Influence of centrifugal field on free-radical polymerization kinetics

It has been observed that when a prepolymer mix of styrene, poly(styrene), toluene, and benzoyl peroxide is transferred from a conventional stirred tank reactor (STR) to a spinning disc reactor (SDR), the rate of polymerization is substantially increased. Furthermore, the molecular weight and the molecular weight distribution of the polymer formed at conversions up to about 80% in the SDR is virtually unchanged from that of the polymer formed at 60% conversion in the STR. These results seem to indicate that the increase in polymerization rate is not the result of the well-known Trommsdorff-Norrish effect, which would be expected to lead to an increase in polydispersity. We believe that shear and centrifugal forces experienced by the film provide intense mixing and extension flow effects, which are responsible for the above-described observations. In this report an explanation has been put forward to describe the observed effects. (C) 2002 Wiley Periodicals, Inc.