Kinetics of the ultrasonic degradation of poly (alkyl methacrylates)

The influence of the alkyl group substituents on the ultrasonic degradation of poly (alkyl methacrylate)s, namely poly (methyl methacrylate) (PMMA), poly (ethyl methacrylate) (PEMA) and poly (butyl methacrylate) (PBMA) was studied. The rate coefficient increased with an increase in the number of carbon atoms in the alkyl group: thus the order of degradation was PBMA>PEMA>PMMA. This was attributed to the scission of the main chain, which increases with the length of the side chain. The ultrasonic degradation of PBMA was investigated in various solvents, at different temperatures and at different ultrasound intensities. The degradation rate coefficients increased logarithmically with the decrease in vapor pressure and increased linearly with an increase in viscosity of the solvent and ultrasound intensity. The effect of three different initiators, benzoyl peroxide (BPO), dicumyl peroxide (DCP) and azo-bisisobutyronitrile (AIBN) on the ultrasonic degradation of PBMA was also studied. The degradation of the polymer decreased in the presence of the initiator. A continuous distribution model was developed for the radical mechanism involved in degradation and was used to determine the degradation rate coefficients of PBMA in presence of initiator. The model indicated that the degradation rate coefficient of the interaction of the PBMA radical with the initiator is independent of the dissociation constant of the initiator.