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CARBON DIOXIDE TECHNOLOGY PLATFORM 135 5.1 CO2-Swollen Melt Phase Step Growth Polymerization Polycarbonates are an important class of polymers due primarily to their toughness and optical clarity. Produced at a rate of 2.7 billion pounds per year and expected to increase to 4 billion pounds per year, the polycarbonate market is growing as digital versatile discs and polycarbonate windows become common place (66). Poly(bisphenol A carbonate) is commercially synthesized by two different meth- ods: (a) the interfacial reaction between phosgene dissolved in an organic solvent and bisphenol A dissolved in an aqueous alkali solution and (b) the bulk reaction between diphenyl carbonate and bisphenol A. Copious amounts of aqueous and organic waste are generated in the former synthetic route. Whereas the bulk reac- tion reduces the generation of waste, this type of reaction is limited to intermediate molecular weights as a result of side reactions and high viscosities. High viscosity hinders mixing and removal of condensate from the melt phase polymerization. The combined effect is slower reaction rates. CO2 is a viable aide in polymer processing where it swells a polymer melt and effectively lowers the processing temperature. In a closed system, the polymer swelling correlates to CO2 mass uptake by the polymer. Swelling measurements allow for the determination of the diffusion coefficient of CO2 in the polymer (Figure 15). It has been demonstrated that CO2 is able to swell polycarbonate in the melt phase producing both a reduction in melt viscosity and an increase in free volume of the melt (67). The increase in free volume as a result of the plasticization should provide more polymer surface area for condensate removal and greater mobility of chain ends. Figure 15 Swelling and plasticization of a polymer melt by CO2.PDF Image | OPPORTUNITIES FOR POLLUTION PREVENTION
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