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Polymerization involving carbon dioxide is one of the most important utilizations of carbon dioxide. Polycarbonate formation without using phosgene, an alternating copolymerization with an epoxide, a condensation with benzenedimethanol and an alternating copolymerization with diynes, etc., can be exemplified. Especially, the polycarbonate formation without using phosgene, and the alternating copolymerization with the epoxide were already industrially applied. Asahi Chemical Industry already started the 50,000 tons/year commercial operation of a polycarbonate process without using phosgene and methylene chloride in June 2002 in Taiwan as a new environmentally benign process [157,158,158a]. The Asahi¡¯s polycarbonate process was carried out by the following four production steps: (1) ethylenecarbonate (EC), (2) dimethylcarbonate (DMC) and ethylene glycol (EG) and (3) diphenylcarbonate (DPC) and polymerization, as shown in Scheme 8 [157]. The DPC is manufactured by the reaction of DMC with phenol in the presence of Pb(OPh)2 as a catalyst [158b]. The polymerization proceeds with two processes. The first process is the solid-state polymerization of amorphous polymers in three steps: (1) pre-polymerization; the reaction of the DPC with bisphenol A to produce a clear amorphous prepolymer; (2) crystallization; the molten prepolymer is converted to a porous, white, opaque material by treating it with a solvent such as acetone; (3) solid-state polymerization; the crystallized prepolymer is heated at 210¨C220 8C under a flow of heated nitrogen, or under a reduced pressure to produce a solid polymer. The second process is ¡®¡®self-mixing melt polymerization¡¯¡¯ utilizing gravity and without using a conventional twinscrew type reactor. The polymerization was carried out at 265 8C and 67 Pa. A prepolymer having a number average molecular weight of 6200 is polymerized to the molecular weight 11,700 [158b,158c] [ Last edited by monanfang03 on 2013-5-3 at 19:04 ] |
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monanfang03: ½ð±Ò+5, ·ÒëEPI+1, ¡ïÓаïÖú 2013-05-03 23:07:16
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