COMPOSITIONAL HETEROGENEITY OF BUTADIENE–ACRYLONITRILE COPOLYMERS PREPARED IN EMULSION AT 5°C

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Abstract
The copolymerization of butadiene and acrylonitrile is very similar to the copolymerization of butadiene and styrene. Polymers predominantly butadiene may be studied by conventional solution techniques but the study of polymers rich in acrylonitrile requires improved solvents for these materials. Polymerization rates are greatest for monomer ratios approximating equal proportions. The mercaptan modifier disappears much more slowly than in the butadiene–styrene system, the regulating index approximating unity. The number average molecular weights calculated from the mercaptan disappearance curves indicate uniform polymer molecular weights to relatively high conversions after which there is a decrease. The viscosity data indicate a rise in viscosity with conversion, which effect is overcome for charges rich in acrylonitrile by the lessening of branching, the more rapid disappearance of mercaptan at high conversion, and the tendency of polymers containing over 50% acrylonitrile to show very low dilute solution viscosities in the solvents tested. Viscosity molecular weights have been calculated and estimates of the molecular weight distribution made. These distributions appear to be quite narrow and the usual broadening at higher conversions is prevented by the increased modifier consumption and increased vinyl content of the polymer prepared with 50 parts acrylonitrile in the charge. The bound acrylonitrile has been determined at various conversions and the reactivity ratios have been found to be r1 = 0.28 and r2 = 0.02 for emulsions and r1 = 0.18 and r2 = 0.03 for oil phase portion only. Q is 0.74 and e is 1.47 as calculated by the Alfrey–Price equations.