ORTHOGONAL COLLOCATION SOLUTION FOR THE FREE RADICAL POLYMERIZATION WITH DIFFUSIONAL LIMITATIONS†

Abstract
Free radical polymerizations in bulk as well as in concentrated solutions exhibit an autoacceleration of the rate of polymerization known as the gel effect. This phenomenon is believed to be caused by a decrease in the rate of termination due to diffusional limitations, In this work, we develop a method for simulating the polymerization when the reaction rate constants depend on the size of the species involved in each reaction. From the mass balances, an infinite system of integro-differential equations is obtained; this system is reduced to a set of algebraic equations using orthogonal collocation with Laguerre polynomials and Gauss-La guerre quadratures

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