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Cationic Living Polymerization of Vinyl Ethers with a Polar Pendant

带有极性侧链的乙烯基醚的阳离子活性聚合

基本信息

批准号：
60470110
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：
1985
资助国家：
日本
起止时间：
1985 至 1986
项目状态：
已结题

来源：
https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-60470110/
关键词：
Living Polymerization Cationic Polymerization Vinyl Ethers with a Polar Pendant p-Methylstyrene N-Vinylcarbazole Hydrogen Iodide-Iodine Initiating System Acetyl Perchlorate イオン輸送

项目摘要

Living polymerization is, thus far, the only method to synthesize polymers with well- defined end groups, molecular weight, and narrow molecular weight distribution, all of which are indispensable for specialty polymers with fine functions. Although living polymers can be obtained by anionic polymerization, there have been none by cationic vinyl polymerization except our process for alkyl vinyl ethers using the hydrogen iodide/iodine (HI/ <I_2> ) initiating system. This research project aimed at investigating the possibility of living cationic polymerization of vinyl monomers having a polar pendant and the ion transport property of the poly(vinyl ethers) thus obtained.1. Living Cationic Polymerization of Vinyl Ethers with a Polar PendantWe found that HI/ <I_2> -initiated polymerizations under carefully selected conditions lead to living polymers from vinyl ethers with an ester (2-acetoxyethyl), poly(oxyethylene), or phenoxyethylene group in the pendant. These living processes enabled us to synthesize polymers that have polar pendants coupled with well-designed end groups and narrow molecular weight distribution, for the first time via cationic polymerization.2. Cationic Living Polymerization of Other Vinyl MonomersThe scope of living cationic polymerization was extended to vinyl monomers other than vinyl ethers. We showed suitable combinations of a monomer and a counteranion to provide living polymers; e.g., the nucleophilic iodide anion for N-vinylcarbazole that carry a strongly electron-donating pendant, and the less nucleophilic perchlorate anion for p-methylstyrene that has a weakly electron-donating substituent.3. Transport of Alkali Metal Ions by Poly(vinyl ethers)A poly(vinyl ether) with four oxyethylene units per pendant was found to bind and transport (through a liquid membrane) the potassium ion effectively.

活性聚合是迄今为止合成具有明确端基、分子量和窄分子量分布的聚合物的唯一方法，所有这些都是具有精细功能的特种聚合物所不可缺少的。虽然活性聚合物可以通过阴离子聚合获得，但是除了我们使用碘化氢/碘（HI/）引发体系的烷基乙烯基醚的方法之外，还没有通过阳离子乙烯基聚合<I_2>获得活性聚合物。本研究旨在探讨具有极性侧基的乙烯基单体的活性阳离子聚合的可能性以及由此获得的聚（乙烯基醚）的离子传输性能.具有极性侧基的乙烯基醚的活性阳离子聚合我们发现，<I_2>在仔细选择的条件下，HI/ -引发的聚合导致在侧基中具有酯（2-乙酰氧基乙基）、聚（氧杂环丁烷）或苯氧杂环丁烷基团的乙烯基醚的活性聚合物。这些活性过程使我们能够通过阳离子聚合首次合成具有极性侧基和精心设计的端基以及窄分子量分布的聚合物。2.其它乙烯基单体的阳离子活性聚合活性阳离子聚合的范围扩展到乙烯基醚以外的乙烯基单体。我们展示了单体和抗衡阴离子的合适组合以提供活性聚合物;例如，N-乙烯基咔唑的亲核碘负离子带有强给电子侧基，对甲基苯乙烯的亲核高氯酸负离子带有弱给电子侧基.通过聚（乙烯基醚）传输碱金属离子发现每个侧基具有四个氧杂环丁烷单元的聚（乙烯基醚）有效地结合和传输（通过液膜）钾离子。