Determination of the transfer constant for copolymerization in the presence of a reactive substrate

Important equations recently presented by Bamford et al.¹, for chain transfer with reactive substrates in copolymerizing systems are analogous to the well-known relationship:

$\text{In}\text{[S]}\text{[S ]}\text{o =}\text{Cs In[M]}\text{[M] o}$

which is applicable to homopolymerization. This paper reports the first direct experimental testing of the validity of these equations. Gas/liquid chromatographic measurement of residual substrate concentration as a function of monomer removal, measured dilatometrically for the systems methyl acrylate/styrene/bromotrichloromethane and methyl methacrylate/styrene/bromotrichloromethane has been carried out. Results indicate that the equations accurately describe the course of the reaction and permit evaluation of the appropriate transfer constant.