Chlorocarboxylation of polyethylene, III. kinetics of the process

Abstract

The paper presents the kinetic model and derives the values of the kinetic parameters for the simultaneous reaction of chlorine and maleic anhydride with polyethylene in tetrachloroethyane solution. The sites of attack in the investigated reaction being the hydrogen atoms in the polyethylene chain, the concept of occupied and vacant sites available for the reaction has been used to derive the kinetic model. The temperature dependence of the ratio of rate constants (k_Cl/k_MA) for the attack of chlorine and maleic anhydride is obtained by applying Arrhenius law. The analysis of the results reveals that the activation energy difference (E_Cl - E_MA) is of the order of - 19 kcal/mol and the pre-exponential factor ratio (A_Cl/A_MA) is of the order of 735. The generalized form of the equations is also presented in order to extend this method of kinetic analysis to many other similar systems.