Alternating Copolymerization Realized with Alternating Transformation of Anion-Migrated Ring-Opening Polymerization and Anionic Polymerization Mechanisms
Alternating Copolymerization Realized with Alternating Transformation of Anion-Migrated Ring-Opening Polymerization and Anionic Polymerization Mechanisms
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阴离子迁移开环聚合与阴离子聚合机理交替变换实现交替共聚
DOI：
10.1021/acs.macromol.1c00814
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发表时间：
2021
期刊：
影响因子：
5.5
通讯作者：
Ma Hongwei
中科院分区：
文献类型：
--
作者：
Bai Hongyuan;Han Li;Li Chao;Zhang Songbo;Wang Xuefei;Yin Yu;Zhang Xiaolu;Ma Hongwei
交替序列作为一种明确的单体序列分布，其精确的重复结构赋予聚合物特殊的性能。在这项研究中，我们报告了一种新的交替共聚1，1-二苯基乙烯（DPE）衍生物与1-环丙基乙烯基苯（CPVB）的阴离子迁移开环聚合（AMROP的CPVB）和一般的阴离子聚合（AP的DPE衍生物）的交替转换机制。特别地，首先研究了该共聚体系中的基元反应的动力学，并且证实实现了具有理想的交替共聚动力学（kCD，kDC> 0;kDD，kCC= 0;因此，在20 °C下rC=rD= 0）的交替共聚。此外，DPE衍生物的较低反应性和反应中CPVB的过量进料都基本上不影响交替序列的形成。此外，由于DPE衍生物（DPE，1-[4-[N，N-双（三甲基硅基）氨基]苯基]-1-苯乙烯（DPE-NSi 2）和1-（4-二甲氨基苯基）-1-苯乙烯（DPE-NMe 2））具有不同的反应活性，通过与CPVB的三元共聚可以调节DPE和DPE衍生物单元在链中的序列分布。因此，在交替共聚体系中，由于动力学的限制，在一般聚合反应中不能实现的具有无规、梯度和嵌段分布的DPE单元可以基于上述交替共聚体系得到很好的调节。总之，本研究在高分子化学领域启发和促进了交替共聚。
As a kind of well-defined monomer sequence distribution, an alternating sequence endows polymers with specific properties owing to the precisely repeating structure. In this study, we report a novel alternating copolymerization of 1,1-diphenylethylene (DPE) derivatives with 1-cyclopropylvinylbenzene (CPVB) by means of alternating transformation of anion-migrated ring-opening polymerization (AMROP for CPVB) and general anionic polymerization (AP for DPE derivatives) mechanisms. In particular, the kinetics of the elementary reaction in this copolymerization system were first investigated, and it was confirmed that alternating copolymerization with the ideal alternating copolymerization kinetics (kCD,kDC> 0;kDD,kCC= 0; thus,rC=rD= 0 at 20 °C) was achieved. Additionally, neither the lower reactivity of the DPE derivative nor the excess feeding of CPVB in the reaction substantially influenced the formation of alternating sequences. Furthermore, because the DPE derivatives (DPE, 1-[4-[N,N-bis(trimethylsilyl) amino]phenyl]-1-phenylethylene (DPE-NSi2) and 1-(4-dimethylaminophenyl)-1-phenylethylene (DPE-NMe2)) exhibited different reactivities, the sequence distributions of DPE and DPE derivative units in the chain can be regulated through terpolymerization with CPVB. Therefore, DPE units withrandom, gradient,andblockdistributions in alternating terpolymers, which cannot be achieved in general polymerization reactions because of kinetic limitations, can be well regulated based on the abovementioned alternating copolymerization system. Overall, this study inspires and promotes alternating copolymerization in the field of polymer chemistry.