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Study on the Development of New Counterions That Permit Living Cationic Polymerization

允许活性阳离子聚合的新型抗衡离子的开发研究

基本信息

批准号：
02453107
负责人：
HIGASHIMURA Toshinobu
金额：
$ 3.07万
依托单位：
Kyoto University
依托单位国家：
日本
项目类别：
Grant-in-Aid for General Scientific Research (B)
财政年份：
1990
资助国家：
日本
起止时间：
1990 至 1991
项目状态：
已结题

来源：
https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-02453107/
关键词：
Cationic Polymerization Living Polymerization Initiator Vinyl Ether Counterion Growing Carbocation Lewis Acid Activator

项目摘要

This research project was to develop new initiating systems and counteranions for living cationic polymerization of a wide variety of vinyl monomers on the basis of a new concept, "stabilization of growing carbocations by nucleophilic counteranions". The following summarizes the achievements of the 2-year project :1) New Initiating Systems for Living Cationic Polymerization of Vinyl EthersFive classes of new initiating systems for living cationic polymerization of vinyl ethers have been developed, which consist of various combinations of a protonic acids (initiator) and a weak Lewis acid (activator) : (a) acetic acid derivative/zinc chloride ; (b) ring-substituted benzoic acid/zinc chloride ; (c) hydrogen halide/zinc halide ; (d) trimethylsilyl halide/zinc halide (with a carbonyl compound) ; and (e) hydrogen iodide/metal acetylacetonate. These findings have shown the concept, "stabilization of growing carbocations by nucleophilic counteranions", to be a general principle for living cat … More ionic polymerization of vinyl monomers.2) Living Cationic Polymerization of StyreneLiving cationic polymorization of styrene has been achieved with use of the methanesulfonic acid/tin tetrachloride or the styrene-hydrogen chloride/tin tetrachloride initiating system in methylene chloride solvent in the presence of a salt with the chloride anion. The development of this process is important in that this is the first example of the ideal living cationic polymerization of such poorly reactive monomers as styrene, which lacks an electron-donating (cation-stabilizing) substituent.3) Spectroscopic Analysis of the Growing Species in Living Cationic PolymerizationMixtures of zinc chloride and the adduct of vinyl ether with a protonic acid (as a model of the growing terminal) were directly analyzed by proton nuclear magnetic resonance spectroscopy. The analysis has revealed : (a) The growing end undergoes interaction with zinc chloride and is thereby activated to propagate ; (b) the interaction is a fast reversible process ; and (c) an ionic intermediate is involved in the propagation reaction where the activated growing end attacks a monomer. Less

本研究基于“亲核反阴离子稳定生长中的碳正离子”这一新概念，为各种乙烯基类单体的活性阳离子聚合开发了新的引发体系和反阴离子。1)乙烯基醚活性阳离子聚合的新引发体系已开发出五类用于乙烯基醚活性阳离子聚合的新引发体系，其中包括质子酸(引发剂)和弱Lewis酸(激活剂)的各种组合：(A)醋酸衍生物/氯化锌；(B)环取代苯甲酸/氯化锌；(C)卤化氢/卤化锌；(D)三甲基硅基卤化物/卤化锌；以及(E)碘化氢/金属乙酰乙酰乙酸锌。这些发现表明，“用亲核反阴离子稳定生长中的碳正离子”的概念是活着的猫…的普遍原则。用甲烷磺酸/四氯化锡或苯乙烯-氯化氢/四氯化锡引发体系，在二氯甲烷溶剂中，在含有氯离子的盐存在下，实现了活性阳离子聚合。这一过程的发展很重要，因为这是第一个理想的活性阳离子聚合单体，如缺乏供电子(阳离子稳定)取代的苯乙烯。3)活性阳离子聚合中增长物种的光谱分析直接用质子核磁共振波谱分析氯化锌和乙烯基醚与质子酸的加合物(作为增长末端的模型)。分析表明：(A)生长端与氯化锌发生相互作用，从而被激活以进行繁殖；(B)该相互作用是一个快速可逆的过程；以及(C)在被激活的生长端攻击单体的情况下，离子中间体参与了传播反应。较少