芳氧基钇配合物引发丙烯腈溶液聚合的Monte Carlo模拟

Monte Carlo Simulation of Acrylonitrile Solution Polymerization Initiated by Y(OAr)_3

用Monte Carlo方法模拟了DMF溶剂体系中单组分芳氧基钇引发剂Y(OAr)3引发丙烯腈溶液聚合的全程反应动力学.通过计算机模拟和实验验证,表明聚合反应过程中存在配位阴离子活性中心,且活性中心容易形成,但很快失活.同时,存在向单体转移和向大分子转移两种链转移反应.获得了一组聚合反应动力学参数:ki=0.053 L/(mol.m in),kp=1.63 L/(mol.m in),kd=0.005 8 m in-1,ktrM=0.052 L/(mol.m in),ktrP=0.075 L/(mol.m in),kpp=0 L/(mol.m in).

The acrylonitrile solution polymerization was discussed based on experiments and Monte Carlo simulation. The simulation results indicated that. anionic active species also present in the system. The polymerization is a rapid initiation, and fast deactivation process, and in the polymerization system there are two chain transfer reactions to monomer and to macromolecules respectively. A set of polymerization reaction rate constants was obtained： ki =0.053 L/（mol · min）, kp = 1.63 L/（ mol · min）, kd =0. 005 8 min^-1, ktrm = 0.052 L/（mol· min）, ktrp =0.075 L/（mol · min）, kpp =0 L/（mol · min）.