Journal of Applied Polymer Science, Vol.65, No.6, 1053-1080, 1997
Polymerization of Olefins Through Heterogeneous Catalysis .18. A Kinetic Explanation for Unusual Effects
The development of a detailed kinetic model describing some of the unusual effects observed in catalyzed olefin polymerization is presented. Based on the method of moments, the model describes the rate effects of hydrogen and comonomers, as well as the ability of certain systems to incorporate long chain branches via internal and/or terminal double bond polymerization. Examples are provided demonstrating the model’s ability to predict rates and degrees of polymerization with ethylene, propylene, and l-hexene monomers. In the case of propylene, multiple insertion mechanisms are modeled and compared with experimental sequence length and end group data. In other examples the model is used to simulate an oscillating metallocene catalyst and a metallocene catalyst capable of branch addition via terminal double bond polymerization.
Keywords:ZIEGLER-NATTA CATALYSTS;SOLUTION COPOLYMERIZATION;ETHYLENE POLYMERIZATION;PROPENE POLYMERIZATION;ALPHA-OLEFINS;HYDROGEN;ACTIVATION;COMONOMER;CENTERS