Quantitive kinetic study of vinyl chloride polymerization in suspension

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Abstract
Analysis of various time‐conversion curves obtained with different AIBN‐concentrations at 65°C led to relative rate constants of conversion in the liquid and precipitated phase. Due to the density difference between the two phases, the time‐ and conversion‐dependent volume concentration of the initiator and the conversion‐dependent volume concentration of the free liquid and polymer‐dissolved monomer could be calculated per unit volume of suspended reaction mixture. By this calculation, the molar concentrations of all reactants were given for each point on the time‐conversion curves. On the basis of known kinetic equations a correlation could be achieved between conversion in the range up to 70% conversion and time by using the time integral of the effective initiator concentration. Exact correlation revealed a side reaction of the initiator AIBN, which was supposed to be due to small traces of oxygen. The desactivated initiator amount is nearly constant over all polymerization runs with different initial initiator concentrations. Taking this into account, the experimentally determined time‐conversion curves coincide with the calculated ones.

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