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芳香酰胺的多功能活性聚合方法
作者:小柯机器人 发布时间:2021/6/13 12:39:41

瑞士弗里堡大学Andreas F. M. Kilbinger团队报道了芳香族酰胺的多功能活性聚合方法。相关研究成果发表在2021年6月8日出版的《Nature Chemistry》。

缩聚聚合物通常遵循分步生长动力学,假设所有官能团相互反应的可能性相等。如果能选择性地加快与链端的反应速度,就可以得到活性聚合物。

该文报道了以三苯基膦和三(邻甲氧基苯基)膦为原料合成的两种碘化氯膦试剂。前者在仲芳胺存在下活化芳香羧酸,后者甚至在伯芳胺存在下活化芳香羧酸。这些试剂允许对氨基苯甲酸衍生物形成溶液稳定的活化单体,在胺引发剂存在下以活性方式聚合。当在胺引发剂存在下缓慢地添加到鏻盐中时,其它芳基氨基酸甚至芳基氨基酸的二聚体可以以活性方式聚合。即使存在亲电官能团,也可以制备芳香族氨基酸的二嵌段共聚物和三嵌段三元共聚物。

附:英文原文

Title: A versatile living polymerization method for aromatic amides

Author: Subhajit Pal, Dinh Phuong Trinh Nguyen, Anglique Molliet, Mahshid Alizadeh, Aurlien Crochet, Roberto D. Ortuso, Alke Petri-Fink, Andreas F. M. Kilbinger

Issue&Volume: 2021-06-08

Abstract: Polycondensation polymers typically follow step-growth kinetics assuming all functional groups are equally likely to react with one another. If the reaction rates with the chain end can be selectively accelerated, living polymers can be obtained. Here we report on two chlorophosphonium iodide reagents that have been synthesized from triphenylphosphine and tri(o-methoxyphenyl)phosphine. The former activates aromatic carboxylic acids as acid chlorides in the presence of secondary aromatic amines and the latter even in the presence of primary aromatic amines. These reagents allow p-aminobenzoic acid derivatives to form solution-stable activated monomers that polymerize in a living fashion in the presence of amine initiators. Other aryl amino acids and even dimers of aryl amino acids can be polymerized in a living fashion when slowly added to the phosphonium salt in the presence of an amine initiator. Diblock copolymers and triblock terpolymers of aryl amino acids can be prepared even in the presence of electrophilic functional groups.                                                 

DOI: 10.1038/s41557-021-00712-3

Source: https://www.nature.com/articles/s41557-021-00712-3

期刊信息

Nature Chemistry:《自然—化学》,创刊于2009年。隶属于施普林格·自然出版集团,最新IF:21.687
官方网址:https://www.nature.com/nchem/
投稿链接:https://mts-nchem.nature.com/cgi-bin/main.plex