氨解
高分子化学
化学
聚合
单体
自由基聚合
自由基引发剂
丙烯酸酯
光致聚合物
溶液聚合
战术性
链生长聚合
聚合物
有机化学
催化作用
作者
Yayue Pan,Makoto Ouchi
标识
DOI:10.1002/anie.202308855
摘要
We report syntheses of isotactic polyacrylate and polyacrylamide via a stereospecific radical polymerization of a pendant-transformable monomer, acrylamide carrying isopropyl-substituted ureidosulfonamide (1), followed by post-polymerization modification (PPM). The study in the alcoholysis and aminolysis reactions of the model compound (2) for evaluation of the transformation ability of the electron-withdrawing pendant group on the repeating unit 1 revealed the following points: the pendant of the polymer became more reactive than that of monomer; the pendant was active enough for aminolysis reaction affording the amide compound quantitatively without additive/catalyst; the addition of a lithium triflate [Li(OTf)] and triethylamine (Et3 N) was effective as for promotion of the alcoholysis reaction. Poly(methyl acrylate) (PMA) was quantitatively obtained via the radical polymerization of 1 in the presence of Li(OTf) at 60 °C and the subsequent addition of methanol along with Et3 N. Thus-obtained PMA showed higher isotacticity [m=74 %] than that directly obtained via radical polymerization of methyl acrylate (MA) (m=51 %). The isotacticity was further increased as the temperature and monomer concentration were lower, and eventually m was increased up to 93 %. The aminolysis PPM after the iso-specific radical polymerization of 1 gave various isotactic polyacrylamides carrying different alkyl pendant groups, including poly(N-isopropylacrylamide) (PNIPAM).
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