Yan Tianwei, Guironnet Damien
Department of Chemical and Biomolecular Engineering, University of Illinois, Urbana-Champaign, Urbana, Illinois, 61801, USA.
Angew Chem Int Ed Engl. 2020 Dec 14;59(51):22983-22988. doi: 10.1002/anie.202009165. Epub 2020 Oct 16.
The synthesis of stereoregular telechelic polypropylene (PP) and their use to access triblock amphiphilic copolymers with the PP block located in the center is described. The strategy consists of selectively copolymerizing propylene and a di-functional co-monomer (1,3-diisopropenylbenzene) to yield a α,ω-substituted polypropylene. Initiation of the copolymerization favors insertion of DIB over propylene; propagation steps favor insertion of propylene. Termination via a chain-transfer reaction yields the terminal unsaturation of the polymer. The telechelic polypropylene is then converted into α,ω-hydroxyl-terminated polypropylene and used as a macroinitiator for the synthesis of triblock copolymers. Water-soluble amphiphilic triblock polymers are also synthesized. The use of catalytic reactions simultaneously provides the stereocontrol of the polypropylene and high productivity (multiple chains of block copolymer per metal center).
本文描述了立构规整遥爪聚丙烯（PP）的合成及其用于制备以PP嵌段位于中心的三嵌段两亲共聚物的方法。该策略包括使丙烯与双官能共聚单体（1,3-二异丙烯基苯）选择性共聚，以生成α,ω-取代的聚丙烯。共聚反应的引发有利于二异丙烯基苯而非丙烯的插入；增长步骤有利于丙烯的插入。通过链转移反应终止反应可产生聚合物的末端不饱和键。然后将遥爪聚丙烯转化为α,ω-羟基封端的聚丙烯，并用作合成三嵌段共聚物的大分子引发剂。还合成了水溶性两亲三嵌段聚合物。催化反应的使用同时提供了聚丙烯的立构控制和高生产率（每个金属中心有多条嵌段共聚物链）。
