Polymerization of Vinyl Chloride at Reduced Monomer Accessibility. I. Polymerization at Subsaturation Pressure with Suspension PVC as a Seed

Abstract Vinyl chloride was polymerized at 40–96% of saturation pressure in water suspended systems at 55°C with suspension PVC as a seed. The monomer was continuously charged as vapor from a storage vessel kept at lower temperature. Characterization included molecular weight distribution (MWD) and degree of long-chain branching (LCB) by GPC and viscometry, thermal dehydrochlorination, microscopy, and technical standard tests. A granular seed was necessary to obtain granular polymer and reasonable polymerization rate. In properly seeded systems with monomer-soluble initiator, crust formation is very low. With monomer-soluble initiator the polymerization reactions are restricted to the seed polymer, comprise its total structure, reducing its porosity. At pressure near saturation, molecular weight increased with conversion, and autoacceleration occurred. The changes in molecular weight are presumably due to the lack of a liquid monomer phase, which reduces the mobility of the radicals leading to decreased termination. At decreasing polymerization pressure the mobility is further reduced due to de-swelling of the gel. At low pressure the polymerization rate decreased, the amount of low molecular weight material increased, and considerable long-chain branching occurred as a result of monomer depletion. With water-soluble initiator (at pressure near saturation), new tiny particles were formed in the water phase at the boundary to the seed particles. The seed structure remained unchanged. The polymer formed showed broad MWD and high LCB. No marked reduction in polymerization rate was observed. The dehydrochlorinatlon measurements indicate that the end groups and not the branch points are responsible for the decrease in thermal stability noticed.