ester, an O.f3-unsaturated amide, an O.f3 39. The method of claim 38, wherein the bioderived diol is unsaturated aldehyde, an O.f3-unsaturated ketone, an selected from the group consisting of isosorbide, 2.5-bishy C.B-unsaturated Sulfone, an O.f3-unsaturated Sulfonate, droxymethyltetrahydrofuran, 2.5-bishydroxymethylfuran, a an C.B-unsaturated nitrile, and an O.f3-unsaturated phos diol produced from the hydrogenation of a hydroformylated phate, fatty acid, a diol produced from the hydrogenation of an wherein the first monomer unit reacts with the second epoxidized fatty acid ester, a diol produced from the reduction monomer unit via a Baylis-Hillman type reaction to of an O.()-dicarboxylic acid, and mixtures thereof. form a polymer. 40. The method of claim 38, wherein the bioderived diamine is selected from the group consisting of bis-amino