Abstract
The polymerization of vinylidene fluoride in supercritical carbon dioxide was studied in a continuous stirred tank reactor using diethylperoxydicarbonate as the free radical initiator. Experiments were carried out to investigate the effect of inlet monomer concentration, temperature, average residence time, and agitation on the polymerization rate, the average molecular weights, and the molecular weight distribution of the poly(vinylidene fluoride). A homogeneous kinetic model that includes inhibition due to chain transfer to monomer predicted the polymerization rates reasonably well. However, imperfect mixing, rather than a chemical effect, may have caused the apparent inhibition observed at high monomer concentrations. At inlet monomer concentrations greater than about 1.5 M, broad and bimodal molecular weight distributions were observed. An extended homogeneous kinetic model that includes chain transfer to polymer predicted the polydispersities reasonably well. This model also predicted a region of ino...
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