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., Guanidine and Amidine Organo-Catalysts for Ring Board of Trustees of the Leland Opening Polymerization of Cyclic Esters, 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-guanidines, -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)