Living and Alternating Cationic Copolymerization of <i>o</i>-Phthalaldehyde and Various Bulky Enol Ethers: Elucidation of the “Limit” of Polymerizable Monomers
作者:Keisuke Hayashi、Arihiro Kanazawa、Sadahito Aoshima
DOI:10.1021/acs.macromol.1c02398
日期:2022.2.22
Cationic copolymerization of various bulky enol ethers, which have been difficult to homopolymerize and/or copolymerize, was shown to proceed when o-phthalaldehyde (OPA) was used as a comonomer. A series of enol ethers with various substituents on the β-carbon was synthesized from aliphatic aldehydes and alcohols. The relationships between the structures of the enol ethers and the copolymerization
各种大体积的烯醇醚的阳离子共聚,它们一直难以均聚和/或共聚,表明当o-苯二甲醛(OPA)用作共聚单体。以脂肪醛和脂肪醇为原料,合成了一系列在β-碳上具有不同取代基的烯醇醚。系统研究了烯醇醚结构与共聚行为的关系。结果,发现在 β-碳上具有一个或两个甲基和/或伯烷基的单体与 OPA 进行交替共聚。此外,烯醇醚和OPA的活性阳离子共聚在适当的聚合条件下产生交替共聚物。为了阐明可聚合单体的限制,非常庞大的烯醇醚如 β- t的共聚还检查了具有 OPA 的 -丁基或降冰片亚基型单体。发现 OPA 即使与如此庞大的单体也可共聚,这表明 OPA 衍生的增长碳正离子具有较小的空间位阻的独特反应性是成功共聚的关键因素。