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Merging supercritical carbon dioxide and organocatalysis for the precision and green synthesis of poly(lactide)-based (co)polymers
European Polymer Journal ( IF 6 ) Pub Date : 2017-10-01 , DOI: 10.1016/j.eurpolymj.2017.03.061
B. Grignard , J. De Winter , P. Gerbaux , B. Gilbert , C. Jerome , C. Detrembleur

Abstract Well-defined poly(lactide)-based block copolymers were synthesized by a heterogeneous solvent and metal-free green approach by using organocatalysts in supercritical carbon dioxide (scCO 2 ). We first report on the homopolymerization of both l - and d , l -lactide by organocatalyzed Ring-Opening Polymerization (o-ROP) by using a bicomponent organocatalyst composed of a thiourea derivative and various tertiary amines as cocatalysts. Control over the molar mass and dispersity is achieved until high monomer conversion although the polylactides are insoluble in the polymerization medium. The precision synthesis of PLA-based block copolymers from various CO 2 -phobic hydroxyl end-capped macroinitiators such as polyethylene glycol, polycaprolactone, polybutylene succinate and polyphosphoester was then reported. Merging scCO 2 with this organocatalytic system provides therefore a unique tool for the design under solvent-free conditions of poly(lactide)-based block copolymers that are insoluble in scCO 2 .

中文翻译:

超临界二氧化碳和有机催化相结合,用于聚(丙交酯)基(共)聚合物的精确和绿色合成

摘要 在超临界二氧化碳 (scCO 2 ) 中使用有机催化剂,通过非均相溶剂和无金属绿色方法合成了定义明确的聚(丙交酯)基嵌段共聚物。我们首先报告了使用由硫脲衍生物和各种叔胺组成的双组分有机催化剂作为助催化剂通过有机催化开环聚合 (o-ROP) 均聚 l - 和 d, l - 丙交酯。尽管聚丙交酯不溶于聚合介质,但实现对摩尔质量和分散度的控制直到单体转化率高。然后报道了由各种疏水性羟基封端的大分子引发剂如聚乙二醇、聚己内酯、聚丁二酸丁二醇酯和聚磷酸酯精确合成基于 PLA 的嵌段共聚物。
更新日期:2017-10-01
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