The copolymerization of styrene (St, M 1 ) and N -phenylmaleimide (PMI, M 2 ) in chloroform using 2,2‘-azobis(isobutyronitrile) as an initiator was investigated. A new kinetic model with assumption of homopolymerization and cross-propagation and diffusion-controlled termination was proposed. The reactivity ratios of free monomers and the charge-transfer complex (CTC) in the copolymerization were determined by a new method, and the values were obtained to be r 12 = 0.03370, r 21 = 0.01157, r 1C = 0.002972, and r 2C = 0.003379, respectively. A kinetic treatment based on the model of mechanism was used to quantitatively estimate the ratio of the CTC rate to the total copolymerization rate in the St/PMI copolymerization. It was about 33.0−55.0% in a wide range of monomer feed.
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Shan et al. (1997) studied this question.
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