Recent advances in ring-opening polymerization strategies toward α,ω-hydroxy telechelic polyesters and resulting copolymers
Recent advances in ring-opening polymerization strategies toward α,ω-hydroxy telechelic polyesters and resulting copolymers
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DOI：
10.1016/j.eurpolymj.2012.10.011
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发表时间：
2013-04-01
影响因子：
6
通讯作者：
Guillaume, Sophie M.
中科院分区：
文献类型：
--
作者：
Guillaume, Sophie M.
α,ω - 羟基遥爪聚合物，即每个链端都带有反应性羟基端基的大分子，在工业上作为各种ABA或多嵌段共聚物结构的构建单元具有很高的价值。这篇专题文章综述了我们在过去十年中为制备α,ω - 羟基遥爪聚酯而开发的不同合成策略。几种环酯和碳酸酯，即ε - 己内酯（CL）、β - 丁内酯（BL）或碳酸三亚甲基酯（TMC）的开环聚合（ROP），由基于离散的第III族金属硼氢化物配合物、原位生成的锌醇盐化合物、金属盐或有机催化剂等本质上不同的体系催化，直接得到相应的双官能化羟基遥爪聚（ε - 己内酯）（PCL）、聚（3 - 羟基丁酸酯）（PHB）或聚（碳酸三亚甲基酯）（PTMC），分别为PCL - (OH)₂、PHB - (OH)₂或PTMC - (OH)₂。随后将此类大分子二醇用于共聚单体的聚合反应中，可以制备独特的三嵌段聚酯共聚物。将双 - OH官能化的PCL进行聚合后化学改性为相应的双 - NH₂或双 - Br聚合物，然后进行γ - 苄基 - L - 谷氨酸N - 羧基酐（BLG）的开环聚合，或者进行甲基丙烯酸甲酯（MMA）的自由基聚合，能够分别得到PCL - PBLG₂（PBLG：聚（γ - 苄基 - L - 谷氨酸N - 羧基酐））和PCL - PMMA₂（PMMA：聚（甲基丙烯酸甲酯））三嵌段共聚物。最后，二胺与由PTMC二醇衍生的双 - （环碳酸酯）端基官能化的PTMC进行加聚反应，顺利地得到非异氰酸酯聚氨酯（NIPUs）。因此，我们成功探索的α,ω - 羟基遥爪聚酯所带来的各种不同机会得到了强调。（c）2012爱思唯尔有限公司。保留所有权利。
alpha,omega-Hydroxy telechelic polymers, namely macromolecules with reactive hydroxyl end-groups at each chain-end, are industrially highly valuable as building blocks for various ABA or multiblock copolymer architectures. This feature article reviews the different synthetic strategies that we have been developing over the past decade for the preparation of alpha,omega-hydroxy telechelic polyesters. The ring-opening polymerization (ROP) of several cyclic esters and carbonate, namely epsilon-caprolactone (CL), beta-butyrolactone (BL) or trimethylene carbonate (TMC), catalyzed by intrinsically different systems based on discrete group III metal borohydride complexes, zinc alkoxide compounds generated in situ, metallic salts or organocatalysts, directly affords the corresponding difunctionalized hydroxy telechelic poly(epsilon-caprolactone) (PCL), poly(3-hydroxybutyrate) (PHB) or poly(trimethylene carbonate) (PTMC), PCL-(OH)(2), PHB-(OH)(2) or PTMC-(OH)(2), respectively. Subsequent use of such macrodiols in the polymerization of a co-monomer allows the preparation of unique triblock polyester copolymer's. The post-polymerization chemical modification of di-OH functionalized PCLs into the corresponding di-NH2 or di-Br polymers, followed by the ROP of gamma-benzyl-L-glutamate N-carboxyanhydride (BLG), or by the radical polymerization of methyl methacrylate (MMA), enables to access to PCL-PBLG(2) (PBLG: poly(gamma-benzyl-L-glutamate N-carboxyanhydride)) and PCL-PMMA(2) (PMMA: poly(methyl methacrylate)) triblock copolymers, respectively. Finally, polyaddition of a diamine with the di-(cyclocarbonate) end-functionalized PTMC, derived from PTMC diols, smoothly affords non-isocyanate polyurethanes (NIPUs). The quite different opportunities within reach from alpha,omega-hydroxy telechelic polyesters, that we have successfully explored, are thus highlighted. (c) 2012 Elsevier Ltd. All rights reserved.