@article{saraf_gerard_wojcinski_charpentier_desimone_roberts_2002, title={Continuous precipitation polymerization of vinylidene fluoride in supercritical carbon dioxide: Formation of polymers with bimodal molecular weight distributions}, volume={35}, ISSN={["1520-5835"]}, DOI={10.1021/ma0203602}, abstractNote={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...}, number={21}, journal={MACROMOLECULES}, author={Saraf, MK and Gerard, S and Wojcinski, LM and Charpentier, PA and DeSimone, JM and Roberts, GW}, year={2002}, month={Oct}, pages={7976–7985} }
 @article{saraf_wojcinski_kennedy_gerard_charpentier_desimone_roberts_2002, title={Continuous precipitation polymerization of vinylidene fluoride in supercritical carbon dioxide: Molecular weight distribution}, volume={182}, ISSN={["1521-3900"]}, DOI={10.1002/1521-3900(200206)182:1<119::AID-MASY119>3.0.CO;2-P}, abstractNote={The surfactant-free precipitation polymerization of vinylidene fluoride (VF2) in supercritical carbon dioxide was studied in a continuous stirred autoclave. The polymerization temperature ranged from 65 to 85°C, the average residence time in the reactor varied from 10 to 50 min., and the pressure was between 210 and 305 bar. Diethyl peroxydicarbonate was used as the initiator. The fractional conversion of monomer varied from 7 to 26%, the number-average molecular weight of the polymer was between about 14,000 and 79,000, and the weight-average molecular weight was between about 21,000 and 700,000. In many cases, the polymer exhibited a bimodal molecular-weight distribution, especially at high monomer concentrations.}, journal={MACROMOLECULAR SYMPOSIA}, author={Saraf, MK and Wojcinski, LM and Kennedy, KA and Gerard, S and Charpentier, PA and DeSimone, J and Roberts, GW}, year={2002}, month={Jun}, pages={119–129} }