Experimental investigation of vinyl chloride polymerization at high conversion—reactor dynamics

Abstract A series of suspension polymerizations of vinyl chloride monomer (VCM) was carried out in a 5‐L pilot plant reactor over the temperature range, 40–70°C. The reactor pressure and monomer conversion were monitored simultaneously every 7–8 min. The critical conversion X f , at which the liquid monomer phase is consumed, was considered to occur when the reactor pressure fell to 98% of the vapor pressure of VCM for suspension at the polymerization temperature. The reactor model predictions of pressure are in excellent agreement with the experimental data over the entire conversion and temperature ranges studied. The mechanism of reactor pressure development for VCM suspension polymerization is discussed herein in some detail. For isothermal batch polymerization, the reactor pressure falls in two stages due to the effect of polymer particle morphology on pressure drop. The first stage is due to the volume increase of the vapor phase as a result of volume shrinkage due to conversion of monomer to polymer. The monomer phase is not yet consumed at this stage, but it is trapped in the interstices between primary particles creating a mass transfer resistance; therefore, the reactor pressure drops slowly. The second stage is due to both the volume increase of the vapor phase and to the monomer in the vapor phase diffusing into the polymer phase because of the subsaturation condition with respect to monomer in the polymer phase. The reactor pressure drops dramatically with an increase in monomer conversion at this stage. The present model can be used to predict reactor dynamics during suspension polymerization under varying temperature and pressure conditions.