本体法合成ABS树脂 Ⅱ．预聚合反应动力学研究

Bulk polymerization of ABS resin Ⅱ.Study on prepolymerization kinetics

采用本体聚合方法,以1,1-二(叔丁基过氧基)环己烷(DP275B)引发苯乙烯、丙烯腈在聚丁二烯橡胶上接枝共聚合。考察了不同聚合工艺条件下丙烯腈-丁二烯-苯乙烯三元共聚物(ABS)预聚合反应动力学行为规律,并求出相应的假一级表观增长反应速率常数。结果表明:不同工艺条件下的动力学曲线均符合一级线性关系;镍系高顺式橡胶BR9004体系的预聚合反应速率最快;增加引发剂DP275B浓度、提高引发温度、降低低顺式聚丁二烯橡胶700A用量和聚合搅拌速率均可加快ABS预聚合反应速率;当w(700A)为5.0%,w(DP275B)为0.021%时,共聚单体的表观增长反应活化能为10.84 kJ/mol,频率因子为0.12 min^(-1)。

The graft copolymerization of styrene and acrylonitrile monomer onto polybutadiene rubber was conducted by bulk polymerization method through the initiation of 1,1-bis（tert-butylperoxy）cyclohexane （DP275B）. The main factors influencing the prepolymerization kinetics behavior of acrylonitrile-butadiene-styrene terpolymer （ABS） were studied, and the pseudo first order apparent propagation rate constants were calculated. The results show that the kinetic curve is first order and linear under different technological conditions. The prepolymerization rate in the nickel catalyzed high-cis polybutadiene rubber （PB） system is the rapidest. Furthermore, the prepolymerization rate increases with the increase in DP275B initiator dosage and elevation of reaction temperature, and the decrease in low-cis-PB Asaprene 700A content and stirring speed. When the mass fractions of 700A rubber and DP275B are 5.0% and 0.021%, respectively, the apparent chain propagation activation energy of comonomers is 10.84 kJ/mol, and the chain growth frequency factor is 0.12 min-1.