Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – From phenol – phenol ether – or inorganic phenolate
Reexamination Certificate
2001-08-14
2004-08-31
Boykin, Terressa M. (Department: 1711)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
From phenol, phenol ether, or inorganic phenolate
C528S198000
Reexamination Certificate
active
06784277
ABSTRACT:
BACKGROUND OF INVENTION
Polycarbonate resins are useful materials valued for their physical and optical properties. Methods for the preparation of polycarbonate resins include interfacial processes and melt processes. In interfacial processes, as described, for example, in U.S. Pat. No. 4,360,659 to Sikdar, a bisphenol is reacted with phosgene in the presence of solvents. In melt processes, as described, for example, in U.S. Pat. No. 3,153,008 to Fox, a bisphenol is reacted with a diaryl carbonate. Melt processes are presently preferred because they avoid the use of phosgene and solvents.
Use of a melt process for polycarbonate synthesis requires an industrially efficient process for producing diaryl carbonates. There are several known processes for producing diaryl carbonates. One example of such a process is described by U.S. Pat. No. 4,182,726 to Illuminati et al. In this process, diaryl carbonates are produced by reacting dialkyl carbonates with aryl hydroxides (see Scheme I, below).
U.S. Pat. No. 4,182,726 also demonstrates that diaryl carbonates can be reacted together with dihydric phenols to produce polycarbonates (see Scheme II, below).
A preferred process for making dialkyl carbonates is illustrated in Scheme III, below, and described, for example, in U.S. Pat. No. 5,527,943 to Rivetti et al.; and U.S. Pat. Nos. 4,218,391 and 4,31 8,862 to Romano et al.
U.S. Pat. No. 5,527,943 (the '943 Patent) also describes a known drawback of the dialkyl carbonate process according to Scheme (III): it produces water as a by-product. Also, hydrochloric acid (HCl) may be continuously added to the reaction mixture to maintain a desired molar ratio of chloride to copper. Therefore, HCl, CuCl catalyst, and water are typically found in the stream exiting the reactor vessel. Hydrochloric acid and copper chlorides are very corrosive in the presence of water, so equipment made from corrosion-resistant materials, such as glass-lined vessels, must be used in the reaction section of a chemical plant making dialkyl carbonates by this process. As corrosion-resistant equipment is expensive, there is a desire to use it in as little of the plant as possible.
A typical plant for performing preparing dialkyl carbonates according to Scheme III may contain three sections: a reaction section for converting raw materials to dialkyl carbonate, a separation section for isolating the dialkyl carbonate from unreacted monomers and by-products, and a purification section for removing water and further isolating the dialkyl carbonate. The '943 Patent teaches that one can minimize the amount of corrosion-resistant equipment required by removing the HCl from the process stream immediately after the reaction section. This eliminates the necessity of using expensive corrosion-resistant materials in the separation and purification sections of the plant. The '943 Patent further suggests that removal of HCl and possible copper halide salts from the stream immediately after the reaction section can be accomplished by exposing the gas-liquid mixture produced by the reaction to a liquid stream consisting of one of the process fluids. The '943 Patent also states that the operating conditions employed are preferably adjusted such that the gaseous mixture from the reactor does not condense, or condenses only to a negligible extent, before the acid removal section in order to avoid the necessity of having to reheat the mixture before removing the HCl (col. 3, lines 17-30).
In view of the above, it was desirable to construct a plant wherein the HCl and any copper halide salts would be removed from the stream after the reaction section to avoid corrosion in the separation and purification sections. However, a technique similar to that described by the '943 Patent—removing HCl and copper salts by treatment of a vaporized feed in a column using a counterflowing azeotrope fluid from the reaction mixture—failed to prevent corrosion in the downstream separation and purification sections.
There is therefore a need for a dialkyl carbonate process that recognizes and eliminates additional sources of corrosion.
SUMMARY OF INVENTION
The above-described and other drawbacks and disadvantages of the prior art are alleviated by a method of preparing a dialkyl carbonate, comprising: reacting an alkanol, oxygen, carbon monoxide, and a catalyst to form a mixture comprising a dialkyl carbonate, an alkyl chloroformate, hydrochloric acid, water, carbon dioxide, and carbon monoxide; and removing alkyl chloroformate from said mixture.
After considerable effort, the present inventors have discovered that dialkyl carbonate synthesis can form alkyl chloroformate by-products that lead to problematic corrosion. For example, in the reaction of methanol, carbon monoxide, and oxygen to form dimethyl carbonate (hereinafter “DMC”), methyl chloroformate (hereinafter “MCF”) may be formed as a by-product. The MCF may pass through the HCl removal column into the separator and purification sections, where it reacts slowly with methanol and/or water to form corrosive HCl. Therefore, it was determined that steps were needed to remove MCF prior to the separation and purification sections.
Other embodiments, including an apparatus for preparing dialkyl carbonates, are described below.
REFERENCES:
patent: 2517965 (1950-08-01), Bohl
patent: 3153008 (1964-10-01), Fox
patent: 4182726 (1980-01-01), Illuminati et al.
patent: 4218391 (1980-08-01), Romano et al.
patent: 4318862 (1982-03-01), Romano et al.
patent: 4360659 (1982-11-01), Sikdar
patent: 5210269 (1993-05-01), Di Muzio et al.
patent: 5527943 (1996-06-01), Rivetti et al.
patent: 5536864 (1996-07-01), Paret et al.
patent: 5599965 (1997-02-01), Kricsfalussy
patent: 5685957 (1997-11-01), Rivetti et al.
patent: 5686644 (1997-11-01), Rivetti et al.
patent: 5780663 (1998-07-01), Mori et al.
patent: 5869729 (1999-02-01), Nishihira et al.
patent: 0 634 390 (1994-12-01), None
patent: 1994092905 (1994-04-01), None
patent: WO 03/016256 (2003-02-01), None
Mauri, et al. “Dimethyl carbonate: a new building block for organic chemicals production”. ING. CHIM. ITAL., V. 21, N. 1-3, GEN-MAR. 1985 pp. 6-12.
Cassar, “Dimethylcarbonate: a new intermediate for a cleaner future&Asteriskpseud;”. Rclazione presentata al Congresso Interdivisionalc della Societa Chimica Italana “CISCI '89” Perugia. 7-11 ottobre 1989. LA CHIMICA & L'INDUSTRIA. Doc. 43. pp. 18-22.
“GE licenses Entmont polycarb know-how”. European Chemical News. Nov. 13, 1989. pp. 44.
“Enichem Licenses Its DMC,DPC Route”. Chemical Marketing Reporter. Vol. 236. No. 23. Dec. 4, 1989. pp. 29.
“EniMont-Lizenz an GE Plastics”. Europa Chemical 35/36 p. 585. Dec. 20, 1989 (Translation Attached) Total of 3 pp.
International Search Report dated Nov. 20, 2002.
M. M. Mauri, U. Romano, and F. Rivetti, Quad. Ing. Chim. Ital. (1985), vol. 21, No. 1-3, pp. 6-12.
L. Cassar, Chim. Ind. (Milan) (1990), vol. 72, No. 1, pp. 18-22.
(anonymous) “GE licenses Enimont polycarb know-how”, European Chemical News, Nov. 13, 1989, p. 44.
Translation of excerpts of Building Permit for a new DMC Plant obtained by Polimeri Europa from the Ravenna, Italy local authority on May 22, 2001.
Building Permit for a new DMC Plant obtained by Polimeri Europa from the Ravenna, Italy local authority on May 22, 2001.
Letter to Mr. Paolo Cortesi at Polmeri Europa from Frank A. Smith at General Electric Company dated Mar. 3, 2003 (1 pg.).
Letter to Mr. Paolo Cortesi at Polimeri Europa from Frank A. Smith at General Electric Company dated Mar. 17, 2003 (2 pgs.).
Fax to Mr. Paolo Cortesi at General Electric Company from Paolo Cortesi at Polimeri Europa dated Jun. 10, 2003. (2 pgs.).
Letter to Mr. Paolo Cortesi at Polimeri Europa from Frank A. Smith at General Electric Company dated Jun. 16, 2003. (2 pgs.).
Fax to Mr. Frank A. Smith at General Electric Company from Paolo Cortesi at Polimeri Europa dated Jul. 10, 2003. (2 pgs.).
Letter to Mr. Paolo Cortesi at Polimeri Europa from Frank A. Smith at General Electric Company dated Jul. 15, 2003. (1 pg.).
E-mail from Daniele Delledonne to Ro
Boden Eugene Pauling
Fernandez Ignacio Vic
Boykin Terressa M.
General Electric Company
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