DOCSLIB.ORG

(12) United States Patent (10) Patent No.: US 8,546,513 B2 Hedricket Al

Total Page：16

File Type：pdf, Size：1020Kb

Download full-text PDF Read full-text
(12) United States Patent (10) Patent No.: US 8,546,513 B2 Hedricket Al 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)
Load more

Recommended publications
  • Using Carbon Dioxide As a Building Block in Organic Synthesis
    REVIEW Received 10 Jul 2014 | Accepted 21 Nov 2014 | Published 20 Jan 2015 DOI: 10.1038/ncomms6933 Using carbon dioxide as a building block in organic synthesis Qiang Liu1, Lipeng Wu1, Ralf Jackstell1 & Matthias Beller1 Carbon dioxide exits in the atmosphere and is produced by the combustion of fossil fuels, the fermentation of sugars and the respiration of all living organisms. An active goal in organic synthesis is to take this carbon—trapped in a waste product—and re-use it to build useful chemicals. Recent advances in organometallic chemistry and catalysis provide effective means for the chemical transformation of CO2 and its incorporation into synthetic organic molecules under mild conditions. Such a use of carbon dioxide as a renewable one-carbon (C1) building block in organic synthesis could contribute to a more sustainable use of resources. more sensible resource management is the prerequisite for the sustainable development of future generations. However, when dealing with the feedstock of the chemical Aindustry, the level of sustainability is still far from satisfactory. Until now, the vast majority of carbon resources are based on crude oil, natural gas and coal. In addition to biomass, CO2 offers the possibility to create a renewable carbon economy. Since pre-industrial times, the amount of CO2 has steadily increased and nowadays CO2 is a component of greenhouse gases, which are primarily responsible for the rise in atmospheric temperature and probably abnormal changes in the global climate. This increase in CO2 concentration is largely due to the combustion of fossil fuels, which are required to meet the world’s energy demand1.
    [Show full text]
  • Studying the Ring-Opening Polymerization of 1,5-Dioxepan-2-One with Organocatalysts
    polymers Article Studying the Ring-Opening Polymerization of 1,5-Dioxepan-2-one with Organocatalysts Jinbao Xu *, Yang Chen, Wenhao Xiao, Jie Zhang, Minglu Bu, Xiaoqing Zhang and Caihong Lei * Guangdong Provincial Key Laboratory of Functional Soft Condensed Matter, School of Materials and Energy, Guangdong University of Technology, Guangzhou 510006, China; [email protected] (Y.C.); [email protected] (W.X.); [email protected] (J.Z.); [email protected] (M.B.); [email protected] (X.Z.) * Correspondence: [email protected] (J.X.); [email protected] (C.L.) Received: 23 September 2019; Accepted: 8 October 2019; Published: 10 October 2019 Abstract: Three different organocatalysts, namely, 1-tert-butyl-4,4,4-tris(dimethylamino)-2,2-bis[tris 5 5 (dimethylamino) phosphoranylidenamino]-2L ,4L -catenadi(phosphazene) (t-BuP4), 1,5,7- triazabicyclo[4.4.0]dec-5-ene (TBD) and 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), have been used as 1,5-dioxepan-2-one (DXO) ring-opening polymerization (ROP) catalysts at varied reaction conditions. 1H NMR spectra, size exclusion chromatography (SEC) characterizations, and kinetic studies prove that the (co)polymerizations are proceeded in a controlled manner with the three organocatalysts. It is deduced that t-BuP4 and DBU catalysts are in an initiator/chain end activated ROP mechanism and TBD is in a nucleophilic ROP mechanism. Keywords: 1,5-dioxepan-2-one; t-BuP4; DBU; TBD; organocatalyst 1. Introduction During the last several decades, for the ring-opening polymerization (ROP) of cyclic esters, transition metal and organometallic compounds were commonly used as initiators or polymerization catalysts [1–4].
    [Show full text]
  • UV-Curable Thiol–Ene Networks Based on Renewable Resources
    Macromolecular Design: UV-Curable Thiol–Ene Networks Based on Renewable Resources MAURO CLAUDINO Doctoral Thesis in Polymer Technology Stockholm, Sweden 2013 MACROMOLECULAR DESIGN: UV-CURABLE THIOL–ENE NETWORKS BASED ON RENEWABLE RESOURCES MAURO CLAUDINO Doctoral Thesis Kungliga Tekniska högskolan, Stockholm 2013 AKADEMISK AVHANDLING Akademisk avhandling som med tillstånd av Kungliga Tekniska högskolan i Stockholm, framlägges till offentlig granskning för avläggande av teknologie doktorsexamen torsdagen den 03 oktober 2013, kl. 14.30 i sal F3, Lindstedtsvägen 26, KTH, Stockholm. Avhandlingen försvaras på engelska. Fakultetsopponent: Professor Dr. Michael A. R. Meier från Karlsruhe Institute of Technology (KIT), Germany. Copyright © 2013 Mauro Claudino All rights reserved Paper I © 2010 European Polymer Journal Paper II © 2012 Journal of Polymer Science Part A: Polymer Chemistry Paper III © 2013 RSC Advances Paper IV © 2013 TRITA-CHE Report 2013:36 ISSN 1654-1081 ISBN 978-91-7501-845-4 To my parents Eduardo e Mariana Eles não sabem que o sonho é uma constante da vida tão concreta e definida como outra coisa qualquer, Eles não sabem, nem sonham, que o sonho comanda a vida. Que sempre que um homem sonha o mundo pula e avança como bola colorida entre as mãos de uma criança. – António Gedeão (Rómulo de Carvalho, 1906-2006) Excertos de Poema “Pedra Filosofal”, In Movimento Perpétuo, 1956 Abstract Plant oils and terpenes are ubiquitous natural renewable compounds. The double bonds contained in most of these monomers can be utilized via the photo-induced free-radical thiol–ene reaction to create novel bio-derived polymer thermosets representing a valuable ‘green’ alternative to petrochemical olefins and resulting synthetic plastic materials.
    [Show full text]
  • Concerted Nucleophilic Aromatic Substitution Reactions Simon Rohrbach+, Andrew J
    Angewandte Reviews Chemie International Edition: DOI: 10.1002/anie.201902216 Nucleophilic Aromatic Substitution German Edition: DOI: 10.1002/ange.201902216 Concerted Nucleophilic Aromatic Substitution Reactions Simon Rohrbach+, Andrew J. Smith+, Jia Hao Pang+, Darren L. Poole, Tell Tuttle,* Shunsuke Chiba,* and John A. Murphy* Keywords: Dedicated to Professor Koichi concerted reactions Narasaka on the occasion of ·cSNAr mechanism · his 75th birthday Meisenheimer complex · nucleophilicaromatic substitution Angewandte Chemie &&&& 2019 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim Angew. Chem. Int. Ed. 2019, 58,2–23 Ü Ü These are not the final page numbers! Angewandte Reviews Chemie Recent developments in experimental and computational From the Contents chemistry have identified a rapidly growing class of nucleophilic 1. Aromatic Substitution Reactions 3 aromatic substitutions that proceed by concerted (cSNAr) rather than classical, two-step, SNAr mechanisms. Whereas traditional 2. Some Contributions by SNAr reactions require substantial activation of the aromatic ring Computational Studies 6 by electron-withdrawing substituents, such activating groups are not mandatory in the concerted pathways. 3. Fluorodeoxygenation of Phenols and Derivatives 9 4. Aminodeoxygenation of Phenol 1. Aromatic Substitution Reactions Derivatives 10 Substitution reactions on aromatic rings are central to 5. Hydrides as Nucleophiles 11 organic chemistry. Besides the commonly encountered elec- trophilic aromatic substitution,[1] other mechanisms include 6. P, N, Si, C Nucleophiles 13 [2,3] SNAr nucleophilic aromatic substitutions and the distinct [4] but related SNArH and vicarious nucleophilic substitutions, 7. Organic Rearrangements via Spiro substitutions brought about through benzyne intermedi- Species: Intermediates or Transition ates,[5,6] radical mechanisms including electron transfer- States? 14 [7] based SRN1 reactions and base-promoted homolytic aro- matic substitution (BHAS) couplings,[8] sigmatropic rear- 8.
    [Show full text]
  • Organocatalytic Decomposition of Poly(Ethylene Terephthalate) Using Triazabicyclodecene Proposal
    San Jose State University SJSU ScholarWorks Master's Theses Master's Theses and Graduate Research Fall 2010 Organocatalytic decomposition of poly(ethylene terephthalate) using triazabicyclodecene proposal Julien Matsumoto Lecuyer San Jose State University Follow this and additional works at: https://scholarworks.sjsu.edu/etd_theses Recommended Citation Lecuyer, Julien Matsumoto, "Organocatalytic decomposition of poly(ethylene terephthalate) using triazabicyclodecene proposal" (2010). Master's Theses. 3873. DOI: https://doi.org/10.31979/etd.c3kc-xcdz https://scholarworks.sjsu.edu/etd_theses/3873 This Thesis is brought to you for free and open access by the Master's Theses and Graduate Research at SJSU ScholarWorks. It has been accepted for inclusion in Master's Theses by an authorized administrator of SJSU ScholarWorks. For more information, please contact [email protected]. ORGANOCATALYTIC DECOMPOSITION OF POLYETHYLENE TEREPHTHALATE USING TRIAZABICYCLODECENE A Thesis Presented to The Faculty of the Department of Chemical and Materials Engineering San Jose State University In Partial Fulfillment of the Requirements for the Degree Master of Science by Julien Matsumoto Lecuyer December 2010 © 2010 Julien Matsumoto Lecuyer ALL RIGHTS RESERVED ORGANOCATALYTIC DECOMPOSITION OF POLYETHYLENE TEREPHTHALATE USING TRIAZABICYCLODECENE by Julien Lecuyer APPROVED FOR THE DEPARTMENT OF CHEMICAL & MATERIALS ENGINEERING SAN JOSÉ STATE UNIVERSITY August 2010 Dr. Melanie McNeil Department of Chemical & Materials Engineering Dr. Richard Chung Department of Chemical & Materials Engineering Dr. James Hedrick IBM Almaden Research Center Dr. Kazuki Fukushima IBM Almaden Research Center ABSTRACT ORGANOCATALYTIC DECOMPOSITION OF POLYETHYLENE TEREPHTHALATE USING TRIAZABICYCLODECENE This study focuses on the organocatalytic decomposition of polyethylene terephthalate (PET) using 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD) to form a diverse library of aromatic amides.
    [Show full text]
  • Exploiting Aldolase Variants in the Synthesis of Fluorinated Analogues of N-Acetyl Neuraminic Acid
    Exploiting aldolase variants in the synthesis of fluorinated analogues of N-acetyl neuraminic acid Jennifer Ann Stockwell Submitted in accordance with the requirements for the degree of Doctor of Philosophy The University of Leeds Astbury Centre for Structural Molecular Biology and Department of Chemistry September 2013 The candidate confirms that the work submitted is her own and that appropriate credit has been given where reference has been made to the work of others. This copy has been supplied on the understanding that it is copyright material and that no quotation from the thesis may be published without proper acknowledgement. ©2013 The University of Leeds and Jennifer Ann Stockwell The right of Jennifer Ann Stockwell to be identified as Author of this work has been asserted by her in accordance with the Copyright, Designs and Patents Act 1988. i Acknowledgements I'd like to start off by thanking my supervisors Prof. Adam Nelson and Prof. Alan Berry for all the help and guidance they have given me over the last four years. Without their support, I wouldn't be sitting here writing these acknowledgements. I'd also like to thank my industrial supervisor Dr. Keith Mulholland, it was with his support and friendship that I was able to gain confidence and realise what I wanted to do with my life. My time at AstraZeneca was brilliant and there are too many people to thank individually, so I would like to say thank you all for making me feel so welcome. I would particularly like to thank Dr. Adam Daniels and Claire Windle for all their contributions, to Adam for his brilliant work towards greater understanding of the enzyme mechanism and to Claire for her beautiful crystal structure.
    [Show full text]
  • 2-Methyltetrahydrofuran (2-Methf) As a Versatile Green Solvent for the Synthesis of Amphiphilic Copolymers Via ROP, FRP and RAFT Tandem Polymerizations
    2-methyltetrahydrofuran (2-MeTHF) as a versatile green solvent for the synthesis of amphiphilic copolymers via ROP, FRP and RAFT tandem polymerizations. Georgia Englezou+,1 Kristoffer Kortsen+,2 Ana A C Pacheco+,2 Robert Cavanagh,3 Joachim C Lentz,2 Eduards Krumins,2 Carlos Sanders-Velez,3 Steven M Howdle2, Alisyn J Nedoma*,1 and Vincenzo Taresco*2 1. The University of Sheffield, Department of Chemical and Biological Engineering, Sir Robert Hadfield Building, Sheffield, S1 3JD, UK 2. University of Nottingham, School of Chemistry, University Park, NG7 2RD, UK 3. University of Nottingham, School of Pharmacy, University Park, NG7 2RD, UK + authors contributed equally * Corresponding authors Graphical Abstract We have tested the suitability of 2-MeTHF as a green solvent for organo- and enzymatically catalyzed ROP of simple diblocks and in the production of more interesting A-B-C blockcopolymers using a single or double catalyst system. Labile-ester ROP initiators HEMA and PEGMA were also used to initiate LA macromonomers. To further demonstrate the versatility of 2- MeTHF as “multipolymerization” green solvent the produced macromonomers were tested in FRP and RAFT tandem polymerization. Abstract 2-methyltetrahydrofuran (2-MeTHF) is a readily available, inexpensive, neoteric, bio-based solvent. It has been adopted across a wide range of chemical processes including the batch manufacture of fine chemicals, enzymatic polycondensations and ring opening polymerizations. To reduce the environmental burden related to the synthesis of pharmaceutical-grade polymers based on lactide and caprolactone, we envisaged the use of 2-MeTHF. For the first time, we combined a series of metal- free and enzymatic ROPs with free radical and controlled RAFT polymerizations (carried out separately and in tandem) in 2-MeTHF, in order to easily tune the chemistry and the architecture of the final polymers.
    [Show full text]
  • Readily Prepared and Tunable Ionic Organocatalysts for Ring-Opening Polymerization of Lactones Jiang Zhuo-Lun, Zhao Jun-Peng, Zhang Guang-Zhao
    Readily Prepared and Tunable Ionic Organocatalysts for Ring-opening Polymerization of Lactones Jiang Zhuo-Lun, Zhao Jun-Peng, Zhang Guang-Zhao Cite this article as: Jiang Zhuo-Lun, Zhao Jun-Peng, Zhang Guang-Zhao. Readily Prepared and Tunable Ionic Organocatalysts for Ring-opening Polymerization of Lactones[J]. Chinese J. Polym. Sci, 2019, 37(12): 1205-1214. doi: 10.1007/s10118-019-2285-1 View online: https://doi.org/10.1007/s10118-019-2285-1 Articles you may be interested in Stereoselective Ring-opening Polymerization of rac-Lactide by Bulky Chiral and Achiral N-heterocyclic Carbenes Chinese J. Polym. Sci. 2018, 36(2): 231 https://doi.org/10.1007/s10118-018-2071-5 Polypeptide Brushes Grown via Surface-initiated Ring-opening Polymerization of -Amino Acid N-Carboxyanhydrides Chinese J. Polym. Sci. 2015, 33(7): 931 https://doi.org/10.1007/s10118-015-1654-7 HETEROCYCLIC SCHIFF BASE NEODYMIUM COMPLEX AS CATALYST FOR RING-OPENING POLYMERIZATION OF ε- CAPROLACTONE Chinese J. Polym. Sci. 2008, 26(4): 475 环硅氧烷阴离子开环均聚及共聚研究进展 Progress in Anionic Ring-opening Homo/Co-polymerization of Cyclosiloxanes 高分子学报. 2018(12): 1482 https://doi.org/10.11777/j.issn1000-3304.2018.18165 醇铁化合物引发丙交酯开环聚合的研究 FERRIC ALKOXIDES-INITIATED RING-OPENING POLYMERIZATION OF LACTIDES 高分子学报. 2006(2): 229 氨基甲酰基季铵盐双功能催化剂催化丙交酯开环聚合研究 Ring-opening Polymerization of Lactide by Bifunctional Organocatalyst at Ambient Conditions 高分子学报. 2019, 50(12): 1290 https://doi.org/10.11777/j.issn1000-3304.2019.19080 Chinese Journal of POLYMER SCIENCE ARTICLE https://doi.org/10.1007/s10118-019-2285-1 Chinese J. Polym. Sci. 2019, 37, 1205–1214 Readily Prepared and Tunable Ionic Organocatalysts for Ring-opening Polymerization of Lactones Zhuo-Lun Jiang, Jun-Peng Zhao*, and Guang-Zhao Zhang Faculty of Materials Science and Engineering, South China University of Technology, Guangzhou 510640, China Electronic Supplementary Information Abstract Highly potent ionic organocatalyst is developed for room-temperature controlled ring-opening polymerization (ROP) of lactones, including δ-valerolactone, ε-caprolactone, and δ-hexalactone.
    [Show full text]
  • Incorporated Copolymers and Blends for Bone Regeneration
    University of Kentucky UKnowledge Theses and Dissertations--Biomedical Engineering Biomedical Engineering 2017 SYNTHESIS AND CHARACTERIZATION OF POLY(SIMVASTATIN) - INCORPORATED COPOLYMERS AND BLENDS FOR BONE REGENERATION Theodora Asafo-Adjei University of Kentucky, [email protected] Author ORCID Identifier: https://orcid.org/0000-0001-8124-9040 Digital Object Identifier: https://doi.org/10.13023/ETD.2017.362 Right click to open a feedback form in a new tab to let us know how this document benefits ou.y Recommended Citation Asafo-Adjei, Theodora, "SYNTHESIS AND CHARACTERIZATION OF POLY(SIMVASTATIN) - INCORPORATED COPOLYMERS AND BLENDS FOR BONE REGENERATION" (2017). Theses and Dissertations--Biomedical Engineering. 46. https://uknowledge.uky.edu/cbme_etds/46 This Doctoral Dissertation is brought to you for free and open access by the Biomedical Engineering at UKnowledge. It has been accepted for inclusion in Theses and Dissertations--Biomedical Engineering by an authorized administrator of UKnowledge. For more information, please contact [email protected]. STUDENT AGREEMENT: I represent that my thesis or dissertation and abstract are my original work. Proper attribution has been given to all outside sources. I understand that I am solely responsible for obtaining any needed copyright permissions. I have obtained needed written permission statement(s) from the owner(s) of each third-party copyrighted matter to be included in my work, allowing electronic distribution (if such use is not permitted by the fair use doctrine) which will be submitted to UKnowledge as Additional File. I hereby grant to The University of Kentucky and its agents the irrevocable, non-exclusive, and royalty-free license to archive and make accessible my work in whole or in part in all forms of media, now or hereafter known.
    [Show full text]
  • Tailoring Chain Structures of L-Lactide and Ε-Caprolactone Copolyester
    RSC Advances View Article Online PAPER View Journal | View Issue Tailoring chain structures of L-lactide and 3- caprolactone copolyester macromonomers using Cite this: RSC Adv.,2017,7, 28661 rac-binaphthyl-diyl hydrogen phosphate-catalyzed ring-opening copolymerization with monomer addition strategy† Yanjiao Wang,a Ming Xia,b Xueqiang Kong,b Steven John Severtson*c and Wen-Jun Wang *a Copolymerizations involving polyester macromonomers (MMs) generated from biomass provide a new route for introducing high biomass content into existing polymeric products. Stannous 2-ethylhexanoate-catalyzed ring-opening copolymerization (ROcoP) is commonly utilized to synthesize MMs, but this approach generates polymer chains containing terminal metal residues and limits control of MM chain structures due to the 0 0 Creative Commons Attribution 3.0 Unported Licence. presence of transesterification side reactions (TSRs). Here, rac-1,1 -binaphthyl-2,2 -diyl-hydrogenphosphate (rac-BNPH) was used for the 2-hydroxylethyl methacrylate (HEMA) initiated ROcoP of L-lactide (L-LA) and 3-caprolactone (3-CL) to produce the well-defined MMs. The copolymerization kinetics and monomer feeding strategies, batch and semibatch, were studied, and the influence on MM chain structures was investigated using both 1Hand13C NMR analysis. The rac-BNPH was identified as an effective catalyst for the ROcoP of L-LA and 3-CL, producing narrowly dispersed MMs with a 96% retention of terminal vinyl groups associated with HEMA. The 3-CL was more reactive than L-LA, and the reactions exhibited Received 16th May 2017 characteristics of living polymerization. The TSRs could be significantly suppressed using batch operation Accepted 19th May 2017 or semibatch with fast 3-CL addition.
    [Show full text]
  • WO 2011/008480 Al
    (12) INTERNATIONAL APPLICATION PUBLISHED UNDER THE PATENT COOPERATION TREATY (PCT) (19) World Intellectual Property Organization International Bureau (10) International Publication Number (43) International Publication Date 20 January 2011 (20.01.2011) WO 2011/008480 Al (51) International Patent Classification: (81) Designated States (unless otherwise indicated, for every C08G 59/18 (2006.01) C08G 59/62 (2006.01) kind of national protection available): AE, AG, AL, AM, C08G 59/40 (2006.01) C08L 63/00 (2006.01) AO, AT, AU, AZ, BA, BB, BG, BH, BR, BW, BY, BZ, C08G 59/50 (2006.01) CA, CH, CL, CN, CO, CR, CU, CZ, DE, DK, DM, DO, DZ, EC, EE, EG, ES, FI, GB, GD, GE, GH, GM, GT, (21) International Application Number: HN, HR, HU, ID, IL, IN, IS, JP, KE, KG, KM, KN, KP, PCT/US20 10/040078 KR, KZ, LA, LC, LK, LR, LS, LT, LU, LY, MA, MD, (22) International Filing Date: ME, MG, MK, MN, MW, MX, MY, MZ, NA, NG, NI, 25 June 2010 (25.06.2010) NO, NZ, OM, PE, PG, PH, PL, PT, RO, RS, RU, SC, SD, SE, SG, SK, SL, SM, ST, SV, SY, TH, TJ, TM, TN, TR, (25) Filing Language: English TT, TZ, UA, UG, US, UZ, VC, VN, ZA, ZM, ZW. (26) Publication Language: English (84) Designated States (unless otherwise indicated, for every (30) Priority Data: kind of regional protection available): ARIPO (BW, GH, 61/269,740 29 June 2009 (29.06.2009) US GM, KE, LR, LS, MW, MZ, NA, SD, SL, SZ, TZ, UG, 61/323,3 14 12 April 2010 (12.04.2010) US ZM, ZW), Eurasian (AM, AZ, BY, KG, KZ, MD, RU, TJ, TM), European (AL, AT, BE, BG, CH, CY, CZ, DE, DK, (71) Applicant (for all designated States except US): POLY- EE, ES, FI, FR, GB, GR, HR, HU, IE, IS, IT, LT, LU, MERight, Inc.
    [Show full text]
  • Synthesis of Functionalized Lactones by Thiol-Ene Reaction and Their Application to the Preparation of Tunable Biodegradable Polymers Somprasong Thongkham
    Synthesis of functionalized lactones by thiol-ene reaction and their application to the preparation of tunable biodegradable polymers Somprasong Thongkham To cite this version: Somprasong Thongkham. Synthesis of functionalized lactones by thiol-ene reaction and their appli- cation to the preparation of tunable biodegradable polymers. Polymers. Université Paul Sabatier - Toulouse III, 2019. English. NNT : 2019TOU30295. tel-03098501 HAL Id: tel-03098501 https://tel.archives-ouvertes.fr/tel-03098501 Submitted on 5 Jan 2021 HAL is a multi-disciplinary open access L’archive ouverte pluridisciplinaire HAL, est archive for the deposit and dissemination of sci- destinée au dépôt et à la diffusion de documents entific research documents, whether they are pub- scientifiques de niveau recherche, publiés ou non, lished or not. The documents may come from émanant des établissements d’enseignement et de teaching and research institutions in France or recherche français ou étrangers, des laboratoires abroad, or from public or private research centers. publics ou privés. THÈSE En vue de l’obtention du DOCTORAT DE L’UNIVERSITÉ DE TOULOUSE Délivré par l'Université Toulouse 3 - Paul Sabatier Présentée et soutenue par Somprasong THONGKHAM Le 24 octobre 2019 Synthèse de lactones fonctionnalisées par réaction de thiol-ène et leur application à la préparation de polymères biodégradables de propriétés modulables Ecole doctorale : SDM - SCIENCES DE LA MATIERE - Toulouse Spécialité : Chimie Organométallique et de Coordination Unité de recherche : LHFA - Laboratoire Hétérochimie Fondamentale et Appliquée Thèse dirigée par Didier BOURISSOU et Blanca MARTIN-VACA Jury M. Yohann GUILLANEUF, Rapporteur M. Haritz SARDON, Rapporteur M. Khamphee PHOMPHRAI, Examinateur M. Yves GENISSON, Examinateur Mme Blanca MARTIN-VACA, Directrice de thèse M.
    [Show full text]