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本文研究了对-甲苯磺酰氯、偶氮苯和四氢呋喃三种添加剂。对乙丙共聚反应的活化作用,实验结果表明,偶氮苯的活化作用最显著,能提高催化效率10倍左右,对-甲苯磺酰氯提高3—6倍,四氢呋喃提高1—2倍。 本文对活化机理作了较详细的探讨,讨论了各种活化剂对聚合反应的影响、活化剂对聚合反应动力学行为的影响,并研究了活化剂与催化剂各组分之间的反应。对上述三种活化剂提出了两种可能的活化途径。对-甲苯磺酰氯和偶氮苯的作用主要是使失去活性的V~(2+)氧化成有活性的V~(3+)化合物,从而增加了活性中心浓度使催化效率提高。而四氢呋喃主要是使V~(3+)化合物稳定而延长活性寿命来提高催化效率。最后还提出了前两种活化剂氧化V~(2+)化合物可能的反应历程。
In this paper, p-toluenesulfonyl chloride, azobenzene and tetrahydrofuran three additives. The experimental results show that the activation of azobenzene is the most significant, which can increase the catalytic efficiency by about 10 times, increase the p-toluenesulfonyl chloride by 3-6 times and raise the tetrahydrofuran by 1-2 times. In this paper, the activation mechanism was discussed in detail. The effects of various activators on the polymerization reaction, the effect of activator on the kinetic behavior of the polymerization reaction, and the reaction between the activator and the catalyst components were also discussed. Two possible activation pathways have been proposed for the above three activators. The main role of p-toluenesulfonyl chloride and azobenzene is to oxidize the inactive V 2+ to an active V 3+ compound, thereby increasing the active site concentration to enhance the catalytic efficiency. However, tetrahydrofuran mainly stabilizes V 3+ compounds and prolongs the active life to improve the catalytic efficiency. Finally, the possible reactions of the first two activators to oxidize V ~ (2+) compounds are also proposed.