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(12) United States Patent (10) Patent No.: US 7.494,962 B2 Kinet Al

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(12) United States Patent (10) Patent No.: US 7.494,962 B2 Kinet Al USOO74949.62B2 (12) United States Patent (10) Patent No.: US 7.494,962 B2 Kinet al. (45) Date of Patent: Feb. 24, 2009 (54) SOLVENTS CONTAINING CYCLOAKYL (56) References Cited ALKYLETHERS AND PROCESS FOR PRODUCTION OF THE ETHERS U.S. PATENT DOCUMENTS 3496,223 A * 2/1970 Mitchell et al. ............... 562/22 (75) Inventors: Idan Kin, Ottawa (CA); Genichi Ohta, Tokyo (JP); Kazuo Teraishi, Tokyo (JP); Kiyoshi Watanabe, Tokyo (JP) (Continued) (73) Assignee: Zeon Corporation, Tokyo (JP) FOREIGN PATENT DOCUMENTS (*) Notice: Subject to any disclaimer, the term of this EP 587434 A1 3, 1994 patent is extended or adjusted under 35 U.S.C. 154(b) by 349 days. (Continued) (21) Appl. No.: 10/481,340 OTHER PUBLICATIONS (22) PCT Filed: Jun. 27, 2002 Edited by Kagaku Daijiten Henshu Iinkai, “Kagaku Daijiten 9”. (86). PCT No.: PCT/UP02/06501 Kyoritsu Shuppan Co., Ltd., Aug. 25, 1962, p. 437, "Yozai'. (Continued) S371 (c)(1), (2), (4) Date: Sep. 24, 2004 Primary Examiner Gregory E Webb (74) Attorney, Agent, or Firm—Birch, Stewart, Kolasch & (87) PCT Pub. No.: WO03/002500 Birch, LLP PCT Pub. Date: Jan. 9, 2003 (57) ABSTRACT (65) Prior Publication Data The present inventions are (A) a solvent comprising at least US 2005/OO65060A1 Mar. 24, 2005 one cycloalkyl alkyl ether (1) represented by the general O O formula: R1-O R2 (wherein R1 is cyclopentyl or the like: (30) Foreign Application Priority Data and R2 is C1-10 alkyl or the like); (B) a method of prepara Jun. 28, 2001 (JP) ............................. 2001-196766 tions the ethers (1) characterized by reacting an alicyclic Oct. 30, 2001 (JP) ............................. 2001-332009 olefin with an alcohol in the presence of an acidion-exchange Dec. 11, 2001 (JP) ............................. 2001-377483 resin having a water content of 5 wt % or less. The solvent is Mar. 29, 2002 (JP) ............................. 2002-004269 useful as cleaning solvent for electronic components, preci Apr. 25, 2002 (JP) ............................. 2002-123832 Sion machinery components or the like, reaction solvent using various chemical reactions, extraction solvent for extracting (51) Int. Cl. objective organic Substances, solvent or remover for elec CLID 7/50 (2006.01) tronic and electrical materials, and so on. The process enables (52) U.S. Cl. ....................................... 510/17s. 510,407 industrially advantageous production of the objective (58) Field of Classification Search ................. so 17s, cycloalkylalkyl ethers (1). 510/407 See application file for complete search history. 13 Claims, 2 Drawing Sheets {a} 2 s 2b (b) 3. st (c) se s 2 US 7.494.962 B2 Page 2 U.S. PATENT DOCUMENTS JP 58-118531 A T 1983 JP 59-025345 A 2, 1984 4,306,100 A 12, 1981 Wood JP 61-249945. A 11, 1986 4,511,488 A 4, 1985 Matta JP 3-062897 A 3, 1991 4,640,719 A 2/1987 Hayes et al. JP 3-240754. A 10, 1991 4,740,247 A 4/1988 Hayes et al. JP 5-163188 A 6, 1993 4,762,826 A 8, 1988 Eckhardt ..................... 514.63 JP 6-49495 A 2, 1994 4,990,688 A * 2/1991 Gosch et al. 568,810 JP 11-228478 A 8, 1999 5,284,986 A * 2/1994 Dessau ....... 585, 318 JP 2001-261592. A 9, 2001 5,393,766 A * 2/1995 Hubele .... 514,365 JP 2002-167347 A 6, 2002 5,529,874. A 6/1996 Kobayashi et al. WO 98.51651 A1 11, 1998 5,589,503 A * 12/1996 Mencke et al. .............. 514,450 6,084,144. A * 7/2000 Takashima et al. .......... 585/525 OTHER PUBLICATIONS FOREIGN PATENT DOCUMENTS Edited by Shigeru Ozaki. “Shokubai Kogaku Koza 10 Genso Betsu Shokubai Binran’, Chijinshokan Co., Ltd., Feb. 25, 1967, pp. 727 to EP O994 089 A1 4/2000 729. GB 2017693. A 10, 1979 JP 55-1492.19 A 11, 1980 * cited by examiner U.S. Patent Feb. 24, 2009 Sheet 1 of 2 US 7.494,962 B2 (d) N-2a so No 2b (b) 3C 3b N-b (C) 3e 3d 2c C FIG. I. U.S. Patent Feb. 24, 2009 Sheet 2 of 2 US 7.494,962 B2 -2b N-b FIG. 2 FIG. 3 US 7,494,962 B2 1. 2 SOLVENTS CONTAINING CYCLOAKYL dimethylbenzyl alcohol) only in a low yield. Therefore, ALKYL ETHERS AND PROCESS FOR development of a reaction solvent that can be easily recovered PRODUCTION OF THE ETHERS after use and exhibits excellent reaction selectivity has been desired. TECHNICAL FIELD A solvent extraction is a well-known method for extracting a desired compound from a mixture using an appropriate The present invention relates to a solvent comprising a extraction solvent. Various extraction solvents that can be cycloalkylalkyl ether compound and a process for producing used are known. Examples include halogenated hydrocar the cycloalkyl alkyl ether compound. More particularly, the bons such as dichloromethane and chloroform; aliphatic present invention relates to a solvent containing a cycloalkyl 10 hydrocarbons such as n-hexane and cyclohexane; aromatic alkyl ether compound useful as a cleaning solvent for elec hydrocarbons such as benzene and toluene; esters such as tronic parts, precision machinery components, and the like, a methyl acetate and ethyl acetate, ketones such as acetone and reaction solvent for various chemical reactions, an extraction cyclohexanone; and ethers such as diethyl ether and dipropyl Solvent for extracting objective organic Substances from vari ether. ous mixtures, a solvent or remover agent for electronic and 15 Requirements for the extraction solvents include (i) being electric materials, and the like, to a method for cleaning inactive under the extraction conditions, (ii) being capable of articles, a method for reacting an organic metal, a Grignard Sufficiently dissolving extracted Substances, (iii) having an reaction method, a method for extracting organic compounds, appropriate boiling point, producing vapor that has a minimal and a method for producing parts for electronic and electrical risk of being absorbed during the solvent extraction opera materials using the solvent, and to a process for advanta tion, and being easily evaporated, and (iv) having only a slight geously producing the cycloalkylalkyl ether compound in an possibility of polluting the environment. industrial scale. However, only a few extraction solvents currently available satisfy these requirements. For example, since halogenated BACKGROUND ART hydrocarbons such as dichloromethane and chloroform hav 25 ing excellent capability of dissolving various organic com Conventionally, a cleaning operation using a cleaning Sol pounds have a strong toxicity and a low boiling point, their vent is carried out during manufacturing electronic equip vapor have a risk of being inhaled during the extraction opera ment, precision machines, and the like to prevent degradation tion and cause an environmental pollution problem. Esters of electrical characteristics and mechanical characteristics. Such as ethyl acetate and aromatic hydrocarbons such as Chemically stable chlorine or flonsolvents have been used for 30 toluene are also extraction solvents with wide versatility, but this purpose. The use of a number of these solvents has been exhibit only limited capability of dissolving organic com regulated due to the problems in safety, toxicity, and environ pounds having a moderate polarity and insufficient extraction mental pollution. efficiency. Therefore, development of a novel extraction sol Cleaning solvents and cleaning compositions that are safe, vent advantageous from the viewpoint of extraction operation less toxic, and less pollutant to the environment have been 35 and environmental safety has been desired. proposed as Substitutes for these solvents. For example, Conventionally, various organic solvents such as aromatic cleaning solvents and cleaning compositions described in hydrocarbon Solvents, aliphatic hydrocarbon Solvents, and U.S. Pat. Nos. 4,511,488, 4,640,719, 4,740,247, JP-A halogenated hydrocarbon solvents have been used as a sol 3-62897, JP-A 6-49495, and the like are given. vent and parting agents for electronic materials, electrical However, these cleaning solvents are not necessarily satis 40 materials, and the like. It is desirable that these solvents and factory in their detergency, particularly detergency for oils parting agents exhibit high solubility and dispersibility of and fats. Therefore, development of a novel cleaning solvent electronic and electrical materials and are safe and free from excelling in both safety and detergency has been desired. the problem of environmental pollution. Conventionally, ether solvents that are non-protonic and However, not a few currently available solvents and parting polar have widely been used as reaction solvents for various 45 agents lack solubility and dispersibility of electronic and organic reactions (hereinafter referred to as “reaction') such electrical materials, are strongly toxic, and pollute the envi as a Grignard reaction. Tetrahydrofuran (THF), which is a ronment. Therefore, development of a solvent and parting typical ether solvent, is a non-protonic and polar solvent agent exhibiting high solubility and dispersibility of elec having a moderate boiling point. THF is commonly used as a tronic and electrical materials and being safe and free from reaction solvent, particularly for Grignard reactions, reac 50 the problem of environmental pollution has been desired. tions using an organolithium compound or the like, and other As the method for producing ethers by the addition reac similar reactions. However, if THF is used as a solvent for a tion of an olefin to an alcohol, a method of using crystalline reaction mixture to which water is added, it is difficult to alumino silicate as a catalyst (Japanese Patent Application remove THF from the reaction mixture since THF is mutually Laid-open No. 59-25345), a method ofusing HZSM-5 Zeolite soluble with water and forms an azeotrope. A special distil 55 as a catalyst U.S. Pat. No. 4.306,100), a method of using lation process involving addition of an entrainer or other third special alumino silicate having many acid points on the Sur components is required for industrially separating one com face as a catalyst (Japanese Patent Application Laid-openNo.
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