高枝化官能化聚合物的合成方法学  

Synthesis methodology of dendrigraft functional polymer

作　　者：李婷婷[1] 马红卫[1] 魏志勇[1] 郭方[1] 申凯华[1] 牛慧[1] 李杨[1] 

机构地区：[1]大连理工大学化工与环境生命学部高分子材料系,精细化工国家重点实验室,大连116024

出　　处：《科学通报》2016年第31期3304-3314,共11页Chinese Science Bulletin

基　　金：国家重点基础研究发展计划(2015CB654701);国家自然科学基金(U1462126,U1508204,21404019);中国博士后基金(2014M550154)资助

摘　　要：结构化、功能化、集成化是合成橡胶及弹性体实现高性能化的有效手段,活性阴离子聚合是高分子链实现高枝化和官能化的有效手段.高枝化聚合物具有独特的结构和性能,近年来已在聚合物材料应用中脱颖而出,并且逐渐成为高分子化学领域的研究热点.基于研究现状,本文总结了高枝化官能化聚合物合成方法学的研究进展.采用共聚合方法、基团转换方法、硅氢加成方法、点击化学方法合成的高枝化官能化聚合物,扩展并延伸了原有聚合物橡胶的性能,为合成绿色橡胶提供了新思路、新方法.功能聚合物的高枝化拓扑结构与性能之间的关联规律也为绿色橡胶的设计开发提供了依据和基础.Structuralization,functionalization and integration are efficient pathways to improve the properties of synthetic rubber and elastomer,and the living anionic polymerization is an effective method to prepare polymer chain with topological structure and functional groups. Recently,the dendrigraft polymers attracted more and more attentions in the macromolecular chemistry,owing to their unique structure and properties. Herein,the synthesis methodology of dendrigraft functional polymers was summarized. On the basis of epoxidized polybutadiene/polyisoprene with different structures,novel dendrigraft star-comb polymers were precisely synthesized by the iterative epoxidation-coupling reactions with coupling groups in the polymer chain. High vacuum technique in the living anionic polymerization was explored,establishing the efficient synthesis strategy for the preparation of dendrigraft star-comb polymers. Aiming to achieve in-chain functionalized polymers with the goal of ＂definite function＂,＂accurate quantity＂ and ＂precise position＂,the precise synthesis of in-chain functional polymers with complex topological structure was researched and the relationship between the polymer structure and performance was probed. These dendrigraft functional polymers were prepared by introducing different target functionalized groups into polymer chain via copolymerization,group transfer reaction,hydrosilylation and click chemistry. A series of functionalized DPE derivatives with complex structures were designed and the corresponding synthesis pathway and purification method for the monomers were examined. The copolymerization of DPE derivatives possessing different functional groups with butadiene,isoprene and styrene were also illustrated. Based on the synthesis of a series of liquid crystal macromolecules with alkenyl-teminated units,dendrigraft liquid crystal polystyrene was prepared with hydrosilylation reactions. Based on the synthesis of a series liquid crystal macromolecules with SiH-teminated units,the dendrigraft l

关 键 词：高枝化聚合物 官能化 阴离子聚合 合成方法学 

分 类 号：O631.3[理学—高分子化学] TQ330.1[理学—化学]