Synchronous Control of Chain Length/Sequence/Topology for Precision Synthesis of Cyclic Block Copolymers from Monomer Mixtures
Synchronous Control of Chain Length/Sequence/Topology for Precision Synthesis of Cyclic Block Copolymers from Monomer Mixtures
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DOI：
10.1021/jacs.1c00561
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发表时间：
2021-02-27
影响因子：
15
通讯作者：
Chen, Eugene Y. -X.
中科院分区：
文献类型：
--
作者：
McGraw, Michael L.;Clarke, Ryan W.;Chen, Eugene Y. -X.
具有可预测分子量和低分散度的环状聚合物的精确合成是一项具有挑战性的任务，特别是对于通过快速链增长机制且无需高度稀释的环状极性乙烯基聚合物。更难的是环状嵌段共聚物（cBCP）的精确合成，最好是从共聚单体混合物中合成。在这里，我们报告说，路易斯对聚合（LPP）能够进行热力学和动力学复合序列控制，成功解决了这一长期存在的挑战。因此，丙烯酸酯/甲基丙烯酸酯混合物在环境温度和正常浓度条件下快速、选择性地一步生成具有高分子量（M-n = 247 kg/mol）和低分散性（D = 1.04）的明确的cBCP。此类 cBCP 已通过多种技术进行表征，包括通过成像进行直接结构观察。
Precision synthesis of cyclic polymers with predictable molecular weight and low dispersity is a challenging task, particularly concerning cyclic polar vinyl polymers through a rapid chain-growth mechanism and without high dilution. Harder yet is the precision synthesis of cyclic block copolymers (cBCPs), ideally from comonomer mixtures. Here we report that Lewis pair polymerization (LPP) capable of thermodynamically and kinetically compounded sequence control successfully addressed this longstanding challenge. Thus, LPP of acrylate/methacrylate mixtures under ambient temperature and normal concentration conditions rapidly and selectively affords well-defined cBCPs with high molecular weight (M-n = 247 kg/mol) and low dispersity (D = 1.04) in one step. Such cBCPs have been characterized by multiple techniques, including direct structural observation by imaging.