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5, R.O.S.No. 50A Is USOO673O815B2 (12) United States Patent (10) Patent No.: US 6,730,815 B2 Baimbridge et al. (45) Date of Patent: May 4, 2004 (54) METHOD OF PRODUCING GLYCOL 4,368,337 A 1/1983 Tawara et al. ETHERS 4,409,403 A 10/1983 Vaughan 4,504,685 A 3/1985 Vaughan (75) Inventors: Charles L. Baimbridge, Baton Rouge, : A E. 2 - 12 ee (US)5, s R.O.S.No.s s 5,994,59550A A 11/1999is KinOnda et al. (73) Assignee: Ferro Corporation, Cleveland, OH FOREIGN PATENT DOCUMENTS (US) DE 34.46488 A1 7/1986 (*) Notice: Subject to any disclaimer, the term of this Primary Examiner Taofiq A. Solola patent is extended or adjusted under 35 (74) Attorney, Agent, or Firm-Rankin, Hill, Porter & U.S.C. 154(b) by 97 days. Clark LLP (21) Appl. No.: 10/229,938 (57) ABSTRACT (22) Filed: Aug. 28, 2002 The present invention provides a method of producing 9. ZS, glycol ethers, which are also commonly known as glymes. (65) Prior Publication Data The method according to the invention includes contacting a glycol with a monohydric alcohol in the presence of a US 2004/004.4253 A1 Mar. 4, 2004 polyperfluoroSulfonic acid resin catalyst under conditions (51) Int. Cl. .......................... C07C 41/44; CO7C 43/04 effective to produce the glyme. The method of the invention (52) U.S. Cl. ....................................................... 568/679 can be used to produce, for example, monoglyme, ethyl (58) Field of Search .......................................... 568/679 glyme, diglyme, ethyl diglyme, triglyme, butyl diglyme, tetraglyme, and their respective corresponding monoalkyl (56) References Cited ethers. The present invention also provides a method of producing 1,4-dioxane from mono- or diethylene glycol and U.S. PATENT DOCUMENTS tetrahydrofuran from 1,4-butanediol. 4,321,413 A 3/1982 Vanderpool 4,360,698 A 11/1982 Sedon 22 Claims, No Drawings US 6,730,815 B2 1 2 METHOD OF PRODUCING GLYCOL certain illustrative embodiments of the invention, these ETHERS being indicative, however, of but a few of the various ways in which the principles of the present invention may be employed. BACKGROUND OF THE INVENTION DETAILED DESCRIPTION OF THE 1. Field of Invention INVENTION The present invention relates to a method of producing glycol ethers. Glymes are produced in accordance with the method of 2. Description of Related Art the invention by contacting a glycol with a monohydric alcohol in the presence of a polyperfluoroSulfonic acid resin Glycol ethers, which are also commonly known as catalyst under conditions effective to produce the glyme. A glymes, are used as aprotic Solvents in a variety of appli wide range of glymes can be produced in accordance with cations. Glymes can be produced by a variety of methods, the invention, with the resulting glyme being dependent but are conventionally produced in commercial quantities upon the glycol and monohydric alcohol Selected for use in via the Williamson synthesis or via a reaction that involves 15 the cleavage of epoxides. the reaction. For example, ethylene glycol and methanol react in accor In the Williamson synthesis, a monoalkyl polyalkylene dance with the method of the invention to produce ethylene glycol is treated with a base or an alkali metal, typically glycol dimethyl ether (monoglyme). These two reactants molten Sodium, to form an alkoxide ion, which is then also react to produce ethylene glycol monomethyl ether, reacted with an alkyl halide such as methyl chloride to form which is also known as 2-methoxyethanol or “Methyl CEL the glyme. The by-products from the Williamson synthesis LOSOLVE(E)'. CELLOSOLVE(E) is a trademark of the Dow are hydrogen gas and a Salt. Chemical Company used in connection with a class of Although the Williamson synthesis is one of the conven ethylene glycol monoalkyl ethers. tional methods of producing glymes on a commercial Scale, the proceSS presents Several disadvantages. For example, the 25 Ethylene glycol and ethanol react in accordance with the Williamson Synthesis requires the use of costly and poten method of the invention to produce ethylene glycol diethyl tially hazardous Starting materials. It generates hydrogen gas ether (ethyl glyme). These two reactants also react to pro as a by-product, which presents Safety and handling issues. duce ethylene glycol monoethyl ether, which is also known Moreover, for every mole of glyme produced, the proceSS as 2-ethoxyethanol or “Ethyl CELLOSOLVE(E)”. generates a mole of Salt as a by-product, which presents Diethylene glycol and methanol react in accordance with treatment and disposal issues. Furthermore, the Williamson the method of the invention to produce diethylene glycol Synthesis proceeds at a relatively slow rate. dimethyl ether (diglyme). These two reactants also produce The other conventional method for commercially produc diethylene glycol monomethyl ether, which is also known as ing glymes involves the cleavage of epoxides in presence of methoxyethoxy ethanol or “Methyl CARBITOL(R)”. CAR a low molecular weight ether and a Lewis acid catalyst. This 35 BITOL(R) is a trademark of the Dow Chemical Company reaction enables the insertion of Oxacycloalkanes into chain used in connection with a class of diethylene glycol type ethers. A typical reaction involves dimethyl ether and monoalkyl ethers. ethylene oxide with catalytic amount of boron trifluoride or Diethylene glycol and ethanol react in accordance with boron trifluoride dimethyletherate to yield, among other the method of the invention to produce diethylene glycol ether co-products, monoethyleneglycol dimethylether. 40 diethyl ether (ethyl diglyme). These two reactants also One of the principle disadvantages of the cleavage reac produce diethylene glycol monoethyl ether, which is also tion of epoxides is that it is not particularly Selective. known as “Ethyl CARBITOL(R)”. Insertion of a specific number of Oxacycloalkane units is Diethylene glycol and 1-butanol react in accordance with difficult to control. Therefore, the final product consists of a 45 the method of the invention to produce diethylene glycol mixture of glymes. It is necessary to Separate the reaction dibutyl ether (butyl diglyme). These two reactants also mixture by complex distillation techniqueS or by other produce diethylene glycol monobutyl ether, which is also means in order to obtain pure glymes, which adds time and known as “Butyl CARBITOL(R)”. complexity to the manufacturing process. Triethylene glycol and methanol react in accordance with the method of the invention to produce triethylene glycol BRIEF SUMMARY OF THE INVENTION 50 dimethyl ether (triglyme). These two reactants also produce The present invention provides a method of producing triethylene glycol monomethyl ether, which is also known as glymes that overcomes the disadvantages of both the Will methoxytriglycol. iamson Synthesis and the cleavage reaction of epoxides. The Tetraethylene glycol and methanol react in accordance method according to the invention comprises contacting a 55 with the method of the invention to produce tetraethylene glycol with a monohydric alcohol in the presence of a glycol dimethyl ether (tetraglyme). These two reactants also polyperfluoroSulfonic acid resin catalyst under conditions produce tetraethylene glycol monomethyl ether, which is effective to produce the glyme. The Starting materials used also known as methoxytetraglycol. It will be appreciated in the method according to the invention are commercially that other glymes can be produced in accordance with the readily available, not expensive or hazardous, and the cata 60 method of the invention Simply be Selecting other glycols lyst used in the reaction can be recovered, regenerated, and and monohydric alcohols. reused. The method according to the invention does not The Starting materials used in the reaction, being glycols generate hydrogen gas or Salt, it proceeds at a relatively and monohydric alcohols, are generally inexpensive and rapid rate, and it produces a Single glyme. readily available. These Starting materials do not present The foregoing and other features of the invention are 65 Significant toxicity and handling problems, especially when hereinafter more fully described and particularly pointed out compared to the Starting materials used in the Williamson in the claims, the following description Setting forth in detail Synthesis. US 6,730,815 B2 3 4 Preferably, a molar excess of the monohydric alcohol is reuse in accordance with known methods. Once the activity used in the reaction. Typically, a molar excess of about 3 to of the polyperfluorosulfonic acid declines, the material can about 5 moles of monohydric alcohol is used in the reaction be regenerated by treatment with a strong mineral acid (i.e. for every mole of glycol. nitric acid) to restore the proton sites on the resin. The glycol The polyperfluoroSulfonic acid resin catalyst used in the bottoms are further stripped off residual lights to yield a method of the invention is a Bronsted acid, and not a Lewis concentrated polyperfluoroSulfonic acid resin catalyst Solu acid. Suitable polyperfluoroSulfonic acid resins are available tion. The later is transferred into a dryer, typically a double from E.I. Du Pont de Nemours and Company under the cone dryer, to evaporate the remaining liquid constituents. NAFIONR trademark. These polyperfluorosulfonic acid The resulting Solid can then be treated in a separate vessel resins are believed to be copolymers of tetrafluoroethylene with a strong mineral acid (i.e. nitric acid) at 80° C. for 1 and perfluoro-3,6-dioxa-4-methyl-7-octenesulfonyl fluoride, hour. After Several washes, the regenerated polyperfluoro which have been converted to the proton (H) form. They Sulfonic acid resin catalyst is dried and recycled in the are available in flake, pellet, powder, film, and Solution form. proceSS. The polyperfluoroSulfonic acid resin catalyst is preferably It will be appreciated that the reaction described above used at about 0.5 to about 2.0 equivalents per 100 moles of 15 can also be performed by continuously feeding the glycol, glycol, with about 1.0 equivalent being most preferred monohydric alcohol and polyperfluorosulfonic acid resin during the preparation of monoglyme.
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