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Process for the Production of Pentaerythritol

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Process for the Production of Pentaerythritol Europäisches Patentamt *EP001399456B1* (19) European Patent Office Office européen des brevets (11) EP 1 399 456 B1 (12) EUROPEAN PATENT SPECIFICATION (45) Date of publication and mention (51) Int Cl.7: C07F 9/6574 of the grant of the patent: 07.12.2005 Bulletin 2005/49 (86) International application number: PCT/US2002/019159 (21) Application number: 02744389.4 (87) International publication number: (22) Date of filing: 17.06.2002 WO 2003/002581 (09.01.2003 Gazette 2003/02) (54) PROCESS FOR THE PRODUCTION OF PENTAERYTHRITOL PHOSPHATE ALCOHOL VERFAHREN ZUR HERSTELLUNG VON PENTAERYTHRITOLPHOSOHATALKOHOL PROCEDE DE PRODUCTION D’ALCOOL DE PHOSPHATE DE PENTAERYTHRITOL (84) Designated Contracting States: (56) References cited: AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU EP-A- 0 578 318 US-A- 4 454 064 MC NL PT SE TR • CHEMICAL ABSTRACTS, vol. 135, Columbus, (30) Priority: 29.06.2001 US 896710 Ohio, US; abstract no. 211146, PENG, XIAOPING ET AL: "Preparation method of pentaerythritol (43) Date of publication of application: phosphate" XP002214946 & CN 1 281 861 A 24.03.2004 Bulletin 2004/13 (RESEARCH INST., YUEYANG PETRO-CHEMICAL GENERAL PLANT, PEOP. (73) Proprietor: PABU Services, Inc. REP. CHINA) 31 January 2001 (2001-01-31) Wilmington, Delaware 19801 (US) • TSE H L A ET AL: "Constrained analogues of 2’-nor cyclic nucleoside monophosphates" (72) Inventors: BIOORGANIC & MEDICINAL CHEMISTRY • VYVERBERG, Frederick LETTERS, OXFORD, GB, vol. 7, no. 11, 3 June Chester, NY 10918 (US) 1997 (1997-06-03), pages 1387-1392, • CHAPMAN, Robert, W. XP004136222 ISSN: 0960-894X Mt. Vernon, IN 47620-9657 (US) (74) Representative: von Kreisler, Alek et al Deichmannhaus am Dom, Postfach 10 22 41 50462 Köln (DE) Note: Within nine months from the publication of the mention of the grant of the European patent, any person may give notice to the European Patent Office of opposition to the European patent granted. Notice of opposition shall be filed in a written reasoned statement. It shall not be deemed to have been filed until the opposition fee has been paid. (Art. 99(1) European Patent Convention). EP 1 399 456 B1 Printed by Jouve, 75001 PARIS (FR) EP 1 399 456 B1 Description Claim for Priority 5 [0001] This application claims the benefit of the filing date of U.S. Provisional Patent Application Serial No. 09/896,710, of the same title, filed June 29, 2001. BACKGROUND OF THE INVENTION 10 Field of the Invention [0002] This invention relates to an improved process for the production of pentaerythritol phosphate alcohol. Description of the Related Art 15 [0003] Pentaerythritol phosphate alcohol (PEPA) is a known effective flame retardant for plastics and other combus- tibles when used alone as an additive, or as part of a combination of additives. PEPA may be synthesized by the liquid phase reaction of pentaerythritol and phosphorus oxychloride using a solvent to enable the reaction to go forward but in which the PEPA product has little if any solubility after the reaction solution is cooled. However, various problems 20 with this process have been caused by certain undesirable properties of the solvents employed, e.g., excessive flam- mability in the case of ethers such as dioxane which also has a tendency to form explosive peroxides in contact with air and cannot be easily separated from by product HCl and water making solvent recycle difficult, or problems of purification and recycling due to the high boiling points and viscosities of solvents such as aryl phosphates. Thus, the use of a solvent which avoids some or all of the foregoing problems is very desirable. 25 [0004] U.S. Patent No. 4,454,064, issued June 12, 1984 to Halpern et al., discloses the preparation of PEPA by reacting approximately equimolar amounts of pentaerythritol (PE) and phosphorus oxychloride in a solvent at a tem- perature of about 75°C to about 125°C, cooling the mixture to precipitate the PEPA, and isolating the PEPA. The disclosed solvents are dioxane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, chlorobenzene, tolu- ene, xylene, acetonitrile, sulfolane, and tetrachlorethylene. 30 [0005] U.S. Patent No. 5,237,085, issued August 17, 1993 to Telschow et al., teaches a process for the formation of pentaerythritol-based phosphorus heterocycles, e.g., PEPA, comprising the reaction of a pentaerythritol polyol with either a trivalent or pentavalent phosphorus compound, e.g., phosphorus oxychloride, using an arylphosphate solvent, at elevated temperature. [0006] Chemical Abstracts, vol. 135, Columbus, Ohio, US; abstract no. 211146, Peng, Xiaoping et al: "Preparation 35 method of pentaerythritol phosphate" XP002214946 & CN 1 281 861 A (Research Inst., Yueyang Petrochemical Gen- eral Plant, Peop. Rep. China) 31 January 2001 disclose a process for the preparation of pentaerythritol phosphate alcohol (PEPA) by esterification of pentaerythritol with POCl3 in a halohydrocarbon solvent with a boiling range of 96-140°C. The solvent used by said invention method can be obtained by distilling by-product produced in production of chloropropene, and is a mixture of 1,2-dichloropropane, 1,2-dichloropropene, 1,3-dichloropropene, and/or 40 1,2,3-trichloropropane. BRIEF SUMMARY OF THE INVENTION [0007] In accordance with this invention the following is provided 45 (1) A process for the production of pentaerythritol phosphate alcohol (PEPA) comprising reacting in the liquid phase phosphorous oxychloride (POCl3) with pentaerythritol (PE) at a reaction temperature of at least 100°C in the pres- ence of a solvent which is an alkane substituted with at least one halogen atom and having an atmospheric boiling point of 40 to 150°C, said atmospheric boiling point being below said reaction temperature, the reaction pressure 50 being superatmospheric and sufficiently high to maintain the solvent in the liquid phase, the reaction resulting in the production of PEPA and HCl by-product. (2) The process of (1) wherein said alkane is methane, ethane or propane. 55 (3) The process of (2) wherein said halogen atom is chlorine. (4) The process of (3) wherein said solvent is 1,2-dichloroethane (ethylene dichloride or EDC). 2 EP 1 399 456 B1 (5) The process of (1) wherein said reaction temperature is in the range of 100 to 150°C. (6) The process of (5) wherein said reaction temperature is in the range of 110 to 130°C. 5 (7) The process of (1) wherein said superatomspheric reaction pressure is up to 482,79 kPa (70 psig). (8) The process of (7) wherein said reaction pressure is in the range of 137,94 kPa to 344,85 kPa (20 to 50 psig). (9) The process of (1) wherein the atmospheric boiling point of said solvent is in the range of 80 to 120°C. 10 (10) The process of (1) wherein said molar ratio of POCl3 to PE is in the range of 0.9 to 1.10 moles of POCl3 per mole of PE. (11) The process of (1) carried out by adding the total amount of PE to the solvent, heating the resulting slurry in 15 the reaction zone to a temperature close to the desired reaction temperature while allowing the pressure in the reaction zone to increase to the superatmospheric reaction pressure, adding the POCl3 portionwise to the reaction zone, maintaining the reaction temperature at the desired level, and continuing the reaction until the substantial completion of the evolution of HCl off-gas. 20 (12) The process of (11) wherein the pressure in the reaction zone is allowed to rise to a superatomspheric level by the accumulation of HCl off-gas. (13) The process of (1) wherein the reaction time is in the range of 0.5 to 8 hours. 25 (14) The process of (13) where said range of reaction time is 1 to 3 hours. (15) The process of (11) wherein said POCl3 is added within a time range of 5 minutes to 2 hours. (16) The process of (11) wherein PEPA is produced before further purification in a mass yield of at least 95% of 30 the theoretical yield based on the reactant present in limiting amount and with a PEPA purity of at least 80%. (17) A process for the production of pentaerythritol phosphate alcohol (PEPA) comprising reacting in the liquid phase phosphorus oxychloride (POCl3) with pentaerythritol (PE) at a molar ratio of no more than 1.20 mole of POCl3 per mole ofPE and at a reaction temperature of at least 100°C in the presence of a solvent which is an 35 alkane substituted with at least one halogen atom and having an atmospheric boiling point of 40 to 150°C, said atmospheric boiling point being below said reaction temperature, the reaction pressure being superatmospheric and sufficiently high to maintain the solvent in the liquid phase, the reaction resulting in the production of PEPA and HCl by-product. 40 (18) The process of (17) wherein said molar ratio is no more than 1.15. (19) The process of (17) wherein said alkane is methane, ethane or propane. (20) The process of (19) wherein said halogen atom is chlorine. 45 (21) The process of (20) wherein said solvent is 1,2-dichloroethane (ethylene dichloride or EDC). (22) The process of (17) wherein said reaction temperature is in the range of 100 to 150°C. 50 (23) The process of (22) wherein said reaction temperature is in the range of 110 to 130°C. (24) The process of (1) wherein said superatomspheric reaction pressure is up to 482,79 kPa (70 psig). (25) The process of (24) wherein said reaction pressure is in the range of 137,94 kPa to 344,85 kPa (20 to 50 psig). 55 (26) The process of (1), wherein said solvent is selected from the group consisting of 1,2-dichloroethane (ethylene dichloride or EDC), 1,1-dichloroethane (ethylidene chloride), 1,1,1-trichloroethane (methyl chloroform), trichlo- romethane (chloroform) tetrachloromethane (carbon tetrachloride), 1,1-dichloropropane, 1-bromopropane (n-pro- 3 EP 1 399 456 B1 pylbromide), 2-bromopropane (isopropylbromide), iodoethane (ethyl iodide), 2-iodopropane (isopropyl iodide), and bromochloromethane.
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