非理想活性聚合反应动力学的一般模型 Ⅱ.非稳态理论

GENERAL KINETIC MODEL OF IMPERFECT LIVING POLYMERIZATION Ⅱ. NON STEADY STATE APPROACH

对各种两物种体系非理想活性聚合反应作了非稳态动力学分析，给出了各种分子参数在非稳态条件下的公式。数值计算的结果表明，在链增长反应速率比休眠物种和活性物种之间的相互转化速率大很多时，聚合反应不易达到稳态；当上述两种反应速率比较接近时，体系较快即能达到稳态，只有在反应开始的阶段，稳态和非稳态的理论结果有所差别。

This paper developed a non steady state theory for imperfect living polymerizations with various equilibria between active and dormant species giving expressions of various molecular parameters, such as the number and the weight average degrees of polymerization and the polydispersity index. The comparison of theoretical results of the non steady state approach with those of the stationary state assumption shows that numerical outcomes from both methods conform with each other except at the beginning of the polymerization if the rate constant of chain propagation is comparable with that of reactivity exchange between dormant and active species, and a big difference between the results of the two approaches was observed in the case of k p being much larger than k 1 or k 2.