Abstract
Polymers of vinyl acrylate, methacrylate, and α-chloroacrylate were prepared by radical polymerization at 60°C at various monomer concentrations in benzene. The residual double bond in the polymers was determined to be mainly a vinyl group by infrared spectroscopy and ICl titrimetry. The decrease in the residual double bond with decreasing monomer concentration can be explained in terms of an intramolecular chain monocyclization-bicyclization mechanism. The proposed monocyclization was carried out between the polymer radical and vinyl group of a penultimate monomer unit. Bicyclization was carried out between a monocyclized radical and vinyl group of the polymer end. The ratios of monocyclization rate constant over intermolecular propagation rate constant were evaluated to be 20 for vinyl acrylate, 0.22 for vinyl methacrylate and 0.60 mol dm−3 for vinyl α-chloroacrylate, respectively. The ratios of bicyclization rate constant over intermolecular propagation rate constant were evaluated to be 0.1 mol dm−3 for all the monomers.
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