Lewis Pair Polymerization: Perspective on a Ten-Year Journey
Lewis Pair Polymerization: Perspective on a Ten-Year Journey
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DOI：
10.1021/acs.macromol.0c01156
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发表时间：
2020-08-11
期刊：
影响因子：
5.5
通讯作者：
Chen, Eugene Y-X
中科院分区：
文献类型：
--
作者：
McGraw, Michael L.;Chen, Eugene Y-X
自被称为刘易斯对聚合（LPP）的概念以来已经过去了十年，该对聚合（LPP）使用成对的刘易斯酸和碱不仅活化单体，而且影响链引发、增长和转移事件。与其他聚合方法相比，LPP的协同和协同的双组分催化机制赋予了几个独特或有利的特征，包括催化剂/引发剂体系的非凡可调性，对用于高分辨嵌段共聚物的单体混合物的一锅LPP中的共聚单体序列的复合热力学和动力学控制，多官能乙烯基单体的LPP中的完全化学选择性，聚合活性和目标聚合物分子量的独立调节，在本体聚合中用未活化的单体作为溶剂分子的受控热耗散，并将选择性和活性与活性物种的不死性结合，以产生具有记录数（53）嵌段的高分子量聚合物和嵌段共聚物。聚焦于任何聚合方法的四个基本属性-机制，动力学，控制和选择性-这个视角叙述了LPP的成长和发展，追溯每一项创新的基本原理，使每个概念都可以战略性地应用，并描述了未来研究的新前沿。
Ten years have passed since the conception of what was termed Lewis pair polymerization (LPP) that employs Lewis acid and base in pairs to not only activate monomers but also effect chain initiation, propagation, and transfer events. Compared to other polymerization methodologies, LPP's cooperative and synergistic two-component catalytic mechanism empowers several unique or advantageous features, including extraordinary tunability of catalyst/ initiator systems, compounded thermodynamic and kinetic control over comonomer sequences in one-pot LPP of monomer mixtures for highly resolved block copolymers, complete chemoselectivity in LPP of multifunctional vinyl monomers, independent tuning of polymerization activity and target polymer molecular weight, controlled heat dissipation in bulk polymerization with unactivated monomers functioning as solvent molecules, and coupled selectivity and livingness with immortality of the active species to produce ultrahigh molecular weight polymers and block copolymers with record-number (53) blocks. Focusing on four fundamental attributes of any polymerization methodology-mechanism, kinetics, control, and selectivity-this Perspective narrates the growth and development of LPP, tracing each innovation back to fundamental principles so that each concept can be strategically applied, and describes new frontiers fertile for future research.