Ito Daiki, Ogura Yusuke, Sawamoto Mitsuo, Terashima Takaya
Department of Polymer Chemistry, Graduate School of Engineering, Kyoto University, Katsura, Nishikyo-ku, Kyoto 615-8510, Japan.
Institute of Science and Technology Research, Chubu University, 1200 Matsumoto-cho, Kasugai, Aichi 487-8501, Japan.
ACS Macro Lett. 2018 Aug 21;7(8):997-1002. doi: 10.1021/acsmacrolett.8b00502. Epub 2018 Aug 1.
Acrylate-selective transesterification of methacrylate/acrylate copolymers with alcohols was developed for a site-selective postfunctionalization technique of polymers without using specific monomers. Importantly, a common methyl acrylate efficiently works as a selective modification unit via transesterification coupled with a titanium alkoxide catalyst. The acrylate-selective transesterification is achieved owing to less steric hindrance of the carbonyl groups that are attached to the main chain without an α-methyl group. Typically, the acrylate pendants of dodecyl methacrylate/methyl acrylate (MA) random copolymers were selectively transesterified with benzyl alcohol (BzOH). The conversion of the pendent esters into benzyl esters proportionally increased with MA contents. Additionally, various alcohols were applicable to this MA-selective transesterification system.
开发了甲基丙烯酸酯/丙烯酸酯共聚物与醇的丙烯酸酯选择性酯交换反应，用于聚合物的位点选择性后功能化技术，且无需使用特定单体。重要的是，一种常见的丙烯酸甲酯通过与钛醇盐催化剂偶联的酯交换反应有效地作为选择性修饰单元。由于连接在没有α-甲基的主链上的羰基空间位阻较小，实现了丙烯酸酯选择性酯交换反应。通常，十二烷基甲基丙烯酸酯/丙烯酸甲酯（MA）无规共聚物的丙烯酸酯侧基与苄醇（BzOH）进行选择性酯交换反应。侧酯转化为苄酯的转化率随MA含量成比例增加。此外，各种醇都适用于该MA选择性酯交换反应体系。
