新型ABC三嵌段液晶共聚物的合成与表征.doc

湘潭大学硕士学论文  黄孝华  Abstract The literature reporting the recently researches of block copoloymers, especially the rod-coil triblock copolymers were briefly summarized in this dissertation. A series of novel ABC mesogen-jacketed liquid-crystal triblock copolymers with poly{2,5-bis[(4-methoxyphenyl)oxycabony] styrene}(PMPCS) as rod block were designed and synthesized by atom transfer radical polymerization (ATRP) and its phase behavior was discussed. 1. The macromolecular initiators PEO-Br, bromo-terminated PEO was prepared by esterification between PEO and 2-bromoisobutyryl bromide. The ATRP of an amphiphilic diblock copolymer PEO-b-PS was acchived using CuBr/bpy as catalyst system. The crystalline behavior of PEO block in the copolymer was studied using differential scanning calorimetry(DSC) 、 polarized optical microscope(POM). It showed that the crystalizing velocity, crystallinity degree and crystalline perfection of PEO decreased as the content PS increased. Even there was no crystallization of PEO block. 2. A series of ABC triblock rod-coil liquid-crystalline copolymers with controlled molecular weight and narrow molecular weight distribution were obtained by ATRP using PEO-b-PS-Br as macroinitiators and CuBr/sparteine complex as catalyst system. Gel permeation chromatography(GPC) and 1 HNMR were used to confirmed the structure of rod-coil block PMPCS. The liquid crystalline of this block copolymer was characterized by differential II 提 要 近几年来，随着现代科学技术的飞速发展高分子科学也得到了 前所未有的发展。人们对高分子材料的需求也从过去具有单一性能 的高聚物转而向具有各种综合性能或具有各种特殊用途的高分子 材料的需求，由于嵌段共聚物具有许多与众不同的性能而受到人们 极大的关注。 嵌段共聚物的研究起始于无终止阴离子活性聚合的发现，适当 的A、B单体顺次阴离子聚合便制备出最简单的AB二嵌段共聚物[1]， 制备嵌段共聚物的方法包括活性离子聚合、开环聚合、缩聚及自由 基聚合，但由于制备成本高，反应条件苛刻，只有如SBS和ABS等 这样为数不多的嵌段共聚物进入市场。自由基可控聚合用于合成嵌 段共聚物己有一段历史，但90年代以前报道的自由基方法合成的嵌 段共聚物中或多或少都有均聚物的存在。90年代初发展起来的 TEMPO?及CoⅡ?存在下的可控自由基聚合虽可合成嵌段共聚物， 但存在两大致命的缺点。一是TEMPO 物，CoTEMPO?还 是Co 很容易直接制得三嵌段共聚物。目前对嵌段共聚物的研究集中在自 组装领域。所谓自组装，是分子自发地聚集成稳定的、非共价键相 连的有序聚集体，或是两个或多个分子微单元间的非共价相互作 用，形成了由组