Diphenyl carbonates

Diphenyl carbonate 511, by heating with excess chlorosulfonic acid at 80 °C (2.5 hours), afforded the disulfonyl chloride 512, 35% yield (Equation 161). In this reaction, chlorosulfonation occurred, as expected, para with respect to the electron donating oxygen atom. 

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Both dimethyl carbonate [616-38-6] and diphenyl carbonate [102-09-0] have been used, in place of carbon monoxide, as reagents for the conversion of amines into isocyanates via this route (28,29). Alternatively, aniline [62-53-3] toluene diamines (I JJA), and methylene dianilines (MDA) have also been used as starting materials in the carbonylations to provide a wide variety of isocyanate monomers. 

The historical direct reaction route, which utilised phosgenation of a solution of BPA in pyridine, proved inefficient commercially because of the need for massive pyridine recycle. Calcium hydroxide was used as an HCl scavenger for a period of time. In the historical transesterification process, BPA and diphenyl carbonate are heated in the melt in the presence of a catalyst, driving off by-product phenol, which is recycled to diphenyl carbonate. Using a series of reactors providing higher heat and vacuum, the product polymer was eventually produced as a neat melt. 

The polymerization is carried out in several stages. In the first stage, diphenyl carbonate and BPA ate combined with small amounts (<0.01% molar)... 

The polymer is exposed to an extensive heat history in this process. Early work on transesterification technology was troubled by thermal—oxidative limitations of the polymer, especially in the presence of the catalyst. More recent work on catalyst systems, more reactive carbonates, and modified processes have improved the process to the point where color and decomposition can be suppressed. One of the key requirements for the transesterification process is the use of clean starting materials. Methods for purification of both BPA and diphenyl carbonate have been developed. 

An analogue of the transesterification process has also been demonstrated, in which the diacetate of BPA is transesterified with dimethyl carbonate, producing polycarbonate and methyl acetate (33). Removal of the methyl acetate from the equihbrium drives the reaction to completion. Methanol carbonylation, transesterification using phenol to diphenyl carbonate, and polymerization using BPA is commercially viable. The GE plant is the first to produce polycarbonate via a solventiess and phosgene-free process. 

Reaction with Phenols. Phenols react with diphenyl carbonate in the presence of bases or organometaHic catalysts to produce diaryl carbonates. A specific example is the reaction of diphenyl carbonate with bisphenol A [80-05-7] to produce polycarbonate. 

Bisphenol A Polycarbonate Resins. These resins are manufactured by interfacial polymerization (84,85). A small amount of resin is produced by melt-polymerization of bisphenol with diphenyl carbonate in Russia and the People s RepubHc of China. Melt technology continues to be developmental in Japan and the West, but no commercial activities have started-up to date, although some were active in the late 1960s. No reports of solvent-based PC manufacture have been received. 

Diphenyl carbonate [102-09-0] M 214.2, m 80 . Purified by sublimation, and by preparative gas chromatography with 20% Apiezon on Embacel, and crystn from EtOH. 

Diphenyl carbonate, an alternative source of the carbonate group to phosgene, may be obtained by reacting phenol with phosgene in acqueous caustic soda solution, the reaction being accelerated by tertiary amines. The diphenyl carbonate can be purified by redistillation. 

Because bis-phenol A is somewhat unstable at elevated temperature it is desirable to work with an excess of diphenyl carbonate so that the bis-phenol A is rapidly used up. The reaction may be conveniently carried out using twice or more than twice the theoretical quantity of diphenyl carbonate so that the initial reaction product is the bisfphenyl carbonate) of bis-phenol A (Figure 20.4 (a)). 

Polymerisation then proceeds by splitting out of diphenyl carbonate to give the polycarbonate resin (Figure 20.4 (b)). 

This variation has the obvious disadvantage that the less volatile diphenyl carbonate is more difficult to remove than phenol. 

These materials have the general structure shown in Figure 20.11 and are prepared by reaction of bisphenol A with iso- and/or terephthalic acid and a carbonate group donor (e.g. phosgene or diphenyl carbonate). 

Another method for producing polycarbonates is hy an exchange reaction between bisphenol A or a similar bisphenol with diphenyl carbonate ... 

Diphenol carbonate is produced by the reaction of phosgene and phenol. A new approach to diphenol carbonate and non-phosgene route is by the reaction of CO and methyl nitrite using Pd/alumina. Dimethyl carbonate is formed which is further reacted with phenol in presence of tetraphenox titanium catalyst. Decarbonylation in the liquid phase yields diphenyl carbonate. 

Lexan, a polycarbonate prepared from diphenyl carbonate and bisphenol A, is another commercially valuable polyester. Lexan has an unusually high impact strength, making it valuable for use in telephones, bicycle safety helmets, and laptop computer cases. 

Note-. Bisphenol-A and the diaryl esters of terephthalic acid and isophthalic acid are nonvolatile compounds, so that any excess of these components cannot completely be removed, resulting in a low-molar-mass, unusable polyester. Moreover, excess bisphenol-A causes a strong discoloration of the polyester melt due to thermal degradation at the high reaction temperature used. This can be avoided if the diaryl esters are mixed with 5 mol% of diphenyl carbonate. Any excess of this compound can easily be removed in vacuum at the polycondensation temperature. 

Experiment with addition of diphenyl carbonate Diphenyl terephthalate, 31.8 g (0.1 mol), 28.62 g (0.09 mol) of diphenyl isophthalate, and 2.37 g (0.011 mol) of diphenyl carbonate are polycondensed with 45.6 g (0.2 mol) of 2,2-bis(4-hydroxyphenyl)propane (bisphenol-A) under the preceding conditions. A slighdy brownish, extremely tough, noncrystalline polyester is obtained with an inherent viscosity equal to 0.56 dL/g. The softening point of the polyester is equal to 200°C and the melting range is 215-285°C. 

Solutions of Moiseev s giant Pd colloids [49,161-166] were shown to catalyze a number of reactions in the quasi homogeneous phase, namely oxidative ace-toxylation reactions [162], the oxidative carbonylation of phenol to diphenyl carbonate [166], the hydrogen-transfer reduction of multiple bonds by formic acid [387], the... 

Bisphenol A, whose official chemical name is 2,2-bis(4-hydroxyphenyl)propane, is a difunctional monomer with two reactive hydroxyl groups, as shown in Fig. 20,2. It polymerizes svith dicarbonyl organic monomers, such as phosgene or diphenyl carbonate, which are illustrated in Fig. 20.3. During polymerization, shown in Fig. 20.4, the hydroxyl groups of the bisphenol A deprotonate in the presence of a base. After deprotonation, the oxygen atoms on the bisphenol A residue form ester bonds with the dicarbonyl compounds. The polymerization process terminates when a monohydric phenol reacts with the growing chain end. 

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