Investigations of the copolymerization of acrylonitrile with vinyl acetate and sodium methallylsulfonate

The bulk copolymerizations of acrylonitrile (AN) with vinyl acetate (VAc) initiated by azobisisobutyronitrile (AIBN) and the suspension copolymerization of AN with VAc and sodium methallylsulfonate (SMAS) in water with a Na2S2O5–Na2ClO3 redox initiator system at 65°C, were investigated. The copolymer compositions were determined by 1H-NMR. The reactivity ratios (γs) for the two copolymerization systems were determined analytically, based on Mayo–Lewis equation, by fitting the calculated curves with the experimental data. The γs for the AN and VAc bulk copolymerization were found to be γ12 = 2.85 and γ21 = 0.11. The values of the apparent γs for the suspension copolymerization of AN, VAc, and SMAS were as follows: γ12 = 3.58, γ21 = 0.39, γ13 = 1.45, γ31 = 0, γ23 = 0.92, and the rate constant ratio R3 = k31/k32 = 0.04. A simulated result produced with the obtained γs agreed fairly well with experimental data of bulk copolymerization in a batch reactor. The apparent γs obtained were also successfully used to analyze the results of suspension polymerization in a continuous pilot reactor.© 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 854–860, 2001

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