基于蒙特卡罗模拟的不同聚合温度下的丙烯聚合动力学研究(英文)

Study on kinetics of propylene polymerizationat different temperatures via Monte Carlo simulation

在不考虑其他杂质参与聚合反应的情况下,并基于已有对丙烯聚合反应过程的普适化认识,提出了一个普适的丙烯聚合反应机理(基元反应).在已有的丙烯聚合反应机理基础上,为了证实该聚合反应过程总活性基是否满足“稳态假定”以及考察聚合反应温度对聚合过程的影响,采用蒙特卡罗模拟方法研究了传统Ziegler-Natta催化剂催化下的丙烯聚合动力学.模拟得到的总活性基数目在丙烯聚合初期快速增加到峰值,然后随聚合反应的进行保持恒定,证实了丙烯聚合过程中总活性基符合稳态假定.同时,模拟得到了聚合温度对丙烯聚合过程的转化率、分子量的影响.模拟结果表明:在聚合过程中,丙烯单体的消耗速率随聚合温度升高而增加;不同聚合温度下的数均聚合度峰值相同,但随温度增加,数均聚合度峰值来得早;随聚合温度增加,数均分子量减少,分子量分布变宽.

The elementary reactions of propylene polymerization catalyzed by conventional Ziegler-Natta catalysts was proposed according to the comprehensive view and without considering the effect of any impurity in the material on propylene polymerization. The Monte Carlo simulation technique was employed to investigate the kinetics of propylene polymerization in order to determine the validity of the stationary state assumption and the effects of the polymerization temperature on the polymerization. The simulated total amount of active species, which only increases quickly at the beginning of the polymerization, indicates that the stationary state assumption in the studied system is valid. Moreover, significant effects of polymerization temperature on the polymerization conversion, and the molecular weight and its distribution were also analyzed. The simulated results show that the consumption rate of propylene increases with the increase of polymerization temperature; the maximum values of the number-average degree of polymerization are constant at different polymerization temperatures, however, the peak appears earlier with the higher temperature; as the polymerization temperature increases, the average molecular weight decreases and the molecular weight distribution changes greatly.