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A Reduced Third Order Markov Model for Ethylene‐Norbornene Copolymerization Kinetics with Homogeneous Metallocene Catalysts
Author(s) -
Park Seung Young,
Lee Jongku,
Choi Kyu Yong
Publication year - 2007
Publication title -
macromolecular reaction engineering
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.37
H-Index - 32
eISSN - 1862-8338
pISSN - 1862-832X
DOI - 10.1002/mren.200600002
Subject(s) - norbornene , comonomer , methylaluminoxane , copolymer , polymer chemistry , ethylene , kinetics , metallocene , post metallocene catalyst , materials science , markov chain , polymerization , chemistry , thermodynamics , catalysis , mathematics , organic chemistry , physics , polymer , quantum mechanics , statistics
A reduced third order Markov model is presented to model the kinetics of ethylene‐norbornene copolymerization over rac ‐Et(1‐indenyl) 2 ZrCl 2 /methylaluminoxane catalyst in solution. In our previous work, we developed a penultimate model (second order Markov model) to describe the copolymerization rate behavior and the copolymer composition. Although the penultimate model provides better predictions of the polymerization kinetics than a simple terminal model, it tends to give underestimated norbornene incorporation rates at high norbornene/ethylene mole ratios in the bulk liquid phase. In this work, we propose a modified third order Markov model to improve the model's capability of calculating norbornene incorporation rate and comonomer sequence distribution. The model parameters have been estimated using a parameter optimization technique. The model simulation results indicate that the rate constant for norbornene insertion into a growing chain depends upon the norbornene microblock length at the propagating center.