Abstract
This review focuses on the world’s first process succeeded in development and industrialization by Asahi Kasei Corp. for producing an aromatic polycarbonate (PC) using CO2 as starting material.1 The carbonate group of PC links directly to the residual aromatic groups of the bisphenol. Until Asahi Kasei’s new process is revealed, all of carbonate groups of PC in the world were derived from CO as starting material. Furthermore, more than about 90% of PC has been produced by so-called “phosgene process”, and the PC contains Cl-impurities. It needs to use not only highly toxic and corrosive phosgene made from CO and Cl2 as a monomer, but also very large amounts of CH2Cl2 and water, and needs to clean a large amount of waste water. The new process enables high-yield production of the two products, Cl-free and high-quality PC and high-purity monoethylene glycol (MEG), starting from ethylene oxide (EO), by-produced CO2 and bisphenol-A. PC produced by the new process has many excellent properties compared with conventional PCs. The new process not only overcomes drawbacks in the conventional processes, but also achieves resource and energy conservation. The reduction of CO2 emissions (0.173 t/PC 1 t) is also achieved in the new process, because all CO2 is utilized as the component consisting main chains of the products. The newly constructed commercial plant of Chimei-Asahi Corp. (Taiwan), a joint venture between Asahi Kasei Corp. and Chi Mei Corp., has been successfully operating at full-production since June 2002. The initial capacity (PC:50,000 t/y) is now increased to 150,000 t/y. A typical example of the Green and Sustainable Chemistry (GSC) contributing to society and mankind has been realized.
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The newspapers say that the construction costs of the PC production new plants are as follows: (a) Phosgene process (i) About 20 thousand million yen (¥) for 60,000 ton/year plant of “T. Co.” in Singapore. Sekiyu-Kagaku-Shinbun (Japanese) [The “Petro-Chemical Press” (weekly)], Dec. 6, 1999. (ii) About 20 thousand million ¥ for 40,000 ton/year plant of “S.D. Co.” in Japan. Kagaku Kogyo Nippo (Japanese) [The Chemical Daily], Oct. 7, 1993. (b) Non-phosgene Asahi Kasei process About 9 thousand million yen (¥) for 50,000 ton/year plant of Chimei-Asahi Corp. in Taiwan. Kagaku Kogyo Nippo (Japanese) [The Chemical Daily], Nov. 8, 1999.
In the Asahi Kasei process, all raw materials (EO, CO2 and Bis-A) are converted to the products (PC and MEG). The cost for purchasing EO can be fully covered by selling the monoethyleneglycol (MEG). This is reasonable because MEG is the product and EO is the raw material and the price of the product is usually higher than the price of the raw material. The CO2 is also by-product emitted into the atmosphere at EO production step. However, in the phosgene process, Cl2 and NaOH (raw materials) are wasted as NaCl. At least this point shows that Asahi Kasei Process is more economical than the phosgene process.
European Chemical News (ECN) describes our process in the article of Polycarbonate” July 2002/Process Review pp. 32–34, the extraction is as follows: “Phosgene is a toxic chemical that requires rigorous process design standards to protect the health and safety of workers. Investment requirements are increased by the need for close analytical monitoring and control, equipment designs for lethal service, and treatment of vent streams by caustic scrubbing or incineration. Toughening of environmental restrictions worldwide has added impetus to the search for non-phosgene routes to polycarbonate. In addition to phosgene concerns, the interfacial polymerization process typically uses a chlorinated solvent, methylene chloride, another material with exposure limits. A further incentive to eliminate the use of phosgene is the economic penalty incurred because the chlorine content of the phosgene is wasted and converted to sodium chloride. Caustic soda is consumed in the conversion, and the disposal of waste salt solutions presents ecological problems in itself. In a second stage reactor, the ethylene carbonate is transesterified with methanol to give two products—dimethyl carbonate and ethylene glycol. Since a large portion of ethylene oxide is normally converted to ethylene glycol for use in polyester production, this approach in essence converts methanol to dimethyl carbonate with virtually no addition raw material costs. And, as an extra bonus, selectivity to ethylene glycol is very high, avoiding diethylene glycol and triethylene glycol, which are by-products of conventional ethylene glycol processes via hydrolysis of ethylene oxide.”
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Fukuoka, S., Tojo, M., Hachiya, H. et al. Green and Sustainable Chemistry in Practice: Development and Industrialization of a Novel Process for Polycarbonate Production from CO2 without Using Phosgene. Polym J 39, 91–114 (2007). https://doi.org/10.1295/polymj.PJ2006140
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DOI: https://doi.org/10.1295/polymj.PJ2006140
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