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建立了一种合成高交联度单分散聚苯乙烯的方法--半连续无皂乳液聚合法, 用此法合成的聚苯乙烯交联度可达到50%以上。调整交联剂的加入时间可有效地控制聚苯乙烯粒子的粒度, 制备出高质量高交联度三维有序亚微米级聚苯乙烯微球。揭示了半连续无皂乳液聚合法中合成聚苯乙烯的聚合机理。聚合反应动力学表明:聚合反应开始后加入交联剂, 可以使聚苯乙烯单体在低转化率情况下快速进入第二成核期。交联剂的加入时间和含量影响聚苯乙烯粒子的粒度、单分散性、球形度和溶解性能。

Semi–continuous method, by which monodisperse highly crosslinked polystyrene can be synthetized, is presented in this paper. The crosslingking degree of polystyrene synthetized by this method is more than 50%. The average size of the polystyrene can be controlled by adjusting the time of adding cross–linking agent. High–quality and highly crosslinged three–dimensionally ordered polystyrene microspheres can be synthetized. Mechanism of semi–continuous soap–free emusion polymerization method is investigated. The results show that the secondary nucleation is emerged under low conversion of monomer by delayed divinyl benzene entry. The content of cross–linking agent and the time of adding cross–linking agent affect the average size of the polystyrene, monodispertion properties, shape and solubility.

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