Journal of Applied Polymer Science, Vol.59, No.5, 861-885, 1996
Bulk-Polymerization of Styrene in Presence of Polybutadiene - Calculation of Molecular Macrostructure
In our previous publication the detailed molecular macrostructure generated in a solution polymerization of styrene (St) in the presence of polybutadiene (PB) at 60 degrees C, was theoretically calculated. In this work, an extended kinetic mechanism that incorporates monomer thermal initiation, chain transfer to the rubber, chain transfer to the monomer, and the gel effect is proposed, with the aim of simulating a bulk high-impact polystyrene (HIPS) process. The mathematical model enables the calculation of the bivariate weight chain-length distributions (WCLDs) for the total copolymer and for each of the generated copolymer topologies and the univariate WCLDs for the free polystyrene (PS), the residual PB, and the crosslinked PB topologies. These last topologies are characterized by the number of initial PB chains per molecule; copolymer topologies are characterized by the number of PS and PB chains per molecule. The model was validated with published literature data and with new pilot plant experiments that emulate an industrial HIPS process. The literature data correspond to a dilute solution polymerization at a constant low temperature with chemical initiation and a bulk polymerization at a constant high temperature with thermal initiation. The new experiments consider different combinations of prepolymerization temperature, initiator concentration, and solvent concentration. One of the main conclusions is that most of the initial PB is transformed into copolymer. For example, for a prepolymerization temperature of 120 degrees C with addition of initiator, the experimental measurements indicate that the final total rubber mass is approximately three times higher than the initial PB. Also, according to the model predictions, the final weight fractions are : free PS, 0.778; graft copolymer, 0.220; initial PB, 0.0015; and purely crosslinked PB, 0.0005. The final graft copolymer exhibits the following characteristics : average molecular weights, (M) over bar(n,C) = 492,000 and (M) over bar(w,C) = 976,000; average weight fraction of St, 0.722; and average number of PS and PB branches per molecule, 5.19 and 1.13, respectively.
Keywords:FREE-RADICAL POLYMERIZATION;RUBBER PARTICLE-SIZE;BIFUNCTIONAL INITIATORS;IMPACT POLYSTYRENE;CROSS-LINKING;KINETICS;CIS-1;4-POLYBUTADIENE;MECHANISM;POLYMERS