USOO8546513B2

(12) United States Patent (10) Patent No.: US 8,546,513 B2 Hedricket al. (45) Date of Patent: *Oct. 1, 2013

(54) CATALYTIC POLYMERIZATION OF 5,559,159 A 9, 1996 Sublett et al. POLYMERS CONTAININGELECTROPHC E8 1939: R tal LINKAGES USING NUCLEOPHILIC 6,911,546s’ s B2 6/2005 HedricketCC al. ca. REAGENTS 6,916,936 B2 7/2005 Hedricket al. 6,969,705 B2 11/2005 Pecquet et al. (71) Applicant: International Business Machines 7,544,800 B2 6/2009 Hedricket al. Corporation, Armonk, NY (US) 2005.0049418 A1 3/2005 Hedricket al. s s 2011/0004014 A1 1/2011 Hedricket al.

(72) Inventors: at:; Russe It is. Pratt, EOR&A Oakland, FOREIGN PATENT DOCUMENTS (US); Robert M. Waymouth, Palo Alto, EP 629645 A1 6, 1994 CA (US) OTHER PUBLICATIONS Modern Polyesters: Chemistry and Technology of Polyesters and (73) Assignees: International Business Machines Copolyesters, p. 90, John Wiley & Sons Ltd., 2003. Corporation, Armonk, NY (US); The Lohmeijer et al., and Amidine Organo-Catalysts for Ring Board of Trustees of the Leland Opening Polymerization of Cyclic , Macromolecules 39:8574 Stanford Junior University, Palo Alto, 8583 (2006). CA (US) Lohmeijer et al., Organocatalytic Living Ring-Opening Polymeriza tion of Cyclic Carbosiloxanes, Organic Letters 8:4683-4686 (2006). (*) Notice: Subject to any disclaimer, the term of this Pratt et al., Triazabicyclodecene: A Simple Bifuncational patent is extended or adjusted under 35 Organocatalyst for Acyl Transfer Ring-Opening Polymerization of U.S.C. 154(b) by 0 days Cyclic Esters, J. Am. Chem. Soc. 128:4556-4557 (2006). M YW- Schuchardt et al., Transesterification of Vegetable Oils: A Review, J. This patent is Subject to a terminal dis- Braz. Chem. Soc. 9(1): 199-210 (1998). claimer. Chumaetal. The Reaction Mechanism for the Organocatalytic Ring Opening Polymerization of L-Lactide Using a Guanadine-Based (21) Appl. No.: 13/735,904 Catalyst: Hydrogen-Bonded or Covalently Bound?, J. Am. Chem. Soc. 130(21):6749-6754 (2008). (22) Filed: Jan. 7, 2013 Coles, Bicyclic-, -guanidinates and -guanidinium salts: 9 Wide Ranging Applications from a Simple Family of Molecules, O O Chem. Commun. (25):3659-3767 (2009). (65) Prior Publication Data Cornils & Herrmann, Applied Homogeneous Catalysis with US 2013/O123458A1 May 16, 2013 Organometallic Compounds, Wiley-VCH. Weinheim, Germany, vol. 1: Applications, Chapter 1 (2002). O O Kamber et al., Organocatalytic Ring-Opening Polymerization, Related U.S. Application Data Chem. Rev. 107(12):5813-5840 (2007). (62) Division of application No. 12/496.535, filed on Jul. 1, Kiesewetter et al., Cyclic Guanidine Organic Catalysts: What is 2009, now Pat. No. 8,367,796. Magic About Triazabicyclodecene?, J. Org. Chem. 74(24):9490-949 (2009). (51) Int. Cl. List, Introduction: Organocatalysis, Chem. Rev. 107(12):5413-5415 (2007). C08G 63/00 (2006.01) MacMillan, The Advent and Development of Organocatalysis, (52) U.S. Cl. Nature 455(7211):304-308 (2008). USPC ...... 528/274; 528/308.1:528/308.3: Nederberg et al., Organocatalytic Ring Opening Polymerization of 528/336:564/230: 502/167: 502/200: 548/336.5; Trimethylene Carbonate, Biomacromolecules 8(1): 153-160 (2007). 544/247: 544/281 (58) Field of Classification Search Primary Examiner — Frances Tischler USPC ...... 528/86, 88,271, 272, 274, 308.1, (74) Attorney, Agent, or Firm — Karen Canaan; CanaanLaw, 528/310,332, 336: 548/336.5; 544/247, P.C.; Isaac Rutenberg 544/281: 564/230, 238, 241, 242: 502/162, 502/164, 167, 200 (57) ABSTRACT See application file for complete search history. The disclosure relates to methods and materials useful for polymerizing a monomer. In one embodiment, for example, (56) References Cited the disclosure provides a method for polymerizing a mono mer containing a plurality of electrophilic groups, wherein U.S. PATENT DOCUMENTS the method comprises contacting the monomer with a nucleo 3,254,054 A 5, 1966 Boerma philic reagent in the presence of a guanidine-containing cata 4,652,667 A 3, 1987 Green 4,681,967 A 7, 1987 Green lyst. The methods and materials of the disclosure find utility, 4,797.487 A 1, 1989 ACourt for example, in the field of materials science. 5,319,066 A 6/1994 King 5,418,316 A 5/1995 Kuhling et al. 20 Claims, No Drawings US 8,546,513 B2 1. 2 CATALYTIC POLYMERIZATION OF merization catalysts. Such catalysts may be difficult to pre POLYMERS CONTAININGELECTROPHC pare, may be unstable to long-term storage, or may require LINKAGES USING NUCLEOPHILIC stringent reaction conditions to provide polymer. Moreover, REAGENTS these catalysts are immortal, limiting the versatility of the widely used mechanical recycling, because at high tempera CROSS-REFERENCE TO RELATED tures the residual catalyst causes molecular weight degrada APPLICATION tion. This limits the use of these recycled products to second ary applications (i.e., carpet, playground equipment etc.). This application is a divisional of U.S. patent application Ser. No. 12/496.535, filed on Jul. 1, 2009, which is incorpo 10 SUMMARY OF THE INVENTION rated in its entirety herein. Accordingly, there is a need in the art for improved poly ACKNOWLEDGEMENT OF GOVERNMENT merization methods that involve mild reaction conditions, SUPPORT non-metallic and stable catalysts, and minimal potentially 15 problematic by-products, while allowing for the synthesis of This invention was made with Government support under polymers with controlled molecular weights, low polydisper Grant No. NFS-CHE 0645891 awarded from the United sities, and/or controlled architecture (e.g., end-functional States National Science Foundation; accordingly, the United ized, branched, block copolymers, etc.). States Government has certain rights to this invention. The invention provides an efficient catalytic polymeriza TECHNICAL FIELD tion reaction that does not employ a metallic catalyst. Because a nonmetallic catalyst is employed, the polymeriza This invention relates generally to the polymerization of tion products, in a preferred embodiment, are substantially monomers, and, more particularly relates to an organocata free of metal contaminants. Furthermore, in preferred lytic method for polymerizing monomers. The invention is 25 embodiments, the catalysts are substantially more stable than applicable in numerous fields, including industrial chemistry previous non-metallic catalysts. and manufacturing processes requiring a simple and conve In some embodiments, then, the disclosure provides a nient method for the preparation of polymers. method for forming a polymer. The method comprises con tacting a monomer with a nucleophilic reagent in the presence BACKGROUND OF THE INVENTION 30 of a guanidine-containing compound to form a prepolymer. The method further comprises polymerizing the prepolymer Polymers containing heteroatoms along the backbone play to form a polymer. The monomer comprises at least one an ever-increasingly important role in modern Society, and the electrophilic moiety, and in Some embodiments, the mono variety of Such polymers continues to expand at a high rate. mer comprises two electrophilic moieties separated by a For example, poly(ethylene terephthalate) (i.e., poly(oxy-1, 35 linker. 2-ethanediyl-oxycarbonyl-1,4-diphenylenecarbonyl), O “PET) is a widely used engineering thermoplastic for car In further embodiments, the disclosure provides a compo peting, clothing, tire cords, Soda bottles and other containers, sition comprising a monomer, a nucleophile, and aguanidine film, automotive applications, electronics, displays, etc. The containing compound. The monomer comprises two electro worldwide production of PET has been growing at an annual 40 philic moieties separated by a linker. rate of 10% per year, and with the increase in use in electronic In still further embodiments, the disclosure provides an and automotive applications, this rate is expected to increase improved method for polymerizing a monomer having at significantly to 15% per year. least one electrophilic moiety. The improvement comprises Polymers with heteroatoms along the backbone are com contacting the monomer with a nucleophile in the presence of monly prepared using an addition-type polymerization 45 a guanidine-containing compound. mechanism, in which monomers react to form dimers, which Preferred catalysts herein are guanidine compounds. In can in turn react with other dimers to form tetramers. This Some embodiments, cyclic guanidines, including monocyclic growth process is allowed to continue until polymers with the and polycyclic guanidines are used. Polycyclic guanidines desired molecular weight are formed. Unfortunately (and suitable for the methods of the disclosure include fused and unlike the alternative chain-growth polymerization mecha 50 non-fused polycyclic compounds. Further details of suitable nism), obtaining high molecular weight polymer using this guanidine catalysts are provided below. mechanism requires carrying the polymerization reaction to Additional aspects and embodiments of the invention will very high conversion. be provided, without limitation, in the detailed description of A frequently-used method for commercial synthesis of the invention that is set forth below. (PET) involves a two-step transesterification process from 55 dimethyl teraphthalate (DMT) and excess ethylene glycol DETAILED DESCRIPTION OF THE INVENTION (EO) in the presence of a metal alkanoates or acetates of calcium, zinc, manganese, titanium, etc. This first step gen Unless otherwise indicated, this invention is not limited to erates bis(hydroxyethylene) teraphthalate (BHET) with the specific polymers, catalysts, nucleophilic reagents, or depo elimination of methanol and the excess EO. The BHET is 60 lymerization conditions. The terminology used herein is for heated, generally in the presence of a transesterification cata the purpose of describing particular embodiments only and is lyst, to generate high polymer. This process is generally not intended to be limiting. accomplished in a vented extruder to remove the polyconden As used in the specification and the appended claims, the sate (EO) and generate the desired thermoformed object from singular forms “a” “an.” and “the include plural referents a low viscosity precursor. 65 unless the context clearly dictates otherwise. Thus, for Some polycondensation reactions. Such as the commercial example, reference to “a polymer encompasses a combina method of synthesis of PET described above, require poly tion or mixture of different polymers as well as a single US 8,546,513 B2 3 4 polymer, reference to “a catalyst’ encompasses both a single example, methoxy, ethoxy, n-propoxy, isopropoxy, t-buty catalyst as well as two or more catalysts used in combination, loxy, etc. Substituents identified as "C-C alkoxy” or “lower and the like. alkoxy herein may, for example, may contain 1 to 3 carbon In this specification and in the claims that follow, reference atoms, and as a further example. Such Substituents may con will be made to a number of terms, which shall be defined to tain 1 or 2 carbonatoms (i.e., methoxy and ethoxy). The term have the following meanings: “alkylthio' as used herein refers to a group —S-alkyl, where As used herein, the phrase “having the formula' or “having “alkyl is as defined above. the structure' is not intended to be limiting and is used in the The term “arylas used herein, and unless otherwise speci same way that the term “comprising is commonly used. fied, refers to an aromatic Substituent generally, although not The term “alkyl as used herein refers to a linear, branched, 10 necessarily, containing 5 to 30 carbonatoms and containing a or cyclic Saturated hydrocarbon group (i.e., a mono-radical) single aromatic ring or multiple aromatic rings that are fused typically although not necessarily containing 1 to about 24 together, directly linked, or indirectly linked (such that the carbon atoms, such as methyl, ethyl, n-propyl, isopropyl. different aromatic rings are bound to a common group such as n-butyl, isobutyl, t-butyl, octyl, decyl, and the like, as well as a methylene or ethylene moiety). Aryl groups may, for cycloalkyl groups such as cyclopentyl, cyclohexyl and the 15 example, contain 5 to 20 carbon atoms, and as a further like. Generally, although not necessarily, alkyl groups herein example, aryl groups may contain 5 to 12 carbon atoms. For may contain 1 to about 18 carbonatoms, and Such groups may example, aryl groups may contain one aromatic ring or two or contain 1 to about 12 carbon atoms. The term “lower alkyl more fused or linked aromatic rings (i.e., biaryl, aryl-substi intends an alkyl group of 1 to 6 carbon atoms. “Substituted tuted aryl, etc.). Examples include phenyl, naphthyl, biphe alkyl refers to alkyl substituted with one or more substituent nyl, diphenylether, diphenylamine, benzophenone, and the groups, and this includes instances wherein two hydrogen like. “Substituted aryl” refers to an aryl moiety substituted atoms from the same carbon atom in an alkyl Substituent are with one or more Substituent groups, and the terms "heteroa replaced, such as in a carbonyl group (i.e., a Substituted alkyl tom-containing aryland "heteroaryl” refer to aryl substitu group may include a C(=O)-moiety). The terms "heteroa ent, in which at least one carbon atom is replaced with a tom-containing alkyl and "heteroalkyl refer to an alkyl 25 heteroatom, as will be described in further detail infra. If not substituent in which at least one carbonatom is replaced with otherwise indicated, the term “aryl includes unsubstituted, a heteroatom, as described in further detail infra. If not oth Substituted, and/or heteroatom-containing aromatic Substitu erwise indicated, the terms “alkyl and “lower alkyl include entS. linear, branched, cyclic, unsubstituted, Substituted, and/or The term “aralkyl refers to an alkyl group with an aryl heteroatom-containing alkyl or lower alkyl, respectively. 30 substituent, and the term "alkaryl” refers to an aryl group with The term “alkenyl as used herein refers to a linear, an alkyl substituent, wherein “alkyl and “aryl areas defined branched or cyclic hydrocarbon group of 2 to about 24 carbon above. In general, aralkyland alkaryl groups herein contain 6 atoms containing at least one double bond, such as ethenyl, to 30 carbon atoms. Aralkyl and alkaryl groups may, for n-propenyl, isopropenyl. n-butenyl, isobutenyl, octenyl, example, contain 6 to 20 carbon atoms, and as a further decenyl, tetradecenyl, hexadecenyl, eicosenyl, tetracosenyl, 35 example, Such groups may contain 6 to 12 carbon atoms. and the like. Generally, although again not necessarily, alk The term “alkylene' as used herein refers to a di-radical enyl groups herein may contain 2 to about 18 carbon atoms, alkyl group. Unless otherwise indicated, such groups include and for example may contain 2 to 12 carbonatoms. The term saturated hydrocarbon chains containing from 1 to 24 carbon “lower alkenyl' intends an alkenyl group of 2 to 6 carbon atoms, which may be substituted or unsubstituted, may con atoms. The term “substituted alkenyl refers to alkenyl sub 40 tain one or more alicyclic groups, and may be heteroatom stituted with one or more Substituent groups, and the terms containing "Lower alkylene' refers to alkylene linkages con "heteroatom-containing alkenyl and "heteroalkenyl refer taining from 1 to 6 carbon atoms. Examples include, to alkenyl in which at least one carbon atom is replaced with methylene (-CH ), ethylene (—CH2CH2—), propylene a heteroatom. If not otherwise indicated, the terms “alkenyl (—CH2CHCH ), 2-methylpropylene (—CH2—CH and “lower alkenyl' include linear, branched, cyclic, unsub 45 (CH)—CH2—), hexylene (-(CH2) ) and the like. Simi stituted, Substituted, and/or heteroatom-containing alkenyl larly, the terms “alkenylene.” “alkynylene.” “arylene.” and lower alkenyl, respectively. “aralkylene, and "alkarylene' as used herein refer to di The term “alkynyl as used herein refers to a linear or radical alkenyl, alkynyl, aryl, aralkyl, and alkaryl groups, branched hydrocarbon group of 2 to 24 carbon atoms con respectively. Collectively, these and other di-radical groups taining at least one triple bond, such as ethynyl. n-propynyl, 50 are referred to herein as “linkers' or “linker groups.” By the and the like. Generally, although again not necessarily, alky term “functional linker group' or “functional linker' is meant nyl groups herein may contain 2 to about 18 carbon atoms, di-radical moieties that contain one or more functional groups and Such groups may further contain 2 to 12 carbon atoms. Such as an oxo (—O—, Such as in an linkage), amine The term “lower alkynyl' intends an alkynyl group of 2 to 6 ( NR—), carbonyl ( C(=O)—), carbonate, and the like. carbon atoms. The term “substituted alkynyl refers to alky 55 The term “amino' is used herein to refer to the group— nyl Substituted with one or more Substituent groups, and the NZZ wherein Z' and Z are hydrogen or nonhydrogen sub terms "heteroatom-containing alkynyl and "heteroalkynyl stituents, with nonhydrogen Substituents including, for refer to alkynyl in which at least one carbon atom is replaced example, alkyl, aryl, alkenyl, aralkyl, and Substituted and/or with a heteroatom. If not otherwise indicated, the terms “alky heteroatom-containing variants thereof. nyl' and “lower alkynyl' include linear, branched, unsubsti 60 The terms “halo' and “halogen' are used in the conven tuted, Substituted, and/or heteroatom-containing alkynyl and tional sense to refer to a chloro, bromo, fluoro or iodo Sub lower alkynyl, respectively. stituent. The term “alkoxy” as used herein intends an alkyl group The term "heteroatom-containing as in a "heteroatom bound through a single, terminal ether linkage; that is, an containing alkyl group' (also termed a "heteroalkyl group) “alkoxy” group may be represented as —O-alkyl where alkyl 65 or a "heteroatom-containing aryl group' (also termed a "het is as defined above. A “lower alkoxy” group intends an alkoxy eroaryl group) refers to a molecule, linkage or Substituent in group containing 1 to 6 carbon atoms, and includes, for which one or more carbon atoms are replaced with an atom US 8,546,513 B2 5 6 other than carbon, e.g., nitrogen, oxygen, Sulfur, phosphorus (—PO), and phosphino (—PH), mono- and di-(C-C, or silicon, typically nitrogen, oxygen or Sulfur. Similarly, the alkyl)-substituted phosphino, mono- and di-(Cs-Co aryl)- term "heteroalkyl refers to an alkyl substituent that is het Substituted phosphino; and the hydrocarbyl moieties C-C, eroatom-containing, the term "heterocyclic” refers to a cyclic alkyl (including C-Cs alkyl, further including C-C alkyl, Substituent that is heteroatom-containing, the terms "het 5 and further including C-C alkyl), C-C alkenyl (including eroaryland "heteroaromatic' respectively refer to “aryland C-Cls alkenyl, further including C-C alkenyl, and further 'aromatic Substituents that are heteroatom-containing, and including C-C alkenyl), C2-C2-alkynyl (including C-C1s the like. Examples of heteroalkyl groups include alkoxyaryl, alkynyl, further including C-C alkynyl, and further includ alkylsulfanyl-substituted alkyl, N-alkylated amino alkyl, and ing C-C alkynyl), Cs-Clso aryl (including Cs-Co aryl, and the like. Examples of heteroaryl substituents include pyrrolyl, 10 pyrrolidinyl, pyridinyl, quinolinyl, indolyl, furyl, pyrimidi further including Cs-Caryl), and Co-Co aralkyl (including nyl, imidazolyl, 1,2,4-triazolyl, tetrazolyl, etc., and examples C-Caralkyl, and further including C-Caralkyl). In addi of heteroatom-containing alicyclic groups are pyrrolidino, tion, the aforementioned functional groups may, if a particu morpholino, piperazino, piperidino, tetrahydrofuranyl, etc. lar group permits, be further substituted with one or more additional functional groups or with one or more hydrocarbyl “Hydrocarbyl refers to univalent hydrocarbyl radicals 15 containing 1 to about 30 carbon atoms, including 1 to about moieties such as those specifically enumerated above. Analo 24 carbon atoms, further including 1 to about 18 carbon gously, the above-mentioned hydrocarbyl moieties may be atoms, and further including about 1 to 12 carbon atoms, further substituted with one or more functional groups or including linear, branched, cyclic, Saturated and unsaturated additional hydrocarbyl moieties such as those specifically species, such as alkyl groups, alkenyl groups, aryl groups, and enumerated. In addition, the aforementioned functional groups may, ifa the like. “Substituted hydrocarbyl refers to hydrocarbyl sub particular group permits, be further substituted with one or stituted with one or more Substituent groups, and the term more additional functional groups or with one or more hydro "heteroatom-containing hydrocarbyl refers to hydrocarbyl carbyl moieties such as those specifically enumerated above. in which at least one carbon atom is replaced with a heteroa Analogously, the above-mentioned hydrocarbyl moieties tom. Unless otherwise indicated, the term “hydrocarbyl is to 25 may be further substituted with one or more functional groups be interpreted as including Substituted and/or heteroatom or additional hydrocarbyl moieties such as those specifically containing hydrocarbyl moieties. The term “hydrocarbylene’ enumerated. refers to a di-radical hydrocarbyl group. When the term “substituted' appears prior to a list of pos By “substituted as in “substituted hydrocarbyl,” “substi sible Substituted groups, it is intended that the term apply to tuted alkyl.” “substituted aryl, and the like, as alluded to in 30 every member of that group. For example, the phrase “sub Some of the aforementioned definitions, is meant that in the stituted alkyl and aryl” is to be interpreted as “substituted hydrocarbyl, alkyl, aryl, or other moiety, at least one hydro alkyl and substituted aryl gen atom bound to a carbon (or other) atom is replaced with Unless otherwise specified, reference to an atom is meant one or more non-hydrogen Substituents. Examples of Such to include isotopes of that atom. For example, reference to H Substituents include, without limitation: functional groups 35 is meant to include "H. H. (i.e., D) and H (i.e., T), and Such as halo, hydroxyl, Sulfhydryl, C-C alkoxy, C-C, reference to C is meant to include ''C and all isotopes of alkenyloxy, C-C alkynyloxy, Cs-Co aryloxy, acyl (includ carbon (such as 'C). ing C-C alkylcarbonyl (-CO-alkyl) and Co-Co arylcar By “substantially free of a particular type of chemical bonyl (-CO-aryl)), acyloxy (—O-acyl), C-C alkoxycar compound is meant that a composition or product contains bonyl (—(CO)—O-alkyl). Co-Co aryloxycarbonyl 40 less 10 wt % of that chemical compound, for example less (—(CO)—O-aryl), halocarbonyl ( CO)—X where X is than 5 wt %, or less than 1 wt %, or less than 0.1 wt %, or less halo), C-C alkylcarbonato (—O—(CO)—O-alkyl). than 0.01 wt %, or less than 0.001 wt %. For instance, the Co-Co arylcarbonato (—O—(CO)—O-aryl), carboxy polymerization product herein is “substantially free of metal (—COOH), carboxylato (-COO), carbamoyl (—(CO)— contaminants, including metals per se, metal salts, metallic NH), mono-Substituted C-C alkylcarbamoyl (-(CO)— 45 complexes, metal alloys, and organometallic compounds. NH(C-C alkyl)), di-substituted alkylcarbamoyl Unless otherwise specified, the terms 'guanidine com (—(CO)—N(C-C alkyl)), mono-substituted arylcarbam pound,' 'guanidine catalyst.” “guanidine-containing com oyl (—(CO)—NH-aryl), thiocarbamoyl ( (CS) NH), pound, and the like refer to compounds containing aguanidi carbamido ( NH-(CO) NH), cyano ( -C=N), isocy nyl moiety, i.e., compounds containing the structure ano ( N=C), cyanato ( O C=N), isocyanato ( O— 50 N"=C), isothiocyanato ( S C=N), azido ( N=N* —N), formyl (—(CO)—H), thioformyl (—(CS)—H), amino (-NH), mono- and di-(C-C alkyl)-substituted amino, mono- and di-(Cs-Co aryl)-substituted amino, C-C alkylamido (-NH-(CO)-alkyl), Cs-Co arylamido 55 ( NH (CO)-aryl), imino ( CR-NH where Rhydrogen, C-C2 alkyl, Cs-Co aryl, Co-Co alkaryl, Co-Co aralkyl, etc.), alkylimino (—CR=N(alkyl), where R=hydrogen, alkyl, aryl, alkaryl, etc.), arylimino ( CR=N (aryl), where R hydrogen, alkyl, aryl, alkaryl, etc.), nitro 60 Accordingly, the invention features a method for preparing ( NO), nitroso ( NO), sulfo ( -SO, OH), sulfonato a polymer having a backbone containing electrophilic link (—SO O), C-C alkylsulfanyl ( S-alkyl; also termed ages. The electrophilic linkages may be, for example, “alkylthio'), arylsulfanyl ( S-aryl; also termed “arylthio'). linkages (—(CO)—O—), carbonate linkages (—O—(CO)— C-C alkylsulfinyl (—(SO)-alkyl), Cs-Co arylsulfonyl O)—, urethane linkages (—O—(CO)- NH), substituted (—(SO)-aryl), C-C alkylsulfonyl ( -SO-alkyl), Cs-Co 65 urethane linkages (—O—(CO) NR—, where R is a nonhy arylsulfonyl (—SO-aryl), phosphono ( P(O)(OH)), phos drogen Substituent such as alkyl, aryl, alkaryl, or the like), phonato ( -P(O)(O)), phosphinato ( -P(O)(O)), phospho amido linkages (—(CO) NH ), substituted amido link US 8,546,513 B2 7 8 ages (—(CO) NR— where R is as defined previously), boxylates) Such as poly(2.2.2-bicyclooctane-1,4-dimethyl thioester linkages (—(CO)—S ), Sulfonic ester linkages ene ethylenedicarboxylate); lactic acid polymers and copoly (—S(O) O—), ketone linkages (—C(=O)—), and the mers such as (S)-polylactide, (R.S)-polylactide, poly like. Other electrophilic linkages will be known to those of (tetramethylglycolide), and poly(lactide-co-glycolide); and ordinary skill in the art of organic chemistry and polymer 5 polycarbonates of bisphenol A, 3,3'-dimethylbisphenol A, science and/or can be readily found by reference to the per 3.3',5,5'-tetrachlorobisphenol A, 3,3',5,5'-tetramethylbisphe tinent texts and literature. nol A; polyamides such as poly(p-phenylene terephthala In some embodiments, the monomer comprises two elec mide); poly(alkylene carbonates) such as poly(propylene car trophilic moieties separated by a linker moiety, and has the bonate); polyurethanes; and polyurethane/polyester structure X-L-X, wherein X" and X’ are independently 10 copolymers. electrophilic moieties and L is the linker moiety. In some embodiments, L is selected from C-Cohydrocarbylene and The monomers for polymerization may be obtained from functional linker groups. In some embodiments, L is C-Clso any Suitable source. In one preferred embodiment, the mono hydrocarbylene. For example, L is selected from C-C alky mers are depolymerization products from recycled post-con lene, C-C soalkenylene, Ca-Cao alkynylene, Cs-Cao arylene, 15 Sumer waste. In another embodiment, the monomers are Vir and combinations thereof (such as C-C alkylene linked gin feedstock. with a Cs-Co arylene), wherein any of these groups may Polymerization of the monomer is carried out, as indicated contain one or more heteroatoms and one or more substitu herein, in the presence of a nucleophilic reagent and a cata ents. Linker moieties may also be functional groups, such as lyst. Nucleophilic reagents are those that comprise one or heteroatom groups, including thioether ( -S ), ether more nucleophilic groups, such as hydroxyl, ether, carboxy (—O—), and amino ( NR—) groups. In some embodi lato (e.g., -COO), amine, azide, Sulfhydryl, and the like. ments, L is Substituted or unsubstituted phenylene (14-, 1.3-, Nucleophilic reagents therefore include monohydric alco or 1.2-connectivity), or substituted or unsubstituted lower hols, diols, polyols, amines, diamines, polyamines, Sulfhydr alkylene (e.g., methylene, ethylene, propylene, butylene, yls, disulfhydryls, polysulfhydryls, and combinations pentylene, hexylene, Septylene, or octylene, including cyclic 25 thereof. Thus, the nucleophilic reagents may contain a single versions of Such linkers). nucleophilic moiety or two or more nucleophilic moieties, In some embodiments, X" and X’ are independently e.g., hydroxyl, Sulfhydryl, and/or amino groups. selected from ester moieties (—(CO)—O—R, wherein R is In some embodiments, the nucleophilic reagent consists of lower alkyl or the like), or carbonic acid a single nucleophilic group, and has the structure R-Nu', (—COOH or —OCOOH), carbonate moieties (—O— 30 wherein R is a C-Co hydrocarbyl group and Nu' is any (CO) O—R, wherein R is lower alkyl or the like), urethane nucleophilic group such as those previously described. moieties (-O-(CO) NH R, wherein R is H. lower alkyl, or the like), substituted urethane moieties (—O—(CO)— In Some embodiments, nucleophilic reagents comprise two NR' R, where R' is a nonhydrogen substituent such as alkyl, nucleophilic groups separated by a linker, and have the struc aryl, alkaryl, or the like), amido moieties (—(CO)—NH R. 35 ture Nu'-L'-Nui, wherein Nu' is as described previously, wherein R is H. lower alkyl, or the like), substituted amido Nu is a nucleophilic group (such as those described for Nu') moieties (—(CO)—NR' R where R' is as defined previ and wherein L' is as described previously for L. Examples of ously), thioester moieties (—(CO)—S R, wherein R is H. Such difunctional nucleophilic reagents include alkyl diols, lower alkyl, or the like), sulfonic ester moieties (—S(O)— aryl diols, alkyl diamines, aryl diamines, amino alcohols, O—R, wherein R is H. lower alkyl, or the like), and the like. 40 amino thiols, and the like. For example, X and X’ are lower alkyl esters (e.g., methyl In some embodiments, the nucleophilic reagent comprises esters or ethyl esters) or amine groups. three nucleophilic groups, and has the structure Examples of polymers that can be prepared using the meth odology of the invention include, without limitation: poly (alkylene terephthalates) such as poly(ethylene terephthalate) 45 Nul-L-Nu? (PET), fiber-grade PET (a homopolymer made from mono ethylene glycol and terephthalic acid), bottle-grade PET (a Nu copolymer made based on monoethylene glycol, terephthalic acid, and other comonomers such as isophthalic acid, cyclo (also written Nu-L(Nul)Nu) wherein Nu' and Nuare hexene dimethanol, etc.), poly(butylene terephthalate) 50 as described previously, Nu is a nucleophilic group (such as (PBT), and poly(hexamethylene terephthalate); poly(alky those described for Nu'), and Li may be any of the linkers lene adipates) Such as poly(ethylene adipate), poly(1,4-buty described previously for L', provided that linker L has at lene adipate), and poly(hexamethylene adipate); poly(alky least three non-hydrogen substituents (i.e., Nu'-Nui). Such lene Suberates) such as poly(ethylene Suberate); poly nucleophilic reagents allows cross linking reactions to occur. (alkylene sebacates) Such as poly(ethylene sebacate); poly(e- 55 Any combination of nucleophilic reagents (having the same ) and poly(3-propiolactone); poly(alkylene or a different number of nucleophilic groups) may be used. isophthalates) Such as poly(ethylene isophthalate); poly In some embodiments, the nucleophilic reagent will be (alkylene 2,6-naphthalene-dicarboxylates) Such as poly(eth present in excess of the monomer, meaning that the number of ylene 2,6-naphthalene-dicarboxylate); poly(alkylene Sulfo nucleophilic groups exceeds the number of electrophilic nyl-4,4'-dibenzoates) such as poly(ethylene Sulfonyl-4,4'- 60 groups at the beginning of the reaction. In some other dibenzoate); poly(p-phenylene alkylenedicarboxylates) Such embodiments, the ratio of nucleophilic groups to electro as poly(p-phenylene ethylene dicarboxylates); poly(trans-1, philic groups is 1:1. 4-cyclohexanediyl alkylene dicarboxylates) such as poly A few specific examples of Suitable nucleophilic groups (trans-1,4-cyclohexanediyl ethylene dicarboxylate); poly(1, include methanol, ethanol, propanol, butanol, ethylene gly 4-cyclohexane-dimethylene alkylenedicarboxylates) Such as 65 col, propylene glycol, methylamine, ethylamine, ethylenedi poly(1,4-cyclohexane-dimethylene ethylene dicarboxylate); amine, propylenediamine, methanethiol, ethanethiol, as well poly(2.2.2-bicyclooctane-1,4-dimethylene alkylene dicar as the following: US 8,546,513 B2 9 10 heteroatom-containing, provided that any two of R", R', HN HS HN R. R. R7, R7, R', and R' may be taken togetherto form 2 N1) on N1\on. 2 N1\si. a ring. HS N1\s. OH, In some embodiments of formula (Ia), n1 is Zero and n2 is 5 1. In some embodiments of formula (Ia), n2 is Zero and n1 is HO 1. In some embodiments of formula (Ia), n1 and n2 are both Zero. In some embodiments of formula (Ia), n1 and n2 are OH, both 1. In some embodiments of formula (Ia), one of R" and R' HN 10 is Cs-Co aryl, and the other is Hydrogen, and one of R'' and NH2, and R’ is Cs-Co aryl, and the other is H. In some such embodi ments, the Cs-Co aryl group is phenyl. HN In some embodiments of formula (Ia), R. R. R', and R" are each H. Examples of such embodiments include the SH. 15 following compounds: HS

Preferred catalysts for the polymerization reactions are organic compounds containing a guanidine moiety. In some preferred embodiments, the polymerization catalysts are organic guanidines having the structure of formula (I)

25 (I) In some embodiments of formula (I), R and Rare taken together to form a cycle. For example, preferred embodi 30 ments include compounds having the structure of formula (Ib) wherein R. R. Rand Rare independently selected from hydrogen and C-Clso hydrocarbyl, provided that any two of (Ib) R. R. RandR may be linked to form a cycle. In preferred 35 embodiments, at least two of R. R. R. and Rare linked to form a cycle. Such that the compound is a cyclic guanidine compound. For example, R. R. Rand Rare independently selected from Substituted or unsubstituted C-Clso alkyl, C-Co alk 40 enyl, C-Clso alkynyl, Cs-Co aryl, Co-Coaralkyl, and Co-Co alkaryl, any of which may be heteroatom-containing. As mentioned previously, the alkyl, alkenyl, and alkynyl groups wherein include linear, branched, and cyclic Such groups. The aryl, n3 is selected from 0 and 1: aralkyl, and alkaryl groups include multicyclic groups such as 45 X' and X’ are independently selected from —NR'' and annulated and linked ring systems. —C(R')(R') , wherein R', R'', and R'' are indepen In some embodiments of formula (I), R and Rare taken dently selected from H and alkyl; and together to form a cycle, and Rand Rare taken together to R", R. R', and R” are independently selected from form a cycle. Such that an annulated ring system is formed. alkyl, aryl, aralkyl, and alkaryl, provided that any two of R". Preferred embodiments include compounds having the struc 50 R,R,R,R,R'', and R' may be taken together to form ture of formula (Ia) a cycle. In some embodiments of formula (Ib), RandR'' are both H, andX' and X’ are both —CH2—, such that the compounds (Ia) 55 have the structure of formula (Ic)

(Ic)

p3 60

wherein n1 and n2 are independently selected from Zero and 1; and R, R, R, R, R7, R7, R7, and R7 are indepen dently selected from H. Substituted or unsubstituted C-Co 65 alkyl, C2-Cso alkenyl, C-Clso alkynyl, Cs-Clso aryl, C-Clso aralkyl, and Co-Co alkaryl, any of which may be may be US 8,546,513 B2 11 12 Further examples of embodiments of formula (Ib) include The initial formation of the prepolymer may be carried out compounds having the structures in a suitable solvent, or without any solvent. The nucleophilic reagent may function as a solvent. When a separate solvent is used, it is preferable that the solvent is removed prior to Ph N polymerization of the prepolymer. Thus, in some embodi OH ments, the polymerization reaction is started in a solvent for a predetermined period of time, after which time the solvent is N Ph N N removed (such as by applying reduced pressure and/or increased temperature), and the polymerization is allowed to N N R5 or R& N ls N -R. 10 continue for a period of time sufficient to provide polymer of H H the desired molecular weight. The polymerization reaction may be carried out in an inert In some embodiments of the structures shown above, R atmosphere. In carrying out the reactions, combination of the and Rare independently selected from substituted or unsub reactants may be accomplished in any order. For example, the stituted C-C alkyland substituted or unsubstituted heteroa 15 reactants can be combined by dissolving a catalytically effec tom-containing C-C soalkyl. For example, RandR may be tive amount of the selected catalyst in a solvent, combining Cs-Coalicyclic, Such as cyclopropyl, cyclobutyl, cyclopen the monomer and the catalyst solution, and then adding the tyl, cyclohexyl (Cy), cycloheptyl, or cyclooctyl. Also, for nucleophilic reagent. In a particularly preferred embodiment, example, R and R may be methyl, ethyl, propyl (i-propyl, the monomer, the nucleophilic reagent, and the catalyst are combined and dissolved in a suitable solvent, and polymer n-propyl), or butyl (t-butyl, n-butyl, sec-butyl), or may be ization thus occurs in a one-pot, one-step reaction. heteroatom-containing such as 3-dimethylaminopropyl or a The reaction mixture is typically, although not necessarily, salt thereof. agitated (e.g., stirred), and the progress of the reaction can be In some embodiments, the guanidine-containing com monitored by standard techniques, although visual inspection pounds described herein are chemically more stable than 25 is generally Sufficient. Examples of solvents that may be used other catalysts capable of causing depolymerization, Such as in the polymerization reaction include organic, protic, or N-heterocyclic carbene catalysts. In some embodiments, aqueous solvents that are inert under the polymerization con compared with N-heterocyclic carbene catalysts under simi ditions, such as aromatic hydrocarbons, chlorinated hydro lar conditions, the guanidine-containing compounds decom carbons, , aliphatic hydrocarbons, or mixtures thereof. pose at a substantially lower rate. Preferred catalysts are 30 Preferred solvents include toluene, methylene chloride, tet substantially stable under some or all of the depolymerization rahydrofuran, methylt-butyl ether, Isopar, gasoline, and mix conditions described herein. tures thereof. Reaction temperatures are in the range of about The guanidine-containing compounds described herein 25°C. to about 300°C. The total polymerization reaction time may be synthesized by any appropriate method, and Such will generally, although again not necessarily, be in the range methods are readily ascertainable from the relevant literature. 35 of about 1 to 24 hours. For example, cyclic guanidines may be prepared using the In some embodiments, the reactions are carried out by first methods disclosed in U.S. Pat. No. 4,797.487 entitled “Pro combining the monomer with the nucleophilic reagent and duction of Bicyclic Guanidines from Bis(aminoalkyl)amine.” the catalyst in a solvent. After allowing sufficient time for the It will be appreciated that the handling of certain guanidine monomer to react with the nucleophilic reagent to form a 40 prepolymer, the reaction conditions are changed to encourage containing compounds may require precautions to avoid polymerization of the prepolymer. For example, elevated decomposition. For example, mixing of the reaction compo temperature and/or reduced pressure may be applied in order nents may require an inert atmosphere. to force the condensation of prepolymer molecules. In some The polymerization catalysts of the disclosure (i.e., guani embodiments, the temperature of the reaction after formation dine-containing compounds) are typically present in the reac 45 of the prepolymer is raised to between 100° C. and 200°C., or tion mixture in an amount (i.e., a “catalyst loading) that is greater than about 150° C., or greater than about 170° C. The less than 5 mol%, or less than 2 mol%, or less than 1 mol%. amount of time required to form the prepolymer from the or less than 0.5 mol%, or less than 0.1 mol %, with less than monomer and the nucleophilic reagent will vary depending 1 mol % being particularly preferred. Such catalyst loadings upon the reactants and conditions, but may be estimated or are measured as mol% relative to the total amount of mono 50 determined by the usual analytical methods. The temperature mer used in the reaction. during formation of the prepolymer may be room temperature The polymerization reaction occurs by initial formation of or higher, for example between 30° C. and 100° C. a prepolymer comprising the product of a reaction between The polymerization product from reactions according to the monomer and nucleophilic reactant, and Subsequent con the invention contains product polymer and the guanidine densation polymerization of the prepolymer. In some 55 containing catalyst, which may be removed from the polymer embodiments, the prepolymer comprises one or more elec product in the usual manner. trophilic groups and one or more nucleophilic groups; for Because the polymerization catalysts disclosed herein do example the prepolymer comprises two nucleophilic groups not contain metals, the methods of the disclosure allow for the and two electrophilic groups. In such embodiments, the con polymerization of a monomer starting material to provide a densation reaction may occur as the electrophilic group of 60 polymerization product that is substantially free of metal one prepolymer molecule reacts with the nucleophilic group contaminants. In particular, the concentration of metal con of another prepolymer molecule. In embodiments where the taminants in the polymer products is equal to or less than the condensation reaction produces non-polymeric byproducts concentration of metal contaminants in the starting materials (particularly Small organic molecules such as water, H2, eth prior to polymerization. For example, when a sample of dim ylene glycol, propylene glycol, etc.), such products may be 65 ethyl terephthalate (DMT) is polymerized according to the removed during the reaction to help the polymerization invention, and the sample of DMT has a certain concentration achieve higher molecular weight polymers. of metal contaminant (e.g., residual metals from any reaction US 8,546,513 B2 13 14 that was used to prepare the DMT, such as a metal catalyst DMT (0.5 grams, 0.0025 mol) was added to around bottom used in a depolymerization reaction recycling PET into DMT flask together with ethylene glycol (0.62 grams, 0.01 mol). To via depolymerization), the polymerization reaction according this slurry, TBD (0.006 grams, 0.00005 mol) was added. The to the invention does not increase the total concentration of reaction was heated to 40°C. under vacuum (3 hours), 100° C. metal contaminants. The polymer products (e.g., PET) con (1 hour) and 200° C. for 3 hours. tain the same or lower concentration of metal contaminants as the starting materials. A lower concentration of metal con Example 2 taminant may be observed if the polymer products are sub jected to any purification steps (such as precipitation, filtra Sample 2 was also PET that was polymerized with 1.5 mol tion, etc.). As a further example, a sample of DMT having no 10 % catalyst relative to DMT. The maximum polymerization metal contaminants (or an undetectable level of metal con temperature in this case was 275°C. taminants) may be polymerized according to the invention to DMT (3.0 grams, 0.015 mole) and ethylene glycol (6.5 yield polymer products having no metal contaminants (or an grams, 0.01 mol) was added to a round bottom flask together undetectable level of metal contaminants). with TBD (0.01 grams, 0.000075 mol). The reaction was In some embodiments, the polymerization reactions of the 15 disclosure allow preparation of polymer products having a heated to 40° C. under nitrogen (2 hours), heated to 60° C. metal contaminant concentration that is immeasurable or under vacuum (30 min) and heated to 100° C. (vacuum, 1 equal to or less than the metal contaminant concentration of hour). The reaction was then heated to 150° C. (vacuum, 35 the starting materials used to prepare the polymer. Such poly min. where it became homogeneous. The reaction was then mer products may have Substantially less metal contaminant heated to 200° C. (1.5 hours) and then 275° C. (1 hour) to concentrations than similar polymers prepared using conven finish the reaction. tional (i.e., metal catalyzed) polymerization methods. The product polymers were characterized by H NMR. For example, depending on the method of manufacture, Example 3 conventional PET used for drinking bottles may have a residual metal contamination level of up to 50 ppm, or up to 25 Combining bis(hydroxy ethylene) terephthalate (BHET) 20 ppm, or up to 5 ppm. In some embodiments, the methods with 1,5,7-triazabicyclo4.4.0dec-5-ene (TBD) and heating of the invention provide PET suitable for food and beverage the mixture under vacuum results in the formation of poly storage since the level of metal contamination of the poly (ethylene terephthalate). Polymerization can also be carried merization products will be no higher than the level of metal out by heating dimethyl terephthalate with ethylene glycol in contamination of the original monomer. Thus, in some 30 the presence of TBD catalysts followed by heating under embodiments, the methods of the invention provide polymers having a metal contamination concentration of s50 ppm, or vacuum. This process is shown in Scheme 1. s20 ppm, or ss ppm, or below 1 ppm. The methods described herein find utility, for example, in the preparation of polymers and items made from polymers, 35 the use of recycled polymer depolymerization products, and similar areas as described herein throughout. All patents, patent applications, and publications men tioned herein are hereby incorporated by reference in their entireties. However, where a patent, patent application, or 40 -- publication containing express definitions is incorporated by OH reference, those express definitions should be understood to Ho-1N1 apply to the incorporated patent, patent application, or pub lication in which they are found, and not to the remainder of N the text of this application, in particular the claims of this 45 application. It is to be understood that while the invention has been CO described in conjunction with the preferred specific embodi O O ments thereof, that the foregoing description as well as the examples that follow, are intended to illustrate and not limit 50 the scope of the invention. It will be understood by those in-1 ( ) -- skilled in the art that various changes may be made and equivalents may be substituted without departing from the Scope of the invention, and further that other aspects, advan O O tages and modifications will be apparent to those skilled in the 55 art to which the invention pertains. HO OH EXAMPLES {-no ornpi

Example 1 60 Example 4 Sample 1 is a PET that was polymerized (bulk) with 2 mol % of catalysts relative to DMT. Since the concentration of Synthesis of 1,4,6-triazabicyclo[3.3.0-oct-4-ene (TBO). ethylene glycol tends to vary during the course of the poly With stirring at room temperature under nitrogen atmosphere, merization, all catalysts loadings are relative to dimethyl 65 xylenes (300 mL), diethylenetriamine (20.6 g. 21.7 mL, 0.2 terephthalate (DMT). The maximum polymerization tem mol), and carbon disulfide (15.2 g, 12.0 mL, 0.2 mol) were perature in the case was 200° C. added to a three-necked flask. A white precipitate formed US 8,546,513 B2 15 16 immediately and the Suspension was heated to reflux. Evolu tion of HS from the reaction exhaust was monitored using filter paper soaked in a methanolic Suspension of lead(II) acetate. After 10 days of reflux under nitrogen, GC/MS analy sis confirmed quantitative conversion to the target compound. CO Upon cooling to room temperature a white solid crystallized from Solution, and the Supernatant was decanted. The Solid was washed with 2x50 mL portions of acetone and pentane, ()--() respectively, and dried under vacuum overnight. (8.65 g, 39%). H NMR 400 MHz (CDC1).differential. (ppm)=6.02 10 brs, 1H, N-H, 3.79t, 2H, backbone CH, J–7.0 Hz), 3.05 Synthesis of Guanidinium 3: DCC (0.70 g, 3.39 mmol) It, 2H, backbone CH, J=70 Hz). ''C NMR 100.6 MHz and (S)-(-) O.C.-diphenyl-2-pyrrolidinemethanol (0.86 g. (CDC1).differential. (ppm)=171.18 central sp’ C, 52.62 3.39 mmol) were heated (under N) at 80° C. for 20 h. Tem backbone CH, 49.38 backbone CH). LRMS (m/z): 112.1 15 peratures above 100° C. resulted in decomposition. The prod (positive ion, M+H). uct was purified using column chromatographs (ethyl acetate/ Example 5 hexane (60/40)) to yield a white crystalline solid T=104 106° C. The product guanidine compound has the structure Synthesis of Guanidine catalysts. The general procedure is shown below. shown in Scheme 2.

25

Scheme 2 R R H n N Y 30 Cy-N=C=N-Cy + N He 1s R 1 N.,R Cy-N SNcy H We claim: 35 1. A composition comprising a monomer, a nucleophile, and a guanidine-containing compound according to Formula (Ib) DCC was reacted neat (110°C.) with a secondary amine. Once the DCC melted a homogeneous solution was formed 40 and the reaction was allowed to proceed overnight to generate (Ib) a viscous oil/gel. The reaction was followed by GC/MS and quantitative conversion of starting material was accom plished in about. 12 hours. Compounds were purified either by kugelroh distillation or by column chromatography. 45 Synthesis of Guanidinium 1: Dicyclohexylcarbodiimide (3 g, 14.8 mmol) and pyrrolidine (10 ml, 120 mmol) were heated to reflux overnight under N. The excess pyrrolidine was distilled off and the product was purified by Kugelroh distil lation (265°C.) to yield a colorless oil. The product guanidine 50 wherein the monomer comprises two electrophilic moi compound has the structure shown below. eties separated by a linker and further wherein: n3 is selected from 0 and 1: X' and X’ are independently selected from the group 55 consisting of NR'' and C(R')(R') , wherein R', R'', and R'' are independently selected from Hand alkyl: R° and Rare independently selected from the group con sisting of Substituted and unsubstituted C-Clso alkyl, 60 and Synthesis of Guanidinium 2: DCC (0.93 g, 4.52 mmol) and R. R. R', and Rare independently selected from the TBD (0.66g, 4.76 mmol) were allowed to react for 20 (125° group consisting of H and Substituted and unsubstituted C. under N). The gel like product was purified by Kugelroh alkyl, aryl, aralkyl, and alkaryl, any of which may be distillation 265°C. to yield a white crystalline solid T=69 65 heteroatom-containing, provided that any two of R, 71° C. The product guanidine compound has the structure R,R,R,R,R'', and R' may be taken together to shown below. form a cycle. US 8,546,513 B2 17 18 2. The composition of claim 1, wherein the guanidine anediyl alkylene dicarboxylates), poly(1,4-cyclohexane containing compound has the structure dimethylene alkylene dicarboxylates), poly(2.2.2]- bicyclooctane-1,4-dimethylene alkylene dicarboxylates), polycarbonates of bisphenol A, polyamides, poly(alkylene carbonates), lactic acid polymers and copolymers, polyure Ph thanes and polyurethane/polyester copolymers, poly(e-ca OH Or prolactone), and poly(B-propiolactone). C-é CO 11. A polymer comprising the composition of claim 1, wherein the polymer comprises poly(ethylene terephthalate) R N - R. 2 R5. 2SN N1 RS lss 1 10 (PET). H 12. A polymer comprising the composition of claim 1, wherein the polymer comprises poly(butylene terephthalate) 3. The composition of claim 1, wherein the guanidine (PBT). containing compound is present in an amount effective to 13. A polymer comprising the composition of claim 1, cause reaction of the electrophilic moiety with the nucleo 15 wherein the polymer comprises poly(hexamethylene tereph phile. thalate). 4. The composition of claim 1, wherein the guanidine 14. A polymer comprising the composition of claim 1, containing compound is present in an amountless than about wherein the polymer is selected from the group consisting of 1 mol % relative to the amount of monomer. poly(ethylene adipate), poly(1,4-butylene adipate), and poly 5. The composition of claim 1, wherein the nucleophile (hexamethylene adipate). comprises at least one hydroxyl group. 15. A polymer comprising the composition of claim 1, 6. The composition of claim 1, wherein the electrophilic wherein the polymer is selected from the group consisting of moieties are selected from ester, carbonate, urethane, substi poly(ethylene suberate), poly(ethylene sebacate), poly(ethyl tuted urethane, phosphate, amido, substituted amido, ene isophthalate), and poly(ethylene sulfonyl-4,4'-diben thioester, sulfonate ester, and combinations thereof. 25 Zoate). 7. The composition of claim 1, wherein the monomer has 16. A polymer comprising the composition of claim 1, the structure X-L-X, wherein X and X’ are electrophilic wherein the polymer is selected from the group consisting of moieties independently selected from esters, carbonates, ure poly(ethylene 2,6-naphthalene-dicarboxylate), poly(p-phe thanes, Substituted urethanes, phosphates, amido groups, nylene ethylene dicarboxylates), poly(trans-1,4-cyclohex Substituted amido groups, thioesters, and sulfonate esters, 30 anediyl ethylene dicarboxylate), poly(1,4-cyclohexane-dim and L is a linker moiety selected from C-Cohydrocarbylene ethylene ethylene dicarboxylate), and poly(2.2.2]- and functional linker groups. bicyclooctane-1,4-dimethylene ethylene dicarboxylate). 8. The composition of claim 7, whereinX' and X’ are ester 17. A polymer comprising the composition of claim 1, moieties. wherein the polymer is selected from the group consisting of 9. The composition of claim 7, wherein L is selected from 35 3,3'-dimethylbisphenol A: 3,3',5,5'-tetrachlorobisphenol A: substituted and unsubstituted C-C alkylene, substituted and 3,3',5,5'-tetramethylbisphenol A. and unsubstituted Cs-Carylene, substituted and unsubsti 18. A polymer comprising the composition of claim 1, tuted Cs-C alkarylene, and substituted and unsubstituted wherein the polymer comprises poly(p-phenylene tereph Cs-Caralkylene. thalamide). 10. A polymer comprising the composition of claim 1, 40 19. A polymer comprising the composition of claim 1, wherein the polymer is selected from the group consisting of wherein the polymer comprises polypropylene carbonate). poly(alkylene terephthalates), poly(alkylene adipates), poly 20. A polymer comprising the composition of claim 1, (alkylene Suberates), poly(alkylene sebacates), poly(alkylene wherein the polymer is selected from the group consisting of isophthalates), poly(alkylene sulfonyl-4,4'-dibenzoates), (S)-polylactide, (R.S)-polylactide, poly(tetramethylgly poly(alkylene 2,6-naphthalene-dicarboxylates), poly(p-phe 45 collide), and poly(lactide-co-glycolide). nylene alkylene dicarboxylates), poly(trans-1,4-cyclohex