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Chain Length Distributions of Polyolefins Made with Coordination Catalysts at Very Short Polymerization Times – Analytical Solution and Monte Carlo Simulation
Author(s) -
Soares João B. P.,
Hamielec Archie E.
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.200600001
Subject(s) - polymerization , monte carlo method , polymer , materials science , catalysis , kinetic monte carlo , thermodynamics , polymer chemistry , statistical physics , chemistry , physics , mathematics , organic chemistry , composite material , statistics
Abstract We developed an analytical solution to describe how the CLD of polymers made with coordination polymerization catalysts vary as a function of time for very short polymerization times before the CLD becomes completely developed. We compared the analytical solution with a dynamic Monte Carlo model for validation, obtaining excellent agreement. Our analytical solution can be used to determine when the steady‐state hypothesis, commonly used in polymerization models, becomes valid as a function of polymer chain length. We also extended our model to describe polymerization with multiple‐site‐type catalysts. Depending on the polymerization kinetic parameters of the different site types on the catalyst, the fully developed CLD is reached through very different intermediate CLDs. This modeling approach, although rather simplified, can be used to interpret results from short polymerization time experiments such as the ones done in stopped‐flow reactors.