Proton Transfer Anionic Polymerization of Methyl Methacrylate with Ligands for Dual Control of Molecular Weight and Tacticity  

作　　者：Katsutoshi Sagawa Mineto Uchiyama Hironobu Watanabe Chihiro Homma Masami Kamigaito 

机构地区：[1]Department of Molecular and Macromolecular Chemistry,Graduate School of Engineering,Nagoya University,Nagoya 464-8603,Japan [2]Department of Chemical Science and Engineering,School of Materials and Chemical Technology,Institute of Science Tokyo,2-12-1-S1-13 Ookayama,Meguro-ku,Tokyo 152-8552,Japan

出　　处：《Precision Chemistry》2024年第12期628-633,共6页精准化学(英文)

基　　金：supported by a JSPS KAKENHI Grant-in-Aid for Scientific Research(C)(No.JP22K05209);Transformative Research Areas(A)“Green Catalysis Science for Renovating Transformation of Carbon-Based Research”(No.JP23H04915)for M.U.;Scientific Research(A)(No.JP22H00333)for M.K.K.S.acknowledges the“Graduate Program of Transformative Chem-Bio Research(GTR)”at Nagoya University.

摘　　要：Dual control of the molecular weight and tacticity in proton transfer anionic polymerization(PTAP)of methyl methacrylate(MMA)was investigated by using various ligands in the presence of a bulky potassium base catalyst and an organic compound with a weakly acidic C−H bond as dormant species in toluene at 0℃.The tacticity of the resulting poly(MMA)(PMMA)produced without ligands was nearly atactic(rr/mr/mm=22/54/24).However,the use of 18-crown-6 as a ligand afforded predominantly syndiotactic PMMA(rr≈58%),whereas the use of chiral bis(oxazoline)ligands gave slightly isotactic-rich PMMA(mm≈32%).Molecular weight control of PMMA was achieved(Đ=1.1−1.2)by adding 1,1-diphenylethanol as a reversible terminator while maintaining control of the tacticity with the above ligands.Stereoblock PMMA consisting of atactic and syndiotactic segments was successfully synthesized via sequential PTAP using macroinitiator/macro-CTA methods.

关 键 词：living polymerization anionic polymerization stereospecific polymerization METHACRYLATE stereoblock polymer 

分 类 号：O63[理学—高分子化学]