About 80% of production involves suspension polymerization. Emulsion polymerization accounts for about 12% and bulk polymerization accounts for 8%. Suspension polymerizations affords particles with average diameters of 100– 180 μm, whereas emulsion polymerization gives much smaller particles of average size around 0.2 μm. VCM and water are introduced into the reactor and a polymerization initiator, along with other additives. The reaction vessel is pressure tight to contain the VCM. The contents of the reaction vessel are continually mixed to maintain the suspension and ensure a uniform particle size of the PVC resin. The reaction is exothermic, and thus requires cooling. As the volume is reduced during the reaction (PVC is denser than VCM), water is continually added to the mixture to maintain the suspension.
The polymerization of VCM is started by compounds called initiators that are mixed into the droplets. These compounds break down to start the radical chain reaction.