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US5608116.Pdf |||||||||| US005608116A United States Patent (19) 11 Patent Number: 5,608,116 Halling et al. 45 Date of Patent: Mar. 4, 1997 54) PROCESS FOR THE ALKOXYLATION OF 4,483,941 11/1984 Yang ....................................... 502/171. FLUORNATED ALCOHOLS 4,490,561 12/1984 Yang et al. ... ... 568/615 4,533,759 8/1985 Harris...................................... 568/648 (75) Inventors: Robert A. Halling, Wilmington; 5,097,090 3/1992 Beck ....................................... 568/842 Hsu-Nan Huang, Newark, both of Del. FOREIGN PATENT DOCUMENTS 73 Assignee: E. I. Du Pont de Nemours and 0161459 4/1985 European Pat. Off. ........ C07C 43/11 Company, Wilmington, Del. 2459900 12/1974 Germany .......... C08G 65/12 2153373 8/1985 United Kingdom............ C07C 65/26 WO95/35272 12/1995 WIPO ............................. C07C 43/11 21 Appl. No.: 405,327 |22) Filed: Mar 16, 1995 OTHER PUBLICATIONS *Derwent Publications Abstract "Surface Active Alkoxy Related U.S. Application Data lated Fluoro Alcohols-Useful for Making Fluoropolymers for Textile Finishing’ & DD,A,111522 (Greiner A.), 20 Feb. (63) Continuation-in-part of Ser. No. 263,091, Jun. 21, 1994. 1975. 51 Int. Cl. .................... C07C 41/03 Primary Examiner-Porfirio Nazario-Gonzalez 52 ve 568/615; 568/614 Assistant Examiner-Dwayne C. Jones 58 Field of Search ............................................... 568/615 (57) ABSTRACT 56) References Cited The present invention relates to the preparation of fluoro alkylalkoxylates in which one reacts at least one fluorinated U.S. PATENT DOCUMENTS alcohol with at least one alkylene epoxide in the presence of 2,723,999 11/1955 Cowen et al. .......................... 260/615 a novel catalyst system comprising an iodine source and an 3,948,668 4/1976 Hayek et al. ............................. 06/20 alkali metal borohydride. 4404407 9/1983 Harris .................. ... 568/648 4,478,760 10/1984 Blancou et al. .... ... 558/357 16 Claims, No Drawings 5,608,116 1. 2 PROCESS FOR THE ALKOXYLATION OF remove the organic solvent during their manufacturing FLUORNATED ALCOHOLS operations; this can be expensive and result in increased worker safety and environmental hazards. Even when dis CROSS-REFERENCE TO RELATED solved in organic solvent mixtures, known fluoroalkyla APPLICATIONS lkoxylates tend to form sediments. Such sediments are not easily filterable, and they tend to form continuously over This is a continuation-in-part of application Ser. No. time, which makes it impractical to remove the sediments 08/263,091 filed 21 Jun, 1994 now allowed. from fluoroalkylalkoxylate solutions before shipment to the user. There are other fluoroalkylalkoxylates disclosed in the FIELD OF THE INVENTION 10 prior art which have higher water solubility, e.g. those The present invention relates to a process for the prepa having a large average number of the hydrophilic oxyalky ration of fluoroalkylalkoxylates by the reaction of fluori lene groups, typically greater than about 18 such groups. nated alcohols with alkylene epoxides in the presence of a Another example is Fluorotenside FT-219 marketed by catalyst system. Bayer AG; however, the structures of that product and 15 related compositions incorporate additional hydrophilic functional groups, such as sulfonylamido linkages. In addi BACKGROUND OF THE INVENTION tion, a high degree of alkoxylation may result in the fluo Alcohol alkoxylates are an important class of materials roalkylalkoxylate composition forming a gel during prepa having use in a wide variety of industrial applications, for ration that makes them difficult or impossible to use. example as nonionic surfactants. They are typically prepared 20 by the reaction of an alcohol with an alkylene epoxide such BRIEF SUMMARY OF THE INVENTION as ethylene oxide (i.e. oxirane) or propylene oxide (i.e. 2-methyloxirane) in the presence of one or more catalysts. The present invention relates to a novel catalyst useful for Compositions prepared by the reaction of an alcohol incor the preparation of fluoroalkylalkoxylates. In particular, one porating a fluorinated alkyl group with an alkylene epoxide 25 reacts at least one fluorinated alcohol with at least one (fluoroalkylalkoxylates) are especially useful in several alkylene epoxide in the presence of a novel catalyst system important industrial applications, including use as nonionic comprising an iodine source and an alkali metal borohy fluorosurfactants in the manufacture of PVC films, electro dride. In addition to its general usefulness for the preparation chemical cells, and various photographic coatings. of mixtures of fluorinated alcohol alkoxylates, the catalyst 30 system of this invention can be successfully employed for There are numerous known catalyst systems and pro the alkoxylation of discrete perfluoroalkyl-ethanols. cesses for the alkoxylation of fluorinated alcohols. Lewis acids have been shown to be effective catalysts, e.g. boron trifluoride or silicon tetrafluoride, alone or in combination DETAILED DESCRIPTION OF THE INVENTION with metal hydrides, fluorides, alkyls or alkoxides. Unfor 35 tunately, such acidic materials also catalyze side reactions The process of the present invention comprises reacting a during the alkoxylation, such as dimerization of alkylene fluorinated alcohol or mixture of fluorinated alcohols with epoxides to form dioxanes. The side reactions lead to excess one or more alkoxylating agents in the presence of a catalyst waste generation, product contamination, and higher con system comprising a mixture of an alkali metal borohydride sumption of reactants, thereby significantly increasing costs 40 and at least one iodine source selected from the group and making operation of the processes more difficult. While consisting of alkali metal iodides, alkaline earth metal the use of strong bases as catalysts for the alkoxylation of iodides, and elemental iodine at temperatures in the range hydrocarbon alcohols minimizes some side reactions, the between about 90° C. and 200° C. and pressures of from use of strong base alone is not satisfactory for alkoxylation atmospheric pressure to about 100 psig. The catalyst system of flurorinated alcohols. 45 is effective in the absence of promoters or other catalysts A commercially important class of fluoroalkoxylates con such as strong bases, although such materials can be present sists of a mixture thereof derived by the alkoxylation of a if desired. commercial mixture of perfluoroalkylethanols having the The alkali metal borohydrides suitable for use in the general structure RCHCH-OH wherein R is a linear or catalyst system of the present invention include sodium branched perfluoroalkyl group having from 4 to 30 carbon 50 borohydride, potassium borohydride, and lithium borohy atoms. The mixture of perfluoroalkyl-ethanols is alkoxylated dride, with sodium borohydride being preferred. The mole using strong base catalysts, alone or in combination with ratio of alkali metal borohydride to fluorinated alcohol can sodium borohydride. Unfortunately, that alkoxylation pro vary widely. Normally the mole ratio will be in the range cess is plagued with variability in respect of reaction rates between about 0.005 and 0.25 or higher, the upper limit and induction period which makes commercial manufacture 55 being imposed only by practical considerations such as the of these fluoroalkoxylates unpredictable and difficult. cost of excessive borohydride use, contamination of product It is more convenient and economical to manufacture, and waste streams with excess borohydride, and potential store, and ship fluoroalkylalkoxylates in a solution of higher difficulty in controlling the rate of the exothermic alkoxy concentration, typically at about 40 percent by weight. In lation reaction. The optimum mole ratio of borohydride to order to achieve this high solution concentration, known fluorinated alcohol may be determined by standard experi fluoroalkylalkoxylates must be dissolved in an organic sol mental methods familiar to those skilled in the art of alcohol vent, such as isopropyl alcohol (IPA), or in a solvent mixture alkoxylation reactions, and will be affected by such factors comprising water in combination with one or more of such as the structures of the fluorinated alcohol and alkoxylating organic solvents. However, the resulting solution may be agent, and the temperature, pressure and cooling efficiency flammable or have increased toxicity, and thus be more 65 of the reaction vessel. For the reaction of an alkylene oxide, difficult and expensive to ship and use safely. In addition, the such as ethylene, with fluorinated alcohols useful for the users of said fluoroalkylalkoxylate solutions frequently must purposes of this invention at 130° C. to 145° C. under 5,608,116 3 4. atmospheric pressure, the preferred mole ratio is in the range -continued between about 0.025 and about 0.1. O Iodine sources suitable for use in the catalyst system of the present invention include elemental iodine, lithium iodide, sodium iodide, potassium iodide, and calcium iodide. The preferred iodine source is iodine or sodium wherein iodide or a mixture of the same. The mole ratio of iodine R is linear or branched perfluggalkyl having from 4 to source to alkali metal borohydride is in the range between 20 carbon atoms; each of R, and R.? is independently linear or branched perfluoroalkyl having from 4 to 12 carbon about 0.1 and about 300. The optimum mole ratio of iodine 10 atoms, preferably from 6 to 10 carbon atoms; and source to alkali metal borohydride may be determined
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