Anionic polymerization of methyl methacrylate and chain-end modification via terminal-selective transesterification with bulky zincate

被引：1

作者：

Hirano, Tomohiro ^{[1
,2
]}

Watanabe, Masayoshi ^{[1
]}

Oshimura, Miyuki ^{[1
,2
]}

Ute, Koichi ^{[1
]}

机构：

[1] Tokushima Univ, Dept Appl Chem, 2-1 Minamijosanjima, Tokushima 7708506, Japan

[2] Tokushima Univ, Res Cluster Dev Pract Mol Transformat Proc, 2-1 Minamijosanjima, Tokushima 7708506, Japan

来源：

EUROPEAN POLYMER JOURNAL | 2023年 / 201卷

关键词：

Anionic polymerization; Chain -end analysis; Postpolymerization modification; HETEROTACTIC POLY(ETHYL METHACRYLATE); TETRA-TERT-BUTYLZINCATE; RADICAL POLYMERIZATION; N-ISOPROPYLACRYLAMIDE; STEREOREGULAR OLIGOMERS; POLY(N-ISOPROPYLACRYLAMIDE); MECHANISM; POLYMERS; SPECTRA; COPOLYMERS;

D O I：

10.1016/j.eurpolymj.2023.112581

中图分类号：

O63 [高分子化学（高聚物）];

学科分类号：

070305 ; 080501 ; 081704 ;

摘要：

The anionic polymerization of methyl methacrylate (MMA) was investigated using dilithium tetra-tert-butylzincate (TBZL), which is a bulky zincate, as an initiator. Poly(methyl methacrylate) (PMMA) with a narrow molecular weight distribution was obtained by conducting the polymerization in toluene at -80 degrees C. Chain-end analysis revealed the formation of PMMA with a tert-butyl group at the alpha-end and a hydrogen atom at the te-end. These results suggest the living nature of the present polymerization. However, a prolonged polymerization time or elevated temperature caused backbiting reactions. Postpolymerization modification of the formed PMMA was also investigated using TBZL as a transesterification catalyst. Chain-end analysis revealed that terminal-selective transesterification occurred only at the monomeric unit at the terminating chain end. Therefore, TBZL appears to play dual roles in the production of chain-end-modified PMMA: an initiator for anionic polymerization and a catalyst for terminal-selective transesterification.

引用

页数：11

共 53 条

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