结晶性生物可降解聚羟基脂肪酸酯的化学合成  

Chemical Synthesis of Crystalline Biodegradable Polyhydroxyalkanoates

作　　者：廖曦 秦娇娇 唐小燕 Xi Liao;Jiao-jiao Qin;Xiao-yan Tang(Beijing National Laboratory for Molecular Sciences,College of Chemistry and Molecular Engineering,Peking University,Key Laboratory of Polymer Chemistry and Physics of Ministry of Education,Beijing 100871)

机构地区：[1]北京分子科学国家研究中心、北京大学化学与分子工程学院、高分子化学与物理教育部重点实验室,北京100871

出　　处：《高分子学报》2023年第10期1426-1467,共42页Acta Polymerica Sinica

基　　金：国家自然科学基金(基金号52173093)资助项目.

摘　　要：天然聚羟基脂肪酸酯(PHAs)是一种源于微生物合成的等规高分子材料,表现出优异的生物相容性和生物可降解性,具有替代石油基高分子材料的潜力.化学合成PHAs因合成效率高、可控性好以及产品质量易于控制等特点而具有巨大的应用价值.由于PHAs的立构规整性以及结晶性对其热学性能、机械性能和降解效率等都有很大的影响,因此控制PHAs的立构规整性以及结晶性是合成过程中的一个关键问题,也是一个难点问题.本综述从单体分类的角度总结了近六十年化学合成立构规整性PHAs的研究进展,包括四元环内酯单体(β-丁内酯(β-BL)及其衍生物(BPL和MLA),以及其他不同α-、β-和α,β-取代的β-丙内酯(β-PL)),八元环和十二元环内酯单体(即β-BL的二、三聚体(8DL,TBL))以及环氧烷烃/CO等立体选择性开环(共)聚合,重点关注和评述了不同催化剂体系对立构选择性的影响,总结了相应聚合物的机械性能和热力学性能,最后对PHAs的降解回收策略做概述,并对立构规整PHAs的合成策略进行了展望.Recently,biodegradable polymer materials have drawn much attention due to their environmental friendliness.Among them,natural polyhydroxyalkanoates(PHAs),a type of isotactic polyesters produced by microorganisms,exhibit excellent biocompatibility and biodegradability,and thus are promising alternatives to petroleum-based plastics.Chemical synthesis of PHAs possesses enormous application value due to their high synthesis efficiency,great controllability and easy control of product quality.Since the stereoregularity and crystallinity of PHAs strongly affects their thermal and mechanical properties as well as degradation rates,controlling the stereoregularity and/or crystalline PHAs is a key and also challenging issue in their synthesis process.This review provides a comprehensive overview of the advancements in the chemical synthesis of stereoregular and/or crystalline PHAs in the last 60 years from the perspective of monomer classification.It covers the stereoselective ring-opening(co-)polymerization of four-membered lactones(e.g.,β-butyrolactone(β-BL)and its derivatives(BPL,MLA),β-propiolactones with differentα-,β-,andα,β-substitutions),eight-membered lactones(β-BL's dimer,8DL),twelve-membered lactone(β-BL's trimer,TBL)and epoxides/CO.The review places particular emphasis on the effects of different catalyst systems on stereoselectivity,and summarizes the mechanical and thermal properties of the resulting polymers.Furthermore,it briefly touches upon the degradation and recycling strategies of PHAs,followed by an outlook on the approaches for achieving stereoselective controlled synthesis of PHAs.

关 键 词：生物可降解聚合物 聚羟基脂肪酸酯 结晶性聚合物 立构选择性聚合 开环聚合 

分 类 号：O631[理学—高分子化学]