“饥饿”反应器中自由基聚合动力学(Ⅰ)──关于长链假定适用性的讨论

KINETICS OF RADICAL POLYMERIZATION IN A STARVED FEED REACTOR（Ⅰ）── DISCUSSION ON LONG-CHAIN ASSUMPTION

在建立自由基聚合动力学模型时，由于聚合度很大，通常假定聚合速率等于链增长速率，认为用于链引发所消耗的单体量极少，将其忽略不计，即所谓的长链假定．本文对这一假定进行了详尽的分析，通过计算表明：在高温或／和高引发剂浓度下，特别是在“饥饿”反应器中，长链假定不再适用，建立更为精确的聚合动力学模型时，须考虑长链假定适用性．

It is always assumed that polymerization rate is equal to chain propagation rate while setting up kinetics model of radical polymerization.In the assumption the rate of monomer consumption due to the reaction of primary radicals with monomer is very small and can be ignored,and that is the long-chain assumption.This paper deals with the as sumption in detail.The calculated results indicates that in the case of high temperature and／or high initiator concentration,especially in a starved feed reactor,the long-chain assumption needs correcting so that a more accurate kinetics model of radical polymerization can be set up.