Molecular structure of synthetic rubber. I. Light-scattering properties of styrene–butadiene copolymers

The discrepancy between the values reported for the weight-average molecular weight and molecular weight distribution of cold-type styrene-butadiene rubber is examined. The results obtained indicate that aggregation of the rubber due to hydrogen bonding or cluster formation is not a contributing factor to the high weight-average molecular weights obtained. The very broad molecular weight distributions, the M?_w/M?_n of the order of 10–20, are attributable to the presence of a few per cent of very high molecular weight fraction microgel in samples polymerized to moderate conversions. This microgel has been removed to various degrees by several methods: (1) mastication, (2) treatment with CaSO₄, (3) ultracentrifugation, and (4) ultrafiltration. The nature of this microgel is examined in terms of its light-scattering property, intrinsic viscosity, and concentrated solution viscosity. The weight-average molecular weight obtained by light scattering on these samples after removal of microgel are lower by as much as an order of magnitude. The operational definition of the weight-average molecular weight, M?′_w, is therefore introduced, corresponding to the one obtained after removal of the microgel. It is suggested that the actual and the operational weight-average molecular weights be used in conjunction in the characterization of these copolymers.