Abstract: This paper considers pendant double bond as the third double bond in monoene/diene radical crosslinking copolymerization (RCC),and the model can be simplified when the amount of divinyl monomer is less than 5%(mol).Free radical tri-polymerization is introduced instead of free radical crosslinking copolymerization.For MMA/EGDMA free radical crosslinking copolymerization,since the vinyl structure of the MMA and EGDMA is identical,the model is simplified further by considering the vinyls of MMA,EGDMA and pendant double bond have equal chemical reaction ability.An empirical function developed by W.H.Ray is used to describe auto-acceleration phenomena,and diffusion effects should show additional crosslinking influence at this time.Then a coefficient k which comes from Arrhenius activation energy concept was introduced to amend reaction speed parameter,which involves termination reaction and crosslinking reaction,so the effect of crosslinking joint on RCC could be described.Finally,a statistics-kinetic model is established.The relationships between conversion and copolymertization time,average crosslink density with conversion are investigated.The curves predicted by the model fit well with experimental data.

摘要： 以甲基丙烯酸甲酯 /二甲基丙烯酸乙二醇酯自由基交联共聚合为研究对象 ,考虑到单烯与双烯自由基交联共聚合过程第 3种双键———悬挂双键的影响 ,在低双烯单体用量下简化为拟三元自由基共聚合 ,引入具有Arrhenius性质的交联影响因子 ,建立拟三元自由基交联共聚合动力学模型 .经自由基本体和溶液共聚试验验证了拟三元自由基交联共聚合动力学模型 ,通过数值仿真讨论了平均交联密度随转化率的变化关系 ,比较了本体共聚和溶液共聚条件下平均交联密度的变化规律