The kinetics of polysulphone formation - I. The formation of 1-butene polysulphone at 25° C

The formation of 1-butene polysulphone from mixtures of liquid sulphur dioxide and 1-butene has been investigated dilatometrically at 25° C. Photochemical and silver nitrate initiation have been used, most of the work being carried out in mixtures containing an excess of sulphur dioxide. There is a discrepancy, in the case of photochemical initiation, between the molecular weight as estimated from the intrinsic viscosity of the polymer, and that deter­mined from the rate of reaction and rate of absorption of light. This discrepancy is ascribed to an inefficient primary process. The variation of rate with initiator, monomer and retarder concentrations has been investigated. The initiator exponent has a value intermediate between 0.5 and 1.0, indicating the occurrence of at least two termination processes. Kinetic expressions have been deduced for various possible termination mechanisms, and. in order to obtain agreement with experiment it is necessary to assume that the propagation process involves the addition to the growing chain of a 1:1 molecular complex of 1-butene and sulphur dioxide.