Expanding the toolbox of controlled/living branching radical polymerization through simulation-informed reaction design
Expanding the toolbox of controlled/living branching radical polymerization through simulation-informed reaction design
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DOI：
10.1016/j.chempr.2022.02.022
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发表时间：
2022-05-13
期刊：
影响因子：
23.5
通讯作者：
Zhong, Mingjiang
中科院分区：
文献类型：
--
作者：
Cao, Mengxue;Liu, Yutong;Zhong, Mingjiang
具有优异机械、光子和电学性能的支化聚合物在生物医学应用、水处理和催化领域显示出越来越大的优势。将分支功能图案锚定到选定的分子/纳米物体上引入了结构层次以及组合和增强的特性。为了实现支化功能聚合物的有效接枝，需要控制链增长支化聚合，但仍待探索。在本文中，链增长过程是通过原子转移自由基聚合将α-卤代丙烯酸酯与常规乙烯基单体共聚来实现的。我们进行了系统的机理研究，以获得聚合条件的最佳配置，其中采用了活化剂再生方法。在动力学模拟的辅助下，多种乙烯基单体，包括丙烯酸酯、苯乙烯、丙烯腈和丙烯酰胺，成功地与具有高单体转化率的α-卤代丙烯酸酯共聚，生成具有可调节支化度的明确支化聚合物。使用合成的聚（N-异丙基丙烯酰胺）研究了受控支化对热响应性能的影响。
Branched polymers with superior mechanical, photonic, and electrical properties have shown their growing advantages in biomedical applications, water treatment, and catalysis. Anchoring branched functional motifs onto select molecular-/nano-objects introduces structural hierarchy as well as combined and enhanced properties. To realize efficient grafting of branched functional polymers, a controlled chain-growth branching polymerization is desirable but remains underexplored. In this article, the chain-growth process was achieved by copolymerizing alpha-haloacrylate with conventional vinyl monomers via atom transfer radical polymerization. We conducted systematic mechanistic studies to obtain an optimal profile of the polymerization conditions, where an activator regeneration approach was employed. Assisted by kinetic simulations, a variety of vinyl monomers, including acrylates, styrene, acrylonitrile, and acrylamides, were successfully copolymerized with alpha-haloacrylate with high monomer conversion to produce well-defined branched polymers with tunable degrees of branching. The impact of controlled branching on the thermoresponsive properties was studied using the synthesized poly(N-iso-propylacrylamide).