Abstract
Herein is reported a novel dynamic kinetic reactor model for the living anionic solution polymerization of styrene/butadiene/divinylbenzene in a continuous stirred tank reactor train. The model accounts for association of the n-butyllithium, the anionic initiator, and the formation of tetrafunctional long-chain branches via propagation with pendant carbonâcarbon double bonds on divinylbenzene incorporated in the copolymer chains. The model predicts individual molecular weight distributions for polymer chains from zero to nine tetrafunctional branch points and by using ZimmâStockmayer long-chain branching equations, it is possible to predict, gel permeation chromatography (GPC) (DRI (differential refractive index)/VISCOTEK) detector cell contents properties (polymer weight fraction, intrinsic viscosity, and number-average molecular weight vs. retention volume). This permits effective use of GPC for kinetic parameter estimation. The GPC measurements on the copolymer in the effluent of a single continuous stirred tank reactor are used to illustrate the effectiveness of parameter estimation.
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