WO2005110957A2

WO2005110957A2 - Fluorinated ethers

Info

Publication number: WO2005110957A2
Application number: PCT/US2005/016382
Authority: WO
Inventors: Haridasan K. Nair; Rajiv R. Singh
Original assignee: Honeywell International Inc.
Priority date: 2004-05-11
Filing date: 2005-05-11
Publication date: 2005-11-24
Also published as: WO2005110957A3

Abstract

Present invention relates to novel fluorinated ethers and to a process for producing such fluorinated ethers. Such fluorinated ethers find use in as solvents, anesthetics, refrigerants, cleaning compositions, dry cleaning compositions, blowing agents, flame retardants, formulations of dyes used in optical recording media, microemulsions, and heat transfer compositions. The fluorinated ethers have the formula R-O-R1 wherein R = CF3-CXH-CYZ wherein each of X, Y and Z are independently H or halogen; and R1 is a C1 to C16 alkyl group or a halogen substituted C1 to C16 alkyl group.

Description

H0005126 (4640)

FLUORINATED ETHERS BACKGROUND OF THE INVENTION

The present invention relates to novel fluorinated ethers and to a process for producing such fluorinated ethers. The fluorinated ethers find use as solvents, anesthetics, refrigerants, cleaning compositions, dry cleaning compositions, blowing agents, flame retardants, formulations of dyes used in optical recording media, microemulsions, and heat transfer compositions.

Fluorinated ethers are an important class of compounds, which have use in many industrial applications, see Banks, R.E. et al., Organofiuorine Chemistry, Principles and Commercial Applications (1994), Plenum Press, New York. These find use as anesthetics, refrigerants, cleaning compositions, especially dry cleaning compositions, blowing agents, flame retardants, heat transfer compositions, solvents and microemulsion compositions.

Generally, fluorinated ethers are nonflammable, non-toxic, and environmentally benign and have high heat transfer capacity and low viscosity. U.S. patent

3,450,773 describes the use of fluorinated ethers as anesthetics. Hydrofluoroethers are well known anesthetics. These include sevoflurane (CF )₂CHOCH₂F, which is commercially available from Abbott Laboratories of Abbott Park Illinois, and desflurane (CF₃CHFOCHF₂), which is commercially available from Baxter International Inc. Corporation, of Deerfield Illinois. For use as anesthetics also see pages 543-553 of Banks, R.E. et al., above. U.S. patent 5,713,211 describes hydrofluoroethers such as C F₇OCH₃, C₄F OCH₃, and C₄F OC₂H₅ as low temperature heat transfer media in the secondary loop of refrigeration systems.

The preparation of some hydrofluoroethers is described in Banks, R. E. et al., above, at pages 548-554 and Huoben-Weyl-Organo-Fluorine Compounds (2000), Vol El Ob/1, pages 572-573, Editors Bassner et. al, Thieme, Stuttgart and New York.

Reactions of CF₃CH₂OH and (CF₂HC1) in the presence of NaOH affords HCF₂-OCH₂CF₃ as disclosed in U.S. patent 3,637,477. Some hydrofluoroethers are prepared by fluorination in the gas phase, for example reactions of HCF₂CF₂OCH₃ with fluorine in gas phase is reported in JP 11124352 A2 to give a mixture of HCF₂₎CF₂θCF_3!HCF₂CF₂OCF₂H and HCF₂CF₂OCH₂F. Japanese patent JP 09323949 describes the preparation of CF₃CF(OCF₃)CH₂CHl(CH₂)₃ by addition of CF₃CF1(0CF₃) to 1 -hexene in the presence of Cu powder at 70 °C.

U.S. patent 6,054,626 and references therein describes the preparation of fluorinated ethers with a metal fluoride, sulfur tetrafluoride, bromine trifluoride and fluorine gas at high temperature(200-300 °C). These processes generally afford multiple products since the fluorination is not selective.

The present invention provides the fluorinated ethers in a single step from readily available starting materials, namely fluoroolefins and alcohols. The process does not require the use of hazardous and corrosive reagents or high temperature and does not result in multiple byproducts.

The hydrofluoroethers of this invention exhibit one or more of the following properties: chemical stability; little or no substantial ozone depleting potential (ODP); relatively high degree of miscibility with common contaminants, particularly mineral oil and/or silicone oil; low or no flammability, and low or no toxicity. As used herein, ODP is defined in the "Scientific Assessment of Ozone Depletion, 2002", a report of the World Meteorological association, incorporated here by reference. The preferred compounds for use in the present compositions have been found to possess at once several of these desirable beneficial properties. More specifically, the preferred compounds have little or no substantial ozone depletion potential, preferably an ODP of not greater than about 0.1 and more preferably not greater than about 0.05, most preferably not greater than about 0.02.

DESCRIPTION OF THE INVENTION The invention provides a fluorinated ether of the formula R-O-Ri wherein R = CF₃-CXH-CYZ wherein each of X, Y and Z are independently H or a halogen; and R] is a C] to C₁₆ alkyl group or a halogen substituted Ci to C₁₆ alkyl group. Preferably the halogen comprises fluorine. The inventive fluorinated ethers include all isomers thereof.

The invention also provides a method for preparing a fluorinated ether of the formula R-O-R] wherein R = CF₃-CXH-CYZ wherein each of X, Y and Z are independently H or halogen; and Ri is a Ci to C)₆ alkyl group or a halogen substituted C] to Cι₆ alkyl group, the method comprising reacting a fluoroolefin of the formula CF₃CX=CYZ with an alcohol of the formula R]OH, provided the alcohol does not contain a -CF₂OH group, in a solvent and in the presence of base. Ri should not be a perfluoro compound. Preferred fluorinated ethers according to the invention include those having the formulae CF₃CH₂CF₂-0-R,, CF₃CFHCHF-0-Rι_ι CF₃CH₂CFH-0-Rι_j CF₃CFHCH2-O-R1, CF₃CH2CHCI-O-R1, CF₃CHClCHCl-O-R,_, CF₃CHBrCH₂O- R_! wherein Ri is selected from the group consisting of CH₃(CH₂)_n, CF₃CH₂, (CF₃)₂CH, (CF₃)₂CF, CF₃CH CF₂CH_{2 ,} CF₃CH₂CFHCH_2, CF₃CBrHCF₂CH_2, CF₃CC1HCH₂CH₂, CF₃CH2CF_2! CF₃CH₂CFH, CF₃CFHCF₂, CF₃(CF₂)_nCH₂, and CF₃(CF₂)_nCH₂CH₂ wherein n = 1-13.

The more preferred fluorinated ethers according to the invention include those having the formulae CF₃CH2CF₂-0-CH₂CF₃; CF₃CH₂CFH-0-CH₂CF₃;

CF₃CH₂CF2-0-CH(CF₃)2; CF₃CH₂CFH-0-CH(CF₃)₂; CF₃CH2CF₂-O-C(CF₃)₃; CF₃CH₂CFH-O-C(CF₃)₃; CF3CFHCF2-O-CH2CF2CH2CF3; CF₃CH₂CF₂-O- CH₂CF2CH2CF3; CF3CFHCFH-O-CH2CF2CH2CF₃; CF₃CFHCF₂-O- CH2CF₂CH2CF3; CF₃CFHCF2-0-CH₂CF2CH2CF3.

Preferably R includes CF3CH2CF2, CF₃CH₂CHF, CF₃CFHCH₂, CF₃CH₂-CH₂, CF₃CFH-CFH, CF₃CBrH-CFH, CF₃CFHCFH, CF₃CH₂CHC1, and CF₃CC1HCC1H. Preferably R, includes CH₃(CH₂)_n, CF₃CH₂, (CF₃)₂CH, CF₃CH2CF2CH2 , CF₃CH₂CFHCH₂. CF₃CBrHCF₂CH₂, CF₃CC1HCH₂CH₂, CF₃CH₂CF₂, CF₃CH₂CFH, CF3CFHCF2, CF₃(CF₂)_nCH₂, and CF3(CF₂)_nCH₂CH₂ wherein n = 1-13.

The fluorinated ether compounds of the present invention are prepared according to the following reaction scheme: CF₃CX=CYZ + R_jOH *~ CF₃-CXH-CYZ-0-Rj

Typically, the desired fluoroolefin of formula CF₃CX=CYZ (X, Y and Z are as defined above) is added to a solution of the desired alcohol (RiOH) in a polar aprotic solvent in the presence of base.

The fluoroolefins of the formula CF₃CX=CYZ are either available commercially or they can be prepared by procedures known in the art. Fluoroolefins are available commercially from Synquest Lab,- Aldrich Co. and Honeywell International Inc. Other fluorinated ethers can be obtained by procedures known in the art, such as those disclosed in U.S. patent 6,548,719 which is incorporated herein by reference. Preferred fluoroolefins non-exclusively include CF₃CF=CF_2, CF₃CH=CF₂ (HFC 1225), CF₃CH=CFH (HFC 1234), CF₃CF=CH₂, CF₃CF=CFH, CF₃-CF=CFBr, CF₃-CH=CHC1, CF₃-CC1-CHC1, and CF₃CBr=CF₂.

The alcohol is chosen such that R] is a to Cι₆ alkyl group which may be linear or branched, or a halogen (F, CI, Br or I) substituted C_\ to C]₅ alkyl group which may be linear or branched. Preferably Ri is a Cj to C₁₀ alkyl group and more preferably a Ci to C₆ alkyl group. R] should not be fully substituted by the same halogen and contain a terminal -CH₂ group, nor should R] be a terminal CX₂ group where X =halogen.

Preferably the alcohol RjOH is fluorine containing. Typically the alcohol RjOH is chosen such that R, may be CH₃(CH₂)_n, CF₃CH₂, (CF₃)₂CH, CF₃CH₂CF₂CH_{2 ,} CF3CH2CFHCH2, CF₃CBrHCF₂CH₂, CF₃CC1HCH₂CH₂. CF₂CH₂CHC1CH₂, CF₃CF₂CH2OH, CF₃CHC1CF₂CH₂ , CF3CHCICHCICH2, CF₃CH₂CF₂, CF₃CH₂CFH, CF₃CFHCF₂, CF₃(CF₂)_nCH₂, and CF₃(CF₂)_nCH2CH2 wherein n = 1-13.

Fluoroalcochols (R)OH) are commercially available from Synquest Lab, and Aldrich Co., or they can be prepared by art recognized procedures, see, M. Hudlicky, Chemistry of Organic Fluorine Compounds, 2ⁿ edition, (1992), Ellis Horwood. CF₃CH CF2CH₂OH and CF₃CH CFHCH₂OH may be prepared according to the method of U.S. patent application No. 10/247,383 which is incorporated herein by reference

Useful solvents for the reaction are preferably aprotic solvents. Aprotic solvents non-exclusively include acetonitrile, benzonitrile, dimethylformamide, dimetylsulfoxide and the like. In some instances, the starting alcohol (RiOH) can function as a solvent as well as a reactant. The unreacted alcohol can be recycled.

Useful bases non-exclusively include alkali carbonates, alkaline metal carbonates, ammonium carbonates, alkali hydroxides alkaline metal hydroxides, ammonium hydroxide and organic bases. Preferred bases non-exclusively include inorganic bases such as KOH, NaOH, CsOH a2CO₃, K₂CO₃, Cs₂CO₃, organic bases such as trialkylamines such as triethylamine and ^'tributyl amine, cyclic bases such as pyridine, 1,4- diazabicyclo[2,2,2octane (DABCO), l,8-diazabicyclo[5.4.0]undec- 7-ene (DBU) , and the like.

In the reaction, the fluoroolefin is employed in an amount which is an excess over the amount of the alcohol. Preferably the fluoroolefin is present in an amount of from about 1.0 to about 1.5 equivalents with respect to alcohol and more preferably from about 1.0 to about 1.2 equivalents with respect to the alcohol. The solvent is preferably present in an excess. Preferably the base is present in a catalytic amount. More preferably the base is present in an amount of from about 0.01 to about 20 mol % and more preferably from about 1 mol % to about 5 mol % based on the amount of the alcohol in the reaction.

The fluoroolefin can be bubbled into the solution of the alcohol or can be condensed via a cold (dry ice) condenser. The exotherm during the reaction can be moderated by appropriate cooling bath/assembly. The reaction is usually conducted at a temperature of from about -10 °C. to about 150 °C, or more preferably from about -10 °C. to about 75 °C, and most preferably from about -10 °C. to about 35 °C. The reaction is typically conducted for from about 30 minutes to about 48 hours, preferably from about 30 minutes to about 24 hours, and more preferably from about 30 minutes to about 3 hours. The reaction is typically conducted at a pressure of from about 14.7 psia to about 500 psia, preferably from about 14.7 psia to about 100 psia, and more preferably from about 14.7 psia to about 20 psia.

Thereafter the reaction product is subjected to subsequent step of separating and/or purifying the fluorinated ether, such as by filtration, extraction and/or distillation by techniques well known in the art.

The resulting fluorinated ether may be used as an anesthetic composition, a refrigerant composition, a cleaning composition, a dry cleaning composition, a solvent composition, a blowing agent, a flame retardant composition, reducing the flammability of flammable compositions, a heat transfer composition, or a microemulsion composition. The resulting fluorinated ether may be used for reducing the flammability of a fluid comprising adding to the fluorinated ether to the fluid in the desired amount. The resulting fluorinated ether may be used for suppressing a flame by contacting a flame with a fluid including the fluorinated ether.

The fluorinated ethers according to the invention may be employed as a solvent, cleaning composition, or dry cleaning composition. An important characteristic of the fluorinated ethers as they relates to such solvent, cleaning or dry cleaning applications is that they have been found to have a high level of solvent power for many common contaminants and residues while at the same time not having a high degree of acute toxicity, as measured by exposure to mice and rats. In a preferred embodiment, the solvent compositions of the present invention comprises the R-O-Ri ethers, including all isomers thereof, are miscible with mineral or silicone oils. As used herein, miscibility is measured in accordance with visual evaluation of phase formation or separation when two liquids are mixed together, as is known to those skilled in the art. However, it is also contemplated that in many embodiments the composition will include other components in addition to the above-noted compounds. For example, it is contemplated that in certain embodiments the surface treating compositions may include co-solvents, anticorrosive agents, surfactants, stabilizers, inhibitors and other adjuvants which assist with or enhance the functionality of the composition. Examples of co-solvents include linear, branched and cyclic hydrocarbons, halocarbons, including chlorinated and brominated compounds, alcohols, such as methanol, ethanol, propanol, isopropanol, butanol, etc., ketones, esters, ethers and acetals. Examples of stabilizers include nitroalkanes, epoxy alkanes and phosphite esters. Some of these form azeotrope-like compositions with the R-O-Ri ethers. Although it is contemplated that the compositions of the present invention may include the compounds of the present invention in widely ranging amounts, it is generally preferred that the solvent cleaning compositions of the present invention comprise a fluorinated ether compound in an amount that is at least about 10% by weight, and more preferably at least about 30% by weight of the overall cleaning composition with the balance including the abovementioned components in an amount easily determinable by those skilled in the art depending on the desired use. The fluorinated ethers are useful for contaminant removal by contacting the contaminated article with at least one fluorinated ethers compound of the present invention. In preferred embodiments, the methods comprise applying a solvent composition of the present invention to the article containing the contaminant, with vapor degreasing and solvent cleaning^' methods being particularly preferred, especially for cleaning intricate parts and difficult to remove soils. As those skilled in the art will appreciate, the present methods have applicability to a wide variety of different cleaning and residue removal techniques, and all such techniques are within the broad scope of the present invention. Preferred methods of the present invention comprise applying the fluorinated ether composition to an article. Preferred vapor degreasing and solvent cleaning methods are done by exposing an article, preferably at room-temperature, to the vapors of a boiling solvent. Vapors condensing on the object have the advantage of providing a relatively clean, distilled solvent to wash away grease or other contamination. Such processes thus have an additional advantage in that final evaporation of the present solvent composition from the object leaves behind relatively little residue as compared to the case where the object is simply washed in liquid solvent. For applications in which the article includes contaminants that are difficult to remove, it is preferred that the present methods involve raising the temperature of the solvent composition of the present invention above ambient or to any other temperature that is effective in such application to substantially improve the cleaning action of the solvent. Such processes are also generally preferred for large volume assembly line operations where the cleaning of article, particularly . metal parts and assemblies, must be done efficiently and quickly.

In this use, the cleaning methods of the present invention comprise immersing the article to be cleaned in a fluid solvent at an elevated temperature, and even more preferably at about the boiling point of the solvent. In such operations, this step preferably removes a substantial amount, and even more preferably a major portion, of the target contaminant from the article. This step is then preferably followed by immersing the article in solvent, preferably freshly distilled solvent, which is at a temperature below the temperature of the liquid solvent in the preceding immersion step, preferably at about ambient or room temperature. The preferred methods also include the step of then contacting the article with relatively hot vapor of the present solvent composition, preferably by exposing the article to solvent vapors rising from the hot/boiling solvent associated with the first mentioned immersion step. This preferably results in condensation of the solvent vapor on the article. In certain preferred embodiments, the article may be sprayed with distilled solvent before final rinsing. It is contemplated that numerous varieties and types of vapor degreasing equipment are adaptable for use in connection with the present methods. One example of such equipment and its operation is disclosed in U.S. patent 3,085,918, which is incorporated herein by reference. This equipment disclosed in includes a boiling sump for containing a solvent composition, a clean sump for containing distilled solvent, a water separator, and other ancillary equipment. The present cleaning methods may also comprise cold cleaning in which the contaminated article is either immersed in the fluid composition of the present invention under ambient or room temperature conditions or wiped under such conditions with rags or similar objects soaked in solvents. According to another aspect of the invention the fluorinated ethers can be used as solvent for dyes used for optical recording media such as DVD-R, CD-R data storage disks. Specific examples of dyes are found in U.S. patents 6,383,722, 5,855,979 and 5,693,396. Compounds of the present invention can also be used as a coating formulation with appropriate components/additives for optical recording media.

The fluorinated ethers according to the invention may be employed as heat transfer compositions such as refrigerant compositions. When the fluorinated ethers of the present invention are used in heat transfer applications, the heat transfer compositions may include the fluorinated ether compounds of the present invention in widely ranging amounts. It is generally preferred, however, that the heat transfer compositions, especially the refrigerant compositions of the present invention, comprise the fluorinated ether compounds in an amount that is at least about 50% by weight, and even more preferably at least about 70 % by weight, of the overall composition. The heat transfer compositions may include other components for the purpose of enhancing or providing certain functionality to the composition, or in some cases to reduce the cost of the composition. For example, refrigerant compositions according to the present invention, especially those used in vapor compression systems, include a lubricant, generally in amounts of from about 30 to about 50 percent by weight of the composition. Furthermore, the present compositions may also include a compatibilizer, such as propane, for the purpose of aiding compatibility and/or solubility. Such compatibilizers, including propane, butanes and pentanes, are preferably present in amounts of from about 0.5 to about 5 percent by weight of the composition. Combinations of surfactants and solubilizing agents may also be added to the present compositions to aid oil solubility, as disclosed by U.S. Patent No. 6,516,837, the disclosure of which is incorporated by reference. Commonly used refrigeration lubricants such as polyol esters (POEs) and poly alkylene glycols (PAGs) that are used in refrigeration machinery with hydrofluorocarbon (HFC) refrigerants may be used with the refrigerant compositions of the present invention. For compatibilizing compositions of the present invention, it may be preferred to include in such compositions co-solvents, anticorrosive agents, surfactants, stabilizers and other adjuvants which assist with or enhance the functionality of the composition. The preferred heat transfer methods generally comprise providing a composition of the present invention and causing heat to be transferred to or from the composition changing the phase of the composition. For example, the present methods provide cooling by absorbing heat from a fluid or article, preferably by evaporating the present refrigerant composition in the vicinity of the body or fluid to be cooled to produce vapor comprising the present composition. Preferably the methods include the further step of compressing the refrigerant vapor, usually with a compressor or similar equipment to produce vapor of the present composition at a relatively elevated pressure. Generally, the step of compressing the vapor results in the addition of heat to the vapor, thus causing an increase in the temperature of the relatively high pressure vapor. Preferably, the present methods include removing from this relatively high temperature, high pressure vapor at least a portion of the heat added by the evaporation and compression steps. The heat removal step preferably includes condensing the high temperature, high pressure vapor while the vapor is in a relatively high pressure condition to produce a relatively high pressure liquid comprising a composition of the present invention. This relatively high pressure liquid preferably then undergoes a nominally isoenthalpic reduction in pressure to produce a relatively low temperature, low pressure liquid. In such embodiments, it is this reduced temperature refrigerant liquid which is then vaporized by heat transferred from the body or fluid to be cooled. In another process embodiment of the invention, the compositions of the invention may be used in a method for producing heating which comprises condensing a refrigerant comprising the compositions in the vicinity of a liquid or body to be heated. In yet another process embodiment, the compositions may be used to collect sensible heat at one place in the vicinity of the body to be cooled and then transported to another place, to the vicinity of a body to be heated, where it gives up the sensible heat previously collected. For compatiblizing compositions of the present invention, the fluorinated ether compounds are present in an amount that is at least about 25% by weight, and even more preferably at least about 50% by weight of the overall composition.

According to another aspect of the invention, a method is provided for reducing the flammability of fluids by adding a compound or composition of the present invention to said fluid. The flammability associated with any of a wide range of otherwise flammable fluids may be reduced according to the present invention. For example, the flammability associated with fluids such as ethylene oxide, flammable hydrofluorocarbons and hydrocarbons, including: HFC-365 (pentafluorobutane), hexane, octane, and the like can be reduced according to the present invention. For the purposes of the present invention, a flammable fluid may be any fluid exhibiting flammability ranges in air as measured via any standard conventional test method, such as ASTM E-681, and the like. Any suitable amounts of the present compounds or compositions may be added to reduce flammability of a fluid according to the present invention. As will be recognized by those of skill in the art, the amount added will depend, at least in part, on the degree to which the subject fluid is flammable and the degree to which it is desired to reduce the flammability thereof. In certain preferred embodiments, the amount of compound or composition added to the flammable fluid is effective to render the resulting fluid substantially non-flammable. For reducing flammability of compositions, the fluorinated ether compounds are present in an amount that is at least about 50 % by weight, and more preferably at least about 75 % by weight of the overall composition.

According to another aspect of the invention a method is provided of suppressing a flame by contacting a flame with a fluid comprising a compound or composition of the present invention. Any suitable methods for contacting the flame with the present composition may be used. For example, a composition of the present invention may be sprayed, poured, and the like onto the flame, or at least a portion of the flame may be immersqd in the composition. In light of the teachings herein, those of skill in the art will be readily able to adapt a variety of conventional apparatus and methods of flame suppression for use in the present invention. For suppressing a flame, the fluorinated ether compounds are present in an amount in a flame suppressing composition that is at least about 90 % by weight, and more preferably at least about 95 % by weight of the overall composition. Other ingredients may include carbon dioxide, fluorocarbons such as pentafluoropentane, heptafluoropropane, trifluoromethane, dichlorotrifluoroethane or perfluoroethylpropyl ketone, HFC-245fa, HFC-236fa or other such materials known to be used in fire suppression.

In another aspect of the invention, the fluorinated ethers may be employed as part of an anesthetic composition. In an anesthetic composition, the fluorinated ether is employed in an amount of from about 0.5 to about 20volume percent, preferably from about 1 to about 10 volume percent, and more preferably from about 1 to about 5 volume percent based on the overall composition. Other components non-exclusively include oxygen, air, or oxygen enriched air in amounts of from about 99.5 to about 80 volume percent, preferably from about 99 to about 90 volume percent, and more preferably from about 99 to about 95 volume percent based on the overall composition.

In another aspect of the invention, the fluorinated ethers may be employed as part of a microemulsion composition along wit a surfactant or cosurfactant. Many surfactants or cosurfactants are commercially available including fluorpalkyl compounds such as Zonyl ^®, and Fluorad ^® (FC-171) surfactants. In a typical microemulsion, the fluorinated ethers may be in the range of 2-50%; remaining components being water and surfactants. Ingredients for microemulsions comprising fluorinated ethers are further described in U.S patent 5,656, 201 which is incorporated herein by reference.

In another aspect of the invention, the fluorinated ethers may be employed as part of a blowing agent composition. Other components of a blowing agent composition non-exclusively include polyols, optionally with surfactants and catalysts. In a blowing agent composition, the fluorinated ether is employed in an amount of from about 2 parts by weight to about 50 parts by weight per 100 parts by weight of polyol, preferably from about 5 parts by weight to about 30 parts by weight per 100 parts by weight of polyol, and more preferably from about 10 parts by weight to about 25 parts by weight per 100 parts by weight of polyol based on the overall composition. The following non-limiting examples serve to illustrate the invention. It will be appreciated that variations in proportions will be apparent to those skilled in the art and are within the scope of the present invention. EXAMPLE 1

Preparation of CF jCFHCF2-O-CH₂CF?CH_zCF₃

To a stirred mixture of CF₃CH₂CF₂CH₂OH (16.45 g, 100 mmol), acetonitrile (200 mL) and Cs₂CO₃ (lg, 3.0 mmol), at 10 °C under nitrogen, was added CF₃CF=CF₂ (16.6 g, 116 mmol) drop-wise via a dry ice condenser. The addition took approximately lhour. The resultant reaction mixture was filtered, concentrated under reduced pressure, washed with water, dried (MgSO₄) and distilled at 85-90 °C to afford 25 g CF₃CFHCF₂-O-CH₂CF₂CH₂CF₃ as a colorless liquid. Spectral data are consistent with the structure: GC/MS (CI-Mode) m/e at 315 for (M⁺+l) (M = C₇H₅F„O) ¹⁹F NMR (CDC1₃) δ = -62.7 (m, 3F), -75.9 (m, 3F), -81.7(dm, IF), -84.0(dm, IF), -103.8 (m, 2F), -212.6(m. IF) ppm; 1H NMR (CDC1₃) δ = 4.9 (dm, 1H), 4.2 (t, 2H), 2.8(qt, 2H) ppm. By product formed (~ 2-8%) is CF₃CF=CF-O-CH₂CF₂CH₂CF₃ (cis/trans); GC/MS (CI-Mode) m/e at 275 for (M⁺+l).

EXAMPLE 2

The procedure of Example 1 is duplicated, except that an equivalent amount of the fluoroolefins CF₃CH=CF₂, CF₃CH=CFH, CF₃CF=CHF, and CF₃CF=CH₂ are treated with CF₃CH₂CF₂CH₂OH. The following hydrofluoroethers are obtained: CF₃CH₂CF₂-O-CH₂CF₂CH₂CF₃ CF₃CH₂CFH-O-CH₂CF₂CH₂CF₃ CF₃CFHCFH-O-CH₂CF₂CH₂CF₃ CF₃CFHCH₂-O-CH₂CF₂CH₂CF₃ EXAMPLE 3

Preparation of CF3CH9CF7-O-CH2CFHCH9CF.

To a stirred mixture of CF₃CH₂CFHCH₂OH (14.5 g, 100 mmol), acetonitrile (200 mL) and Cs₂CO₃ (lg, 3.0 mmol), at ~ 5 to 10 °C under nitrogen, was added

CF₃CH=CF₂ (HFC 1225) (14.5g, 110 mmol ) drop-wise via a dry ice condenser. The addition took approximately lhour. The resultant reaction mixture was filtered, concentrated under reduced pressure and distilled at 80-85 °C to afford 12,5 g of CF₃CH₂CF₂-O-CH₂CFHCH₂CF₃ as a colorless liquid. Spectral data were consistent with structure: GC/MS (El mode) m/e at 278 for (M⁺) (M = C₇H₇F₁₀O). By product observed (- 10-20%) is CF₃CH=CF-O- CH₂CFHCH₂CF₃(cis and trans); GC/MS (CI-Mode) m/e at 258 for (M⁺+l).

EXAMPLE 4

The procedure of Example 1 is duplicated, except an equivalent amount of the fluoroolefin CF₃CF=CF₂, CF₃CH=CFH, CF₃CF=CHF, and CF₃CF=CH₂ is treated with CF₃CH₂CFHCH₂OH. The following hydrofluoroethers are obtained: CF₃CFHCF₂-O-CH₂CFHCH₂CF₃ CF₃CH₂CFH-O-CH₂CFHCH₂CF₃ CF₃CFHCFH-O-CH₂CFHCH₂CF₃ CF₃CFHCH₂-O-CH₂CFHCH₂CF₃ CF₃CH₂CF₂-O-CH₂CF₂CH₂CF₃

EXAMPLE 5

Preparation of CF^Q CF^OCHpCF^

Into a 250 mL Fisher Porter tube was added CF₃CH₂OH (13 mL) and Cs₂CO₃ (0.46 g). The reactor was partially evacuated and to the stirred mixture of CF₃CH₂OH and Cs₂CO₃ was added CF₃CH=CF₂ (HFC 1225). A pressure of approximately 15 psi was maintained. Gradual consumption of CF₃CH=CF₂ was observed. After overnight stirring (approximately 15 hours) GC analysis indicated the formation of CF₃CH₂CF₂OCH₂CF₃ as the major product. GC/MS (El-Mode) m/e at 232 for M⁺ (C₅H₄F₈O). In this reaction CF₃CH₂OH also serves as the solvent.

EXAMPLE 6

Solubility of Cyanine Dyes in Fluorinated Ethers

Solubility of DVD dyes in the prepared fluorinated ethers was carried out. A coating solvent was prepared by blending in a vessel a measured volume of a liquid carrier (fluorinated ether) and as a surface tension reducing agent 1,1,1,3,3- pentafluoropropane (HFC-245fa) to give a solvent having the constituent volumetric ratios show in the Table below. Solubility was determined by adding dye powder slowly to a weighed 100 ml aliquot of the coating solvent in a vessel. The solvent was stirred to dissolve the dye.. When no more dye would dissolve, the dye addition was stopped and the solvent reweighed to determine the amount of dye that had been dissolved in the solvent. The data in the Table show that even with high levels of the fluorocarbon surface tension reducing agent present, adequate amounts of dye to prepare dye layers can be dissolved in a coating solvent of the present invention. Solubility of cyanine dyes ranged from 1-5 wt%. Examples are given below:

Table

* Cyanine dyes SO619 from FEW Chemicals ** Cyanine dyes SO627 from FEW Chemicals This example shows the increased solubility of cyanine dyes in CF₃CFHCF₂-O-CH₂CF₂CH₂CF₃,

While the present invention has been particularly shown and described with reference to preferred embodiments, it will be readily appreciated by those of ordinary skill in the art that various changes and modifications may be made without departing from the spirit and scope of the invention. It is intended that the claims be interpreted to cover the disclosed embodiment, those alternatives which have been discussed above and all equivalents thereto.

Claims

What is claimed is:

1. A fluorinated ether of the formula R-O-Rj wherein R = CF₃-CXH-CYZ wherein each of X, Y and Z are independently H or a halogen; and Rj is a Ci to Ci₆ alkyl group or a halogen substituted to Cj₆ alkyl group. ^'

2. The fluorinated ether of claim 1 wherein the halogen comprises fluorine.

3. The fluorinated ether of claim 1 wherein R is selected from the group consisting of CF₃CH₂CF_2s CF₃CH₂CHF, CF₃CFHCH₂, CF₃CH₂-CH₂, CF₃CFH- CFH, CF₃CBrH-CFH, CF₃CFHCFH, CF₃CH₂CHC1, and CF₃CC1HCC1H.

4. The fluorinated ether of claim 1 wherein Ri is selected from the group consisting of CH₃(CH₂)_n, CF₃CH₂, (CF₃)₂CH, CF₃CH₂CF₂CH₂ , CF₃CH₂CFHCH₂, CF₃CBrHCF CH_2> CF₃CC1HCH₂CH₂, CF₂CH₂CHC1CH₂, CF₃CF₂CH₂OH,

CF₃CHC1CF₂CH₂ , CF₃CHC1CHC1CH₂, CF₃CH₂CF₂, CF₃CH₂CFH, CF₃CFHCF₂, CF₃(CF₂)_nCH₂, and CF₃(CF₂)_nCH₂CH₂ wherein n = 1-13.

5. The fluorinated ether of claim 1 which is selected from the group consisting of CF₃CH₂CF₂-O-R_I; CF₃CFHCHF-O-R₁, CF₃CH₂CFH-O-Rι_, CF₃CFHCH₂-O-R_1;

CF₃CH₂CHCl-O-Rι_; CF₃CHClCHCl-O-R_lj CF₃CHBrCH₂O-Rι wherein Rt is selected from the group consisting of CH₃(CH₂)_n, CF₃CH₂, (CF₃)₂CH, CF₃CH₂CF₂CH_{2 ,} CF₃CH₂CFHCH_2, CF₃CBrHCF₂CH_2, CF₃CC1HCH₂CH₂, CF₃CH₂CF₂, CF₃CH₂CFH, CF₃CFHCF₂, CF₃(CF₂)„CH₂, and CF₃(CF₂)_nCH₂CH₂ wherein n = 1-13.

6. The fluorinated ether of claim 1 which is selected from the group consisting of CF₃CH₂CF₂-O-CH₂CF₃; CF₃CH₂CFH-O-CH₂CF₃; CF₃CH₂CF₂-O-CH(CF₃)₂; CF₃CH₂CFH-O-CH(CF₃)₂; CF₃CH₂CF₂-O-C(CF₃)₃; CF₃CH₂CFH-O-C(CF₃)₃; CF₃CFHCF₂-O-CH₂CF₂CH₂CF₃; CF₃CH₂CF₂-O-CH₂CF₂CH₂CF₃; CF₃CFHCFH-O-CH₂CF₂CH₂CF₃; CF₃CFHCF₂-O-CH₂CF₂CH₂CF₃ ; CF₃CFHCF₂-O-CH₂CF₂CH₂CF₃.

7. A method for preparing a fluorinated ether of the formula R-O-Rj wherein R = CF₃-CXH-CYZ wherein each of X, Y and Z are independently H or a halogen; and Ri is a Ci to C₁₆ alkyl group or a halogen substituted Ci to C₁₆ alkyl group, the method comprising reacting a fluoroolefin of the formula CF₃CX=CYZ with an alcohol of the formula RjOH, provided the alcohol does not contain a -CF₂OH group, in a solvent and in the presence of base.

8. The method of claim 7 wherein the halogen comprises fluorine.

9. The method of claim 7 wherein the alcohol RiOH is fluorine containing.

10. The method of claim 7 wherein the fluoroolefin is selected from the group consisting of CF₃CF=CF_2, CF₃CH=CF₂, CF₃CH=CFH, CF₃CH=CFH (HFC 1234), CF₃CF=CH₂, CF₃CF=CFH, CF₃-CF=CFBr, CF₃-CH=CHC1, CF₃-CC1=CHC1, and CF₃CBr=CF₂.

11. The method of claim 7 wherein the alcohol RjOH comprises an Rj_. selected from the group consisting of CH₃(CH₂)„, CF₃CH₂, (CF₃)₂CH, CF₃CH₂CF₂CH_{2 ,} CF₃CH₂CFHCH_2j CF₃CBrHCF₂CH_2; CF₃CClHCH₂CH_2ι CF₂CH₂CHClCH₂, CF₃CF₂CH₂OH, CF₃CHC1CF₂CH₂ , CF₃CHC1CHC1CH₂, CF₃CH₂CF₂, CF₃CH₂CFH, CF₃CFHCF₂, CF₃(CF₂)_nCH₂, and CF₃(CF₂)_nCH₂CH₂ wherein n = 1-13.

12. The method of claim 7 wherein the base is selected from the group consisting of alkali carbonates, alkaline metal carbonates, ammonium carbonates, alkali hydroxides alkaline metal hydroxides, ammonium hydroxide and organic bases.

13. The method of claim 7 wherein the base is present in a catalytic amount.

14. The method of claim 7 wherein the base is present in an amount of from about 0.01 to 20 mol % based on the amount of the alcohol.

15. The method of claim 7 wherein the solvent comprises an aprotic solvent.

16. The method of claim 7 wherein the aprotic solvent is selected from the group consisting of acetonitrile, benzonitrile, dimethylformamide, dimethylsulfoxide and combinations thereof.

17. The method of claim 7 which is conducted at a temperature of from about -10 °C. to about 150 °C.

18. The method of claim 7 further comprising the subsequent step of separating and/or purifying the fluorinated ether.

19. The method of claim 7 further comprising the subsequent step of separating and/or purifying the fluorinated ether by at least one step selected from the group consisting of filtration, extraction and distillation.

20. An anesthetic composition, refrigerant composition, cleaning composition, dry cleaning composition, blowing agent composition, flame retardant composition, heat transfer composition, solvent composition or microemulsion composition comprising the fluorinated ether of claim 1.

21. A method for reducing the flammability of a fluid comprising adding to said fluid the fluorinated ether of claim 1.

22. A method for suppressing a flame comprising contacting a flame with a fluid fluorinated ether of claim 1.