AbstractA study of the polymerization of vinyl chloride was made at conditions under which the monomer exists in the gas phase. In the presence of a bed of poly(vinyl chloride) particles, free‐flowing product was obtained. By using free‐radical initiators, such as dialkylperoxy dicarbonates or acetylcyclohexane sulfonyl peroxide, high initiator productivities were obtained in reaction periods of 1.5 to 3 hr. Although some modifiers, such as ethyl bromomalonate and bromoform, were demonstrated to lower molecular weight, satisfactory molecular weight modification was accomplished by adjusting polymerization temperature. Several peroxy compounds of different reactivity were studied. Hydrocarbon additives improve the polymerization rate. It is believed that the hydrocarbon and initiator are absorbed on the PVC particle surface and allow the monomer concentration to be increased at the polymerization locus. PVC particles of small size may be prepared in a liquid bulk polymerization for use as seed polymer for the vapor phase process. This provides a seed of high porosity which enables one to prepare a vapor phase product with suitable plasticizer absorption. The physical properties of products prepared by the vapor phase process were evaluated in a rigid formulat
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