Solvent effects in butyl acrylate and vinyl acetate homopolymerizations in toluene

A series of butyl acrylate (BA) and vinyl acetate (VAc) homopolymerizations in toluene was conducted to investigate the effect of solvent at different solvent and chain transfer agent (CTA) concentrations. Because the experimental determination of the individual propagation and termination rate constants for these systems is challenging, experimental observations were limited to the lumped rate constant (kp/k ). Differences in the lumped rate constant, at different solvent and CTA concentrations, were assumed to be attributed to the effect of solvent on the termination rate constant. Our hypothesis was that the termination rate constant kt was affected by the presence of solvent. At higher solvent concentrations, chain transfer to solvent occurs more frequently and leads to the formation of shorter chains, which move more easily and are able to terminate more quickly compared to longer chains. Thus, kt will increase, leading to a decrease in the lumped rate constant. The experimental results confirmed the presence of a solvent effect on the lumped rate constant. This effect was more pronounced in the case of VAc compared to BA solution homopolymerizations. Under the investigated conditions, increased CTA concentrations did not substantially affect the rate of BA homopolymerizations, whereas a slight synergistic effect between the CTA and solvent at higher CTA and solvent concentrations was apparent for VAc homopolymerizations.