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Study on influence of the tali chain of macromonomers on the radical chain polymerization

大分子单体塔里链对自由基链聚合影响的研究

基本信息

批准号：
12650867
负责人：
TSUKAHARA Yasuhisa
金额：
$ 0.58万
依托单位：
Kyoto Institute of Technology
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (C)
财政年份：
2000
资助国家：
日本
起止时间：
2000 至 2001
项目状态：
已结题

来源：
https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-12650867/
关键词：
macromonomer radical polymerization effect of tail chain structure of propagating chain polymacromonomer diffusion control effect glass transition temperature lyotropic liquid crystal ラジカル連鎖重合テイル鎖重合速度論バルク重合高分子鎖のからみ合い

项目摘要

Macromonomers are composed of a polymerizable end group and a tail chain. In this study, radical chain polymerization of methacrylate as well as vinylbenzyl terminated polystyrene macromonomers was investigated to understand the influence of the tail chain connected to the polymerizable end group. Polymerization rate, Rp, degree of polymerization of the product, DP, and the rate constants for propagation and termination reactions, k_p and k_t, in the polymerization in solution were measured by using GPC and ESR spectrum. The macromonomers with different molecular weights were prepared by the living anionic polymerization technique. It was found that the k_t strongly depended on both the tail chain length and the macromonomer concentration in feed [M], while k_t did not show a clear dependence on the tail chain length and the [M]. Bulk polymerizations in melt state at higher temperature than the glass transition temperature of the tail chain were also carried out, the results of which showed the strong diffusion control effect and the influence of the equilibrium monomer concentration. Furthermore, the molecular properties and the mesomorphic phase formation of the polymerization products, i.e., poly(macromonomer)s, were also investigated to clarify the nature of the multibranched propagating chain and the structure formation in polymerization media.

大分子单体由可聚合端基和尾链组成。在本研究中，研究了甲基丙烯酸酯以及乙烯基苄基封端的聚苯乙烯大单体的自由基链聚合，以了解连接到可聚合端基的尾链的影响。使用GPC和ESR光谱测量溶液聚合中的聚合速率Rp、产物聚合度DP以及增长和终止反应的速率常数k_p和k_t。采用活性阴离子聚合技术制备了不同分子量的大分子单体。研究发现，k_t 强烈依赖于尾链长度和饲料中大分子单体浓度 [M]，而 k_t 并未显示出对尾链长度和 [M] 的明显依赖性。还进行了高于尾链玻璃化转变温度的熔融态本体聚合，结果显示出较强的扩散控制效应和平衡单体浓度的影响。此外，还研究了聚合产物（即聚（大分子单体））的分子性质和介晶相形成，以阐明多支链增长链的性质和聚合介质中的结构形成。