Copolymerization propagation kinetics of styrene with alkyl acrylates

Propagation rate constants have been determined at two temperatures (298 K and 323 K) for the copolymerizations of styrene (STY) with methyl acrylate (MA) and STY with n ‐butyl acrylate (BA) over a range of monomer feed compositions. A pulsed UV laser was used as an initiation source and gel permeation chromatography (GPC) was utilized to analyse the products. None of the copolymerizations conformed to the Mayo‐Lewis model, with respect to their propagation rate constants. The results were interpreted on the basis of a penultimate effect on the propagation reaction. In addition, Mark‐Houwink constants were determined for poly(MA) and poly(BA) in tetrahydrofuran (THF) at 298 K. These constants are given as [ K (dm 3 kg −1 ),α]: 7·88 × 10 −3 , 0·885 and 8·57 × 10 3 , 0·865 for poly(MA) and poly(BA) respectively.