The hydrolysis of a complex of diethyl zinc (DEZ) with propylene sulphide (PS) in PS solution has been investigated. Suitable conditions have been found for the quantitative hydrolysis of DEZ with the formation of a catalyst system containing (ZO)n groups and ZnS bonds and effective for initiating the polymerization of PS. This polymerization was investigated and a tentative scheme for polymerization by a coordinate anionic mechanism is suggested. The structure of polypropylene sulphide (PPS) was investigated by high-resolution NMR spectroscopy and X-rays. The Zn(C2H5)2-H2O system prepared in situ is highly selective in the reactions of breaking the α-thioxide ring. Amorphous PS consists entirely of head-to-tail bonded units with equal content of iso- and syndiotactic diads. It was also shown that extremely high values of the molecular mass of PPS, the unusual dependence of [η] on conversion and the instability of polymer solutions are due to the presence of polymer aggregates formed in the polymerization of PS on complex associated active centres with a steric structure. Conditions were found for the stabilization of PS solutions containing zinc and for the purification of the polymer from traces of the catalyst system. It was shown that it is incorrect to use equations available in the literature to calculate Mη for PPS obtained with the DEZ-H2O system from viscometric data without thorough purification of the polymer. Osmometry and light scattering technique were used to estimate true values of the molecular mass of polymer aggregates and of linear PPS. © 1979.
