Estimation of Reactivity Ratios from Multicomponent Copolymerizations

Abstract

Abstract The composition of the copolymer formed from n monomers in addition polymerization can be expressed in terms of the monomer feed composition and n(n - 1) binary reactivity ratios, according to the familiar simple copolymer model. Reactivity ratios are determined experimentally from cor-responding feed and monomer compositions in binary co-polymerizations. This article reports methods for deriving such reactivity ratios directly from multicomponent polymerization data. Analytical solution of the multi-component copolymer equations is not feasible because of the limited number of experimental points and experimental uncertainty in the copolymer composition. Computer-assisted procedures have been developed to estimate re-activity rates by optimizing the fit of predicted and experimental copolymer compositions, given the monomer feed composition and preliminary values of the reactivity ratios. All n(n - 1) reactivity ratios are adjustable. The methods are demonstrated for styrene/methacrylonitrile/ a-methylstyrene, butadiene/styrene/2-methyl- 5-vinyl- pyridine and acrylonitrile/methyl methacrylate/& methylstyrene systems. Binary reactivity ratios predict ternary copolymer compositions generally well in these cues. Reasons are suggested why reactivity ratios from multicomponent experiments may not match the corresponding parameters from binary copolymerizations.