Jiang Yudian, Cao Kun, Wang Qi
MOE Key Laboratory of Macromolecular Synthesis and Functionalization, Department of Polymer Science & Engineering, Zhejiang University, Hangzhou 310058, China.
State Key Laboratory of Chemical Engineering, College of Chemical and Biological Engineering, Zhejiang University, Hangzhou 310058, China.
Polymers (Basel). 2025 Mar 12;17(6):741. doi: 10.3390/polym17060741.
Exploring new polymerization strategies for currently available monomers is a challenge in polymer science. Herein, a bifunctional initiator (BFI) is introduced for the conventional radical polymerization of a vinyl monomer, resulting in linear radical additions-coupling polymerization (LRAsCP). In LRAsCP, the coupling reaction alongside the addition reaction of the radicals contributes to the construction of polymer chains, which leads to stepwise growth of the multiblock structure. Theoretical analysis of LRAsCP predicted variation of some structural parameters of the resulting multiblock polymer (MBP) with the extent of initiation of the BFI and the termination factor of the radicals. Simultaneous and cascade initiations of the BFI were compared. LRAsCP of styrene was conducted, and a kinetics study was carried out. The increment in with polymerization time demonstrated the stepwise mechanism of the formation of the MBP. The variation of the structural parameters of MBP fitted well with the theoretical prediction. Two-step LRAsCP was conducted and multiblock copolymers (MBcP) were obtained either by in situ copolymerization of styrene and MMA or by a second copolymerization of styrene and BMA. The current results demonstrate that the introduction of a BFI to conventional radical polymerization generates a new polymerization strategy, leading to a new chain architecture, which can be extended to other radical polymerizable monomers.
探索当前可用单体的新聚合策略是高分子科学中的一项挑战。在此，引入了一种双功能引发剂（BFI）用于乙烯基单体的常规自由基聚合，从而实现线性自由基加成-偶联聚合（LRAsCP）。在LRAsCP中，自由基的偶联反应与加成反应共同促成聚合物链的构建，进而导致多嵌段结构的逐步增长。对LRAsCP的理论分析预测了所得多嵌段聚合物（MBP）的一些结构参数随BFI引发程度和自由基终止因子的变化。比较了BFI的同时引发和级联引发。进行了苯乙烯的LRAsCP，并开展了动力学研究。随聚合时间的增加证明了MBP形成的逐步机理。MBP结构参数的变化与理论预测吻合良好。进行了两步LRAsCP，通过苯乙烯与甲基丙烯酸甲酯的原位共聚或苯乙烯与甲基丙烯酸丁酯的二次共聚获得了多嵌段共聚物（MBcP）。当前结果表明，将BFI引入常规自由基聚合产生了一种新的聚合策略，导致了一种新的链结构，这可以扩展到其他可自由基聚合的单体。
