2018-09-012024-05-17https://scholars.lib.ntu.edu.tw/handle/123456789/672506摘要：傳統縮聚合反應(polycondensation)為逐步增長聚合(step-growth polymerization)的反應，因此無法有效控制分子量與分子量分布，以及精準製備團聯共聚物等功能性高分子。然而，如能同時增強聚縮合反應高分子尾端官能基之反應性，並減小單體尾端官能基反應性，可有效將逐步增長聚合反應轉變為鏈增長聚合(chain-growth polymerization)反應。並進一步控制其終止反應，則傳統之聚縮合反應可以轉變為活性之鏈成長反應(living chain-growth polymerization)。近來McCullough 與Yokozawa 等人發現格林納金屬置換聚合法可形成活性連成長反應製備可調控分子量及分布之導電高分子及其共聚高分子。目前之研究，大部分經由活性格林納鏈成長反應之導電性嵌段共聚高分子的研究，都著重在聚合物pol(pphenylene)或poly(thiophene)等高分子與嵌段共聚物。本計畫將引進更多不同的單/雜環及稠環(fused ring)結構分子，並利用變化其鹵素間的相對位置及側鏈官能基的方式，提供合成新型導電精準聚合物之可能性。藉由這三年之研究，建立金屬置換聚合法合成多鏈段導電共聚高分子技術，並探討其自組 裝之特性，以及製備有機/無機混成物，應用於光電元件上。本研究分成三年，各年之目標如下： 第一年：利用格林納置換鏈聚合法，合成導電/導電雙嵌段共聚高分子及聚合機制探討。導電/導電雙嵌 段共聚高分子自組裝行為及光電性質之研究。(1) 第二年：利用格林納置換鏈聚合法，合成ABC 三嵌段導電共聚高分子及聚合機制探討。ABC 三嵌段 導電共聚高分子自組裝行為及光電性質之研究。(2) 第三年：雙/多嵌段導電高分子與有機/無機奈米顆粒之混摻自組裝行為及光電性質探討。(3)<br> Abstract: It was regarded that conventional condensation polymerization was typically a step-growth polymerization such that living condensation polymerization cannot be achieved. However, by simultaneously enhancing the growing chain end reactivity and reducing the reactivity of the monomer functional groups, step-growth polymerization could be transformed into chain-growth polymerization. Furthermore, if one can eliminate the termination step during the condensation polymerization, living condensation can be realized. Recently, McCullough and Yokozawa showed that by using Grignard metathesis polymerization, conducting polymers and block copolymers with controlled molecular weight, distribution can be synthesized. In this proposal, we further explore the possibility of using different conjugated monomer units with fused ring structure for the synthesis of novel conducting multiblock copolymers. The objective of the study is to establish the advanced synthesis method to better control molecular structure of the synthesized conducting multiblock copolymers and to understand the mechanism of the catalyst transfer polymerization method. Furthermore, we plan to explore new in-situ synthesis methods for the fabrication of the block copolymer and inorganic nanoparticle hybrids for the application for the optoelectronics. The project is divided into three parts as follows. In the first year, we plan to synthesize all- conjugated diblock copolymers with fused ring structures and study the self-assembly and optoelectronic property. In the second year, we plan to synthesize all- conjugated multiblock copolymers and study the self-assembly and optoelectronic property. In the third year, we plan to fabricate hybrids consisting of the conductive multiblock copolymers and in-situ grown inorganic nanoparticles to study their self-assembly and optoelectronic property.精準活性聚合法格林納置換聚合法多嵌段導電團聯共聚物Precision living polymerizationGrignard metathesis polymerizationconducting multiblock copolymers