The kinetics of radical copolymerization of acrylonitrile and methylacrylate with tricaprylylmethylammonium chloride as a phase-transfer catalyst

The phase-transfer radical copolymerization of acrylonitrile (AN) and methylacrylate (MA) with tricaprylylmethylammonium chloride was investigated in Na₂S₂O₈ aqueous-organic two-phase system at 25°C and under nitrogen atmosphere. The rate of copolymerization was expressed as the combined terms of quaternary ammonium ion and peroxydisulfate ion in the aqueous phase rather than the fed concentrations of catalyst and Na₂S₂O₈. The observed initial rate of copolymerization was used to analyze the copolymerization mechanism with a cyclic phase-transfer initiation step in the heterogeneous liquid–liquid system. The monomer reactivity ratio r₁ and r₂ obtained from the analysis of copolymerization mechanism were 1.584 and 0.856, respectively. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 3504–3512, 1999