阳离子依赖的双重激活基序用于环状酯的阴离子开环聚合。
A Cation-Dependent Dual Activation Motif for Anionic Ring-Opening Polymerization of Cyclic Esters.
机构信息
Department of Chemistry, Stanford University, Stanford, California 94305-5080, United States.
IBM Almaden Research Center, 650 Harry Road, San Jose, California 95120, United States.
出版信息
J Am Chem Soc. 2022 May 18;144(19):8439-8443. doi: 10.1021/jacs.2c01436. Epub 2022 May 3.
A new organocatalyst for the ring-opening polymerization of lactones has been identified. Under the tested conditions, the anions of 2,2'-bisindole promote fast, living polymerizations (as short as 10 ms) which are selective for chain elongation over transesterification (Đ ≤ 1.1). While structurally related to (thio)urea anion catalysts, anions of 2,2'-bisindole activate the monomer via the counterion rather than through hydrogen bonding. This new activation motif enables modulation of the polymerization rate by 2 orders of magnitude by changing the counterion.
一种用于内酯开环聚合的新型有机催化剂已经被确定。在测试条件下，2,2'-联吲哚的阴离子促进快速、活的聚合（最短为 10 毫秒），其选择性地进行链增长而不是酯交换（Đ ≤ 1.1）。虽然与（硫）脲阴离子催化剂在结构上相关，但 2,2'-联吲哚的阴离子通过抗衡离子而不是通过氢键来激活单体。这种新的激活模式使得通过改变抗衡离子可以将聚合速率调节两个数量级。
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