Solvent effects on the free radical polymerization of styrene

Abstract
The free radical polymerization of styrene in various solvents has been studied. Using the rotating sector technique at 25°C rate coefficients for termination kt and propagation kp were determined. The linear decrease of the former with decreasing medium fluidity shows that termination is diffusion-controlled. Values of kp decrease as the solvents used are increased in concentration. A similar trend in kp is observed when polymerization is initiated thermally at 60°C. The solvent effect on kt is similar to that previously recorded for methyl methacrylate, but solvents such as benzonitrile and diethyl malonate diminish kp of styrene while they enhance kp for methyl methacrylate.

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