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Experimental Validation of Intermediate Termination in RAFT Polymerization with Dithiobenzoate via Comparison of Miniemulsion and Bulk Polymerization Rates

机译:通过细乳液和本体聚合速率比较,RAFT与二硫代苯甲酸酯聚合中终止反应的实验验证

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摘要

To understand if either of two controversial models for the retardation by RAFT agents is applicable, styrene polymerization using dithiobenzoate as the RAFT agent is carried out in both bulk and miniemulsion systems with the same rates of radical generation and the same RAFT agent concentrations. Miniemulsion polymerization with average diameters of the miniemulsion droplets of ≈107 nm is by far faster than in bulk, and the obtained rate of polymerization agrees well with the calculated results assuming a bimolecular termination between propagating radical and intermediate radical, generated by the addition reaction of propagating radical to the RAFT agent, which shows that the intermediate termination is the major reason for rate retardation by the RAFT agent.
机译:为了理解是否有争议的两种RAFT阻滞剂模型是否适用,在本体和细乳液体系中均以相同的自由基生成速率和相同的RAFT剂浓度进行了使用二硫代苯甲酸酯作为RAFT剂的苯乙烯聚合。细乳液聚合的平均直径约107 nm的细乳液聚合要比本体的快得多,并且假设通过自由基加成反应生成的自由基和中间自由基之间存在双分子端接,则聚合速率与计算结果吻合良好。自由基扩散到RAFT剂上,这表明中间终止是RAFT剂降低速率的主要原因。

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