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136 TAYLOR CARBONELL DESIMONE 5.2 Furthermore, CO2 is compatible with the mechanism associated with the synthesis of poly(bisphenol A carbonate) from bisphenol A and diphenyl carbonate. New opportunities in reducing the production/processing costs and improved materials (e.g. optical clarity) could result from the reduction in viscosity of the melt-phase swollen with CO2. Solid State Polymerizations Another approach to avoiding the high temperature and high viscosity encountered in the bulk reaction is to perform solid-state polymerization on low molecular weight polycarbonate oligomers. Polycarbonate does not crystallize by thermal annealing to any appreciable extent; however, it undergoes solvent-induced crys- tallization by organic solvents (68)—which are difficult to handle in a wide-scale commercial plant and undesirable in that they raise potential environmental risks— and by the addition of nucleating agents (69). Additionally, pulling a vacuum for 24 hours at temperatures above 150◦C does not rid the polymer of residual solvent (68, 70). Polycarbonate films have been shown to undergo crystallization upon exposure to CO2 at elevated pressures and temperatures (71). At the end of the crystallization process, CO2 was found to rapidly degas from the polymer after venting. The solid-state polymerization process is efficient when the polymer is in the form of small pellets. As the pellet size increases, a molecular weight gradient and morphological changes develop between the center and the surface of the pellet. The gradient is caused by the condensate molecule diffusing out of the interior particle. The solid-state polymerization progresses by inducing crystallization in the polycarbonate pellet (Figure 16). CO2 cannot only aide in the crystallization of polycarbonate, but also in the removal of the condensate. By utilizing super- critical CO2 as the sweep fluid, the solid-state polymerization of polycarbonate Figure 16 Amorphous polycar- bonate pellets (top) shown to crystallize (bottom) by carbon dioxide.PDF Image | OPPORTUNITIES FOR POLLUTION PREVENTION
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