Fluorinated alkoxy vinyl ethers and methods for preparing fluorinated alkoxy vinyl ethers

Abstract

To provide methods for treating a surface using specific alkoxyvinyl ethers.SOLUTION: A method for treating a surface comprises: providing a surface; and contacting the surface with a treatment composition. The surface includes a treatable material deposited thereon. The treatment composition comprises the alkoxyvinyl ether having one of following chemical structures: CF3C(OCH3)=CHC2F5, CF3C(OCH2CF3)=CHC2F5, CF3C(OC2H5)=CHC2F5, CF3C(OC3H7)=CHC2F5, C2F5C(OCH3)=CHC3F7, and C3F7C(OCH3)=CHC2F5.SELECTED DRAWING: None

Description

[Technical Field]

[0001] (CROSS-REFERENCE TO RELATED APPLICATIONS) This application claims the benefit of U.S. Patent Application No. 62 / 745,733, filed October 15, 2018. The disclosure of U.S. Patent Application No. 62 / 745,733 is incorporated herein by reference.

[0002] FIELD OF THE INVENTION The present invention is directed to alkoxy vinyl ethers and methods for preparing alkoxy vinyl ethers. More particularly, the present invention is directed to fluorinated alkoxy vinyl ethers and methods for preparing fluorinated alkoxy vinyl ethers. [Background technology]

[0003] General structure R f C(OCH3)=CFR f Certain fluorinated materials are known, and such materials can be prepared by the reaction of alcohols with various perfluoroolefins, such as F-pentene-2 ​​(known as a commercial intermediate) or F-heptene (known as a waste stream component to form other materials). As an example, the reaction product of F-heptene with methanol (HFX-110) has been proposed for use as a solvent with low toxicity and low global warming potential.

[0004] However, to date, the general structure R f C(OR)=CHR f '(In the formula, R f Fluorinated species having the general structure R f C(OR)=CHR f There has been no previous disclosure of a basic alcohol reaction route to prepare fluorinated species having the formula: 'wherein R is an alkyl functionality.' [Prior art documents] [Patent documents]

[0005] [Patent Document 1] U.S. Patent Application No. 62 / 745733 Summary of the Invention [Means for solving the problem]

[0006] In an exemplary embodiment, the alkoxy vinyl ether has the chemical structure R f C(OR)=CHR f '[where R f is an at least partially fluorinated functional group having at least one carbon atom, and R f ' is an at least partially fluorinated functional group having at least two carbon atoms, and R is a functional group.

[0007] In another exemplary embodiment, the method for preparing an alkoxy vinyl ether comprises: f CFHCFHR f '+KOH / ROH→R f C(OR)=CHR f '[where R f is a perfluorofunctional group, and R f ' is a perfluoro functional group and R is an alkyl functional group.

[0008] In another exemplary embodiment, the method for preparing an alkoxy vinyl ether comprises: f CF=CHR f '+KOH / ROH→R f C(OR)=CHR f '[where R f is a perfluorofunctional group, and R f ' is a perfluoro functional group and R is an alkyl functional group.

[0009] Another embodiment of the present invention is R f is a perfluorofunctional group having at least one carbon atom, R f' is a perfluorofunctional group having at least two carbon atoms, Any combination of the foregoing alkoxy vinyl ethers wherein R is a functional group having at least one carbon atom.

[0010] Another embodiment of the present invention is R f is a perfluoroalkyl functional group; R f ' is a perfluoroalkyl functional group having at least two carbon atoms, Any combination of the foregoing alkoxy vinyl ethers wherein R is an alkyl functional group.

[0011] Another embodiment of the present invention is R f But C 1-12 is a perfluoroalkyl functional group, R f ', C 2-12 is a perfluoroalkyl functional group, R is C 1-12 Any combination of the aforementioned alkoxy vinyl ethers is alkyl functional.

[0012] Another embodiment of the present invention is R f is selected from the group consisting of CF3, C2F5, n-C3F7, iso-C3F7, n-C4F9, sec-C4F9, iso-C4F9, and tert-C4F9; R f is selected from the group consisting of C2F5, n-C3F7, iso-C3F7, n-C4F9, sec-C4F9, iso-C4F9, and tert-C4F9; Any combination of the foregoing alkoxy vinyl ethers wherein R is selected from the group consisting of CH3, C2H5, n-C3H7, iso-C3H7, n-C4H9, sec-C4H9, iso-C4H9, and tert-C4H9.

[0013] Another embodiment of the present invention is R fis a partially fluorinated functional group having at least one carbon atom, R f and R is a functional group having at least 1 carbon atom.

[0014] Another embodiment of the present invention is R f is a perfluorofunctional group having at least one carbon atom, R f and R is a functional group having at least 1 carbon atom.

[0015] Another embodiment of the present invention is R f is a partially fluorinated functional group having at least one carbon atom, R f ' is a perfluorofunctional group having at least two carbon atoms, Any combination of the foregoing alkoxy vinyl ethers wherein R is a functional group having at least one carbon atom.

[0016] Another embodiment of the present invention is R f is selected from the group consisting of CF3, CF2H, C2F5, C2F4H, n-C3F7, n-C3F6H, iso-C3F7, iso-C3F6H, n-C4F9, n-C4F8H, sec-C4F9, sec-C4F8H, iso-C4F9, iso-C4F8H, and tert-C4F9, tert-C4F8H; R fand R is selected from the group consisting of CH3, C2H5, n-C3H7, iso-C3H7, n-C3F6H, iso-C3F7, iso-C3F6H, n-C4F9, n-C4F8H, sec-C4F9, sec-C4F8H, iso-C4F9, iso-C4F8H, and tert-C4F9, tert-C4F8H.

[0017] Another embodiment of the present invention is R f and R f ' and ' are the same.

[0018] Another embodiment of the present invention is R f and R f ' relates to any combination of the preceding embodiments, where ' is different from '.

[0019] Another embodiment of the present invention relates to any combination of the preceding embodiments, wherein the alkoxy vinyl ether is the E isomer.

[0020] Another embodiment of the present invention relates to any combination of the preceding embodiments, wherein the alkoxy vinyl ether is the Z isomer.

[0021] Another embodiment of the present invention relates to any combination of the preceding embodiments, wherein the alkoxy vinyl ether is a mixture of E and Z isomers.

[0022] Another embodiment of the present invention relates to any combination of the preceding embodiments, wherein the chemical structure is CF3C(OCH3)=CHC2F5.

[0023] Another embodiment of the present invention relates to any combination of the preceding embodiments, wherein the chemical structure is the chemical structure CF3C(OC2H5)=CHC2F5.

[0024] Another embodiment of the present invention relates to any combination of the preceding embodiments, wherein the chemical structure is CF3C(OC3H7)=CHC2F5.

[0025] Another embodiment of the present invention relates to any combination of the preceding embodiments, wherein the chemical structure is C2F5C(OCH3)=CHC3F7.

[0026] One embodiment of the present invention is a method for preparing an alkoxy vinyl ether, comprising: R f CFHCFHR f ' + base / ROH → R f C(OR)=CHR f ' [In the formula, R f is a perfluorofunctional group, R f ' is a perfluorofunctional group, R is an alkyl functional group.

[0027] Another embodiment of the present invention is a process for preparing an alkoxy vinyl ether, comprising the steps of: f CF=CHR f ' + base / ROH → R f C(OR)=CHR f ' [In the formula, R f is a perfluorofunctional group, R f ' is a perfluorofunctional group, R is an alkyl functional group.

[0028] One embodiment of the present invention relates to a solvent comprising any combination of the aforementioned alkoxy vinyl ether and at least one member selected from the group consisting of an alcohol, an ether, tetrahydrofuran (THF), an amide, or an aromatic solvent.

[0029] Another embodiment of the present invention is any combination of the foregoing alkoxy vinyl ethers; at least one solvent comprising at least one of an alcohol, an ether, tetrahydrofuran (THF), an amide, or an aromatic solvent; and at least one base comprising at least one of KOH, NaOH, LiOH, Ca(OH)2, a tertiary amine, or an alkoxide of an alkali metal ROM (M=Li, Na, K, Cs).

[0030] Another embodiment of the present invention is a process for transferring heat, comprising: Providing goods; contacting the article with a heat transfer medium; The heat transfer medium comprises any combination of the foregoing alkoxy vinyl ethers.

[0031] Another embodiment of the present invention relates to the aforementioned process, wherein the alkoxy vinyl ether has a boiling point of from about 72°C to about 81°C.

[0032] Another embodiment of the present invention is a process for treating a surface, comprising: Providing a surface; contacting the surface with a treatment composition; the surface includes a treatable material deposited thereon; The treating composition comprises any of the aforementioned combinations of alkoxy vinyl ethers.

[0033] Another embodiment of the present invention relates to the aforementioned process, wherein the treating composition substantially dissolves the treatable material.

[0034] Another embodiment of the present invention is a process for forming a composition comprising: Providing a solute; contacting the solute with a solvent; The solvent comprises any combination of the aforementioned alkoxy vinyl ethers.

[0035] Another embodiment of the present invention is a process for providing electrical insulation, comprising: providing a first charged surface; providing a second charged surface; contacting the first charged surface and the second charged surface with a dielectric composition; The dielectric composition comprises any combination of the aforementioned alkoxy vinyl ethers.

[0036] Another embodiment of the present invention relates to the aforementioned process, wherein the dielectric composition forms a continuous pathway between the first charged surface and the second charged surface.

[0037] The various embodiments of the invention can be used alone or in combination with each other. Other features and advantages of the present invention will be apparent from the following more detailed description of the preferred embodiment, taken in conjunction with the accompanying drawings which illustrate, by way of example, the principles of the invention. DETAILED DESCRIPTION OF THE INVENTION

[0038] Exemplary fluorinated alkoxy vinyl ethers and methods for preparing fluorinated alkoxy vinyl ethers are provided. Embodiments of the present disclosure have advantageous solvation properties, advantageous boiling point ranges, advantageous degreasing properties, advantageous heat transfer properties, reduced flammability, reduced atmospheric lifetime, increased polarity, or a combination thereof, compared to compositions of matter and methods that do not utilize one or more of the features disclosed herein.

[0039] In some embodiments, alkoxy vinyl ethers may find useful applications as cleaning or degreasing agents, heat transfer media, solvents, and / or dielectrics.

[0040] In one embodiment, the alkoxy vinyl ether has the following chemical structure: R f C(OR)=CHR f '

[0041] Rf includes, but is not limited to, a partially fluorinated functional group having at least one carbon atom, a perfluorofunctional group having at least one carbon atom, a partially fluorinated alkyl group, a perfluoroalkyl group, C 1-12 partially fluorinated alkyl functional groups, C 1-12 The functional group may be a partially fluorinated or perfluoro functional group, including perfluoroalkyl functional groups, CF3, CF2H, C2F5, C2F4H, n-C3F7, n-C3F6H, iso-C3F7, iso-C3F6H, n-C4F9, n-C4F8H, sec-C4F9, sec-C4F8H, iso-C4F9, iso-C4F8H, tert-C4F9, or tert-C4F8H.

[0042] R f ' includes, but is not limited to, a partially fluorinated functional group having at least two carbon atoms, a perfluorofunctional group having at least two carbon atoms, a partially fluorinated alkyl group having at least two carbon atoms, a perfluoroalkyl group having at least two carbon atoms, C 2-12 partially fluorinated alkyl functional groups, C 2-12 The functional group may be a partially fluorinated or perfluoro functional group, including perfluoroalkyl functional groups, C2F5, C2F4H, n-C3F7, n-C3F6H, iso-C3F7, iso-C3F6H, n-C4F9, n-C4F8H, sec-C4F9, sec-C4F8H, iso-C4F9, iso-C4F8H, tert-C4F9, or tert-C4F8H.

[0043] R may be, but is not limited to, a functional group having at least one carbon atom, an alkyl functional group, a C 1-12 Alkyl functional groups are functional groups that may be CH3, C2H5, n-C3H7, iso-C3H7, n-C4H9, sec-C4H9, iso-C4H9, or tert-C4H9.

[0044] The alkoxy vinyl ethers are those having the R, R f , and Rf R may include any suitable combination of the particular species of f and R f ' may be the same as or different from each other.

[0045] In one embodiment, R f is an at least partially fluorinated functional group having at least one carbon atom, and R f ' is an at least partially fluorinated functional group having at least two carbon atoms and R is a functional group.

[0046] In another embodiment, R f is a perfluorofunctional group having at least one carbon atom, and R f ' is a perfluorofunctional group having at least two carbon atoms, and R is a functional group having at least one carbon atom.

[0047] In yet another embodiment, R f is a perfluoroalkyl functional group having at least one carbon atom, and R f ' is a perfluoroalkyl functional group having at least two carbon atoms and R is an alkyl functional group.

[0048] In yet another embodiment, R f is C 1-12 is a perfluoroalkyl functional group, R f ' is C 2-12 is a perfluoroalkyl functional group, and R is C 1-12 It is an alkyl functional group.

[0049] In another embodiment, R f is selected from the group consisting of CF3, C2F5, n-C3F7, iso-C3F7, n-C4F9, sec-C4F9, iso-C4F9, and tert-C4F9; R f' is selected from the group consisting of C2F5, n-C3F7, iso-C3F7, n-C4F9, sec-C4F9, iso-C4F9, and tert-C4F9, and R is selected from the group consisting of CH3, C2H5, n-C3H7, iso-C3H7, n-C4H9, sec-C4H9, iso-C4H9, and tert-C4H9.

[0050] In yet another embodiment, R f is a partially fluorinated functional group having at least one carbon atom, and R f ' is a partially fluorinated functional group having at least two carbon atoms and R is a functional group having at least one carbon atom.

[0051] In yet another embodiment, R f is a perfluorofunctional group having at least one carbon atom, and R f ' is a partially fluorinated functional group having at least two carbon atoms and R is a functional group having at least one carbon atom.

[0052] In another embodiment, R f is a partially fluorinated functional group having at least one carbon atom, and R f ' is a perfluorofunctional group having at least two carbon atoms, and R is a functional group having at least one carbon atom.

[0053] In yet another embodiment, R f is selected from the group consisting of CF3, CF2H, C2F5, C2F4H, n-C3F7, n-C3F6H, iso-C3F7, iso-C3F6H, n-C4F9, n-C4F8H, sec-C4F9, sec-C4F8H, iso-C4F9, iso-C4F8H, and tert-C4F9, tert-C4F8H; R fis selected from the group consisting of C2F5, C2F4H, n-C3F7, n-C3F6H, iso-C3F7, iso-C3F6H, n-C4F9, n-C4F8H, sec-C4F9, sec-C4F8H, iso-C4F9, iso-C4F8H, and tert-C4F9, tert-C4F8H; and R is selected from the group consisting of CH3, C2H5, n-C3H7, iso-C3H7, n-C4H9, sec-C4H9, iso-C4H9, and tert-C4H9.

[0054] The alkoxy vinyl ether may be the E isomer, the Z isomer, or a mixture of E and Z isomers.

[0055] The alkoxy vinyl ether may have any suitable chemical structure, including, but not limited to, CF3C(OCH3)=CHC2F5, CF3C(OC2H5)=CHC2F5, CF3C(OC3H7)=CHC2F5, and C2F5C(OCH3)=CHC3F7.

[0056] In one embodiment, the structure R f C(OR)=CHR f Alkoxy vinyl ethers having the structure R f C(OR)=CFR f The alkoxy vinyl ethers of the present invention may have a heat of combustion of less than about 2.1 kcal / g, such that the compounds of the present invention may have a low or non-flammable rating.

[0057] In one embodiment, the structure R f C(OR)=CHR f Alkoxy vinyl ethers having the structure R f C(OR)=CFR fThe alkoxy vinyl ethers of the present invention may have an atmospheric lifetime ranging from about 10 to 200 days, typically less than 100 days.

[0058] In one embodiment, the structure R f C(OR)=CHR f Alkoxy vinyl ethers having the structure R f C(OR)=CFR f The alkoxy vinyl ethers of the present invention have increased polarity compared to alkoxy vinyl ethers having a dipole moment of 2.5460 D, based on calculated dipole moments. As an example, based on calculated dipole moments, the dipole moment of CF3C(OCH3)=CHC2F5 is 2.5460 D, compared to the dipole moment of CF3C(OCH3)=CFC2F5 of 2.3965 D. The alkoxy vinyl ethers of the present invention can have a dipole moment of from about 2 to about 5 D, and in some cases from about 2 to about 3 D.

[0059] In one embodiment, a method for preparing an alkoxy vinyl ether comprises: R f CFHCFHR f ' + base / ROH → R f C(OR)=CHR f '

[0060] The method may comprise the following preliminary steps: R f CF=CFR f '+H2→R f CFHCFHR f '

[0061] In another embodiment, a method for preparing an alkoxy vinyl ether comprises: R f CF=CHR f ' + base / ROH → R f C(OR)=CHR f '

[0062] Regarding the process for preparing alkoxy vinyl ethers, R fincludes, but is not limited to, a partially fluorinated functional group having at least one carbon atom, a perfluorofunctional group having at least one carbon atom, a partially fluorinated alkyl group, a perfluoroalkyl group, C 1-12 partially fluorinated alkyl functional groups, C 1-12 R may be a partially fluorinated or perfluorofunctional group, including perfluoroalkyl functional groups, CF3, CF2H, C2F5, C2F4H, n-C3F7, n-C3F6H, iso-C3F7, iso-C3F6H, n-C4F9, n-C4F8H, sec-C4F9, sec-C4F8H, iso-C4F9, iso-C4F8H, tert-C4F9, or tert-C4F8H; f ' includes, but is not limited to, a partially fluorinated functional group having at least one carbon atom, a perfluorofunctional group having at least one carbon atom, a partially fluorinated alkyl group, a perfluoroalkyl group, C 1-12 partially fluorinated alkyl functional groups, C 1-12 R may be a partially fluorinated or perfluorofunctional group, including, but not limited to, a perfluoroalkyl functional group, CF3, CF2H, C2F5, C2F4H, n-C3F7, n-C3F6H, iso-C3F7, iso-C3F6H, n-C4F9, n-C4F8H, sec-C4F9, sec-C4F8H, iso-C4F9, iso-C4F8H, tert-C4F9, or tert-C4F8H; 1-12 The functional group may be an alkyl functional group, CH, C2H5, n-C3H7, iso-C3H7, n-C4H9, sec-C4H9, iso-C4H9, or tert-C4H9. f , and R f R may include any suitable combination of the particular species of f and R f ' may be the same or different from each other.

[0063] In one embodiment of the present invention, at least one alkyloxyl vinyl ether can interact or react with the removal of HF. In certain embodiments, the removal of HF can produce at least one alkyloxyl vinyl ether with an additional double bond. In one particular embodiment, at least one of the following groups can remove HF under certain reaction conditions: iso-CFH, n-CFH, sec-CFH, iso-CFH, or tert-CFH. Without being bound by theory or explanation, it is believed that an excess of base can facilitate HF removal.

[0064] The base may be any suitable base, including, but not limited to, KOH, NaOH, LiOH, Ca(OH), tertiary amines, and / or alkoxides of alkali metals ROM (M = Li, Na, K, Cs). The amount of base is at least 2 moles per mole of reactant. If desired, the amount of reactant may exceed the molar amount of base, and unreacted material (if any) may be recycled to improve selectivity.

[0065] In some embodiments, the reaction composition may further comprise any suitable solvent, including, but not limited to, alcohols, ethers (e.g., glyme, diethyl ether, methyl t-butyl ether), tetrahydrofuran (THF), amides, and / or aromatic solvents (e.g., benzene, toluene, xylene). The amount of solvent can range from about 0.5 to about 500 moles per mole of reactant, and in some cases, from about 5 to about 100 moles of solvent.

[0066] In some embodiments, the reaction may be carried out under phase transfer catalyst (PTC) conditions in the absence of a solvent. Suitable phase transfer catalysts include, but are not limited to, tetraalkylammonium salts, phosphonium salts, and / or crown ethers. The amount of catalyst may range from about 0.1 to about 50 mole percent, and in some cases, from about 5 to 15 mole percent, relative to the reactants.

[0067] In some embodiments, the reaction can be carried out at a temperature of at least -20°C, at least 0°C, at least 10°C, at least 20°C, at least 25°C, at least 30°C, at least 40°C, less than 110°C, less than 100°C, less than 90°C, less than 80°C, less than 70°C, less than 60°C, less than 50°C, and combinations thereof. The reaction pressure can be carried out at atmospheric pressure, or, if desired, the pressure can be greater than atmospheric pressure (e.g., from about 1 to about 100 atmospheres).

[0068] Alkoxy vinyl ethers can be useful in a variety of applications. In one embodiment, the alkoxy vinyl ethers can be used in accordance with conventional equipment and methods for transferring heat. The process can include providing an article and contacting the article with a heat transfer medium comprising the alkoxy vinyl ether. In some embodiments, the article can include an electrical device (e.g., a circuit board, a computer, a display, a semiconductor chip, or a transformer), a heat transfer surface (e.g., a heat sink), or an article of clothing (e.g., a bodysuit).

[0069] In another embodiment, the alkoxy vinyl ether may be used in a process for treating a surface. The process may include providing a surface having a treatable material deposited thereon and contacting the surface with a treatment composition comprising the alkoxy vinyl ether. In some embodiments, the treatment composition may substantially dissolve the treatable material. The alkoxy vinyl ethers of the present invention may be used in any suitable apparatus and method, although examples of such methods are disclosed in WO 2012 / 121749 and WO 2010 / 094019, the disclosures of which are incorporated herein by reference.

[0070] In another embodiment, the alkoxy vinyl ether may be used in a process for forming a composition. The process includes providing a solute and contacting the solute with a solvent containing the alkoxy vinyl ether. In some embodiments, the alkoxy vinyl ether can substantially dissolve the solute. With the exception of water, the alkoxy vinyl ethers of the present invention are miscible with conventional organic solvents and fluorinated solvents.

[0071] In one embodiment, the alkoxy vinyl ether may be used in conventional devices and in a process for providing electrical insulation. The process includes providing a first charged surface, providing a second charged surface, and contacting the first charged surface and the second charged surface with a dielectric composition comprising the alkoxy vinyl ether. In some embodiments, the dielectric composition forms a continuous pathway between the first charged surface and the second charged surface. In some embodiments, the first charged surface and the second charged surface may be substantially submerged in the dielectric composition.

[0072] The following examples are provided to illustrate certain aspects of the present invention and are not intended to limit the scope of the appended claims. [Example]

[0073] Example 1. Reaction of CF3CFHCFHC2F5(I) with CH3OH / KOH

[0074]

number

[0075] A solution of 240 g (4.27 mol) of KOH in 1400 mL of methanol was placed in a 3 L round-bottom flask equipped with a reflux condenser, thermocouple, addition funnel, and magnetic stir bar. The flask was immersed in an ice-cooled bath. Vertrel® XF (1,1,1,2,2,3,4,5,5,5-decafluoropentane, 1, 504 g, 2 mol) was added dropwise to the cooled solution (approximately 3 h), maintaining the internal temperature below 10 °C. The reaction mixture was allowed to warm to ambient temperature overnight. The next morning, the reaction mixture was washed in portions with copious amounts of ice water in a separatory funnel. The fluorescent layers were collected, combined, washed with a saturated solution of sodium bicarbonate (1 L x 2), dried over MgSO4, and filtered to yield 448 g of crude product. The crude product from three consecutive runs was combined (1085 g total) and distilled at atmospheric pressure using a 16-inch distillation column. The distillation data and fraction compositions are shown in Table 1.

[0076] [Table 1]

[0077] The combined fractions 8-13 (806 g total, 55% yield) were analyzed by NMR and shown to be an approximately 99% pure mixture of compounds IIa and IIb in an 85:15 ratio.

[0078] Compound IIa: 1 H NMR(CDCl3,J,Hz):3.98(3H,s),5.74(1H,q,8.4),ppm 19 F NMR(CDCl3,J,Hz):-55.34(3F,d,8.1),-83.23(3F,t,1.5),-119.34(2F,s)ppm

[0079] Compound IIb: 1 H NMR(CDCl3,δ,J,Hz):δ 3.92(3H,s),5.57(1H,t,13.3)ppm 19F NMR(CDCl3,J,Hz):-69.42(3F,s,),-85.78(3F,t,2.5),-110.70(2F,dt,13.8,2.5)ppm

[0080] Compound III: 1 H NMR(CDCl3,J,Hz):3.58(3H,s),5.62(1H,dd,28.1,15.6)ppm 19 F(CDCl3,J,Hz):-60.66(3F,m,9.9,4.5),-80.36(3F,d,8.8),-118.90(1F,tm,28.1),-127.24(1F,dd,28.1,15.3)ppm

[0081] Compound IV: 1 H NMR(CDCl3,J,Hz):2.84(2H,m),3.62(3H,q,1.2)ppm 19 F(CDCl3,J,Hz):-73.41(3F,d,9.9),-83.86(3F,t,4.5),-124.71(2F,A:B q,286.0),-130.45(1F,m,9.1)ppm

[0082] Compound V: 1 H NMR(CDCl3,J,Hz):3.41(6H,s),5.48(1H,d,33.2)ppm 19 F(CDCl3,J,Hz):-73.24(3F,d,9.3),-78.23(3F,d,6.8),-120.87(1F,dm,J d =33.2) ppm

[0083] Example 2. Reaction of CF3CFHCFHC2F5 with CF3CH2OH / KOH

[0084]

number

[0085] A 500 mL three-neck round-bottom flask was equipped with an addition funnel, thermocouple, and reflux condenser. Under a nitrogen blanket, 200 mL of 45 wt% KOH / water solution was added along with 2 g of catalyst—tetrabutylammonium bromide (TBAB, phase transfer catalyst). The mixture was cooled to approximately 5°C in an ice bath, and 50 g (approximately 36 mL, 0.5 mol) of trifluoroethanol was added dropwise over 30 min at 10°C. Following the addition of trifluoroethanol, 125 g (0.5 mol) of I was added slowly at 5–10°C (approximately 30 min). The reaction mixture was slowly brought to ambient temperature (approximately 4 h). After stirring at ambient temperature for an additional approximately 3 h, the reaction mixture was poured into 500 mL of water, and the porous layer was separated, washed with water, dried over MgSO4, filtered, and distilled using a Vigreux column. 87 g (56% yield) of the fraction (bp 95–98°C) was isolated. The fraction contained isomers VIa and VIb in a ratio of 72:25, respectively, and about 3% of other isomeric products.

[0086] Compound VIa: 1 H NMR(CDCl3,J,Hz):4.39(2H,q,7.7)5.98(1H,q,7.6,),ppm 19 F NMR(CDCl3,J,Hz):δ -57.32(3F,dq,7.5,1.7),-75.19(3F,t,7.8),-83.16(3F,d,0.7),-118.83(2F,s)ppm

[0087] Compound VIb: 1 H NMR(CDCl3,J,Hz):δ 5.80(1H,t,12.9),4.36(2H,q,7.9)ppm 19 F NMR(CDCl3,J,Hz):-69.20(3F,s),-75.1(3F,t,7.6),-85.54(3F,t,2.3),-112.23(2,F dm,12.9,2.1)ppm

[0088] Example 3. Reaction of CF3CFHCFHC2F5 with CH3CH2OH / KOH

[0089]

number

[0090] Using the procedure of Example 1 above, 126 g (0.5 mol) of I was added to a solution of 70 g (1.07 mol) of KOH in 400 mL of ethanol. The resulting crude product was isolated after washing the reaction mixture with water, drying, filtration, and distillation to give 94.4 g (73% yield) of material with a base temperature of 85-89°C, which was found to be a mixture of VIIa and VIIb in a 75:25 ratio and contained approximately 3% isomeric material (NMR and GC / MS).

[0091] Compound VIIa: 1 H NMR(CDCl3,J,Hz):1.36(3H,t,7.4),4.19(2H,q,7.4),5.74(1H,q,8.0)ppm 19 F NMR(CDCl3,J,Hz):-56.34(3F,dt,8.1,2.2),-83.18(3F,t,1.9),-119.23(2F,s)ppm

[0092] Compound VIIb: 1 H NMR(CDCl3,J,Hz):1.35(3H,t,7.3),4.14(2H,q,7.3),5.74(1H,t,12.8)ppm 19 F NMR(CDCl3,J,Hz):-69.58(3F,s),-85.81(3F,t,2.5),-111.27(2F,dm,J d =13.8) ppm

[0093] Example 4. Reaction of CF3CFHCFHC2F5 with (CH3)2CHOH / KOH

[0094]

number

[0095] Following the procedure described in Example 1 above, Compound I (126 g, 0.5 mol) was added to a solution of 70 g (1.07 mol) of KOH in 400 mL of isopropanol. The isolated crude product was distilled to obtain a 79 g (61% yield) fraction at bp 98-99°C. This fraction was found to contain a mixture of Vila and Vilab in an approximately 70:30 ratio, with 3% other isomeric material (NMR and GC / MS).

[0096] Compound VIIIa: 1 H NMR(CDCl3,J,Hz):1.31(6H,d,6.0),4.63(1H,quint.,6.0),5.76(1H,q,8.0,)ppm 19 F NMR((CDCl3,J,Hz):-57.54(3F,dt,8.0,2.1),-83.00(3F,t,1.9),-117.99(2F,s)ppm

[0097] Compound VIIIb: 1 H NMR(CDCl3,J,Hz):1.31(6H,d,6.0),4.56(1H,quint.,6.0),5.56(1H,t,13.0)ppm 19 F NMR(CDCl3,J,Hz):-68.38(3F,s),-85.57(3F,t,2.5),-111.55(2F,dq,13.0,2.2)ppm

[0098] Example 5. Reaction of C3F7CH=CFC2F5 / C3F7CF=CHC2F5 with MeOH / KOH

[0099]

number

[0100] The procedure described in Example 1 above was followed. Olefin (a mixture of C3F7CH=CFC2F5 and C3F7CF=CHC2F5 in an approximately 1:1 ratio) was added to a solution of KOH (20 g, 0.36 mol) in 300 mL of MeOH. 105 g of crude product was isolated and distilled to give a 61.5 g (46% yield) fraction between 107 and 110 °C. This fraction contained IXa, IXb, and a mixture of isomeric materials in a 45:40:15 ratio (GC / MS, NMR).

[0101] Major isomer (content in the mixture - 45%): 1 H NMR(CDCl3,J,Hz):3.96(3H,t,1.2),5.66(1H,t,14.5)ppm 19 F NMR(CDCl3,J,Hz):-81.14(3F,t,9.5),-85.02(3F,t,1.9),-109.06(2F,dm,J d =14.5),-116.39(2F,q,9.5),-127.05(2F,s)ppm

[0102] Minor isomer (content in the mixture - 40%): 1 H NMR(CDCl3,J,Hz):3.92(3H,t,1.2),5.73(1H,t,14.0)ppm 19 F NMR(CDCl3,J,Hz):δ -80.78(3F,t,9.2),-83.55(3F,m),-107.16(2F,quint.,11.0),-118.55(2F,s),-128.09(2F,s)ppm

[0103] While the present invention has been described with reference to preferred embodiments, those skilled in the art will recognize that various changes can be made and equivalents can be substituted for elements thereof without departing from the scope of the invention. In addition, many modifications can be made to adapt a particular situation or material to the teachings of the invention without departing from essential scope thereof. Therefore, it is not intended that the invention be limited to the particular embodiment disclosed as the best mode contemplated for carrying out this invention, but rather, the invention is intended to include all embodiments falling within the scope of the appended claims.

Claims

1. 1. A method for treating a surface, comprising: Providing a surface; contacting the surface with a treatment composition; the surface includes a treatable material deposited thereon; The method of claim 1, wherein the treatment composition comprises an alkoxy vinyl ether having one of the following chemical structures: CF 3 C(OCH 3 )=CHC 2 F 5 、 CF 3 C(OCH 2 CF 3 )=CHC 2 F 5 、 CF 3 C(OC 2 H 5 )=CHC 2 F 5 、 CF 3 C(OC 3 H 7 )=CHC 2 F 5 、 C 2 F 5 C(OCH 3 )=CHC 3 F 7 、 C 3 F 7 C (O) 3 )=CHHC 2 F 5 。

2. The method of claim 1 , wherein the treatment composition substantially dissolves the treatable material.

Images