Molecular characterization of solution styrene-butadiene rubber: Thermal field-flow fractionation/multi-angle light scattering studies

Solution styrene-butadiene rubber (SSBR) is mainly constituted of a random copolymer of styrene and butadiene. SSBR usually contains microgels, having ultrahigh molecular weight (M > 107 g/mol), affecting rheological properties of the rubber. Thus, determinations of M and size distribution of these microgels are critical in performance evaluation and control for SSBR. We employ thermal field-flow fractionation (ThFFF), combined with online multi-angle light scattering (MALS), as most suited for characterization of solutions containing the microgels since they can be characterized in toto without removing the microgels from the solution. ThFFF-MALS was applied for characterization of linear and branched SBR materials from various commercial sources, and the results were compared to those from size-exclusion chromatography (SEC). ThFFF provides higher resolution than SEC for high molecular fractions and allowed gel content to be measured. The gel content was determined by subtracting the amount of sol from total injection mass, and was measured to be 10–15%. We infer from the characterization results that the microgel content may not be correlated to the microstructure, the styrene and vinyl content of butadiene but to the fraction of high molecular weight in SSBR. Finally, the macromolecular structure and the content of microgel (larger than about 100 nm) were found to significantly affect various rheological parameters such as viscosity, mechanical and dynamic properties.