# US 7,612,242 B2 · Process for preparing fluorohalogenethers

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- Number: US 7,612,242 B2
- Document ID: US7612242B2
- Status: Granted
- Kind: B2
- Application number: 11/634,145
- Filed: 2006-12-06
- Published: 2007-06-28
- Granted: 2009-11-03
- Earliest claimed: 2005-12-22
- Assignees: Solvay Solexis S.p.A.
- Inventors: Vito Tortelli; Pierangelo Calini; Alberto Zompatori; Emanuela Antenucci
- Web page: https://patentgrep.com/patent/US7612242B2

## CPC

- C07C 41/06: by addition of organic compounds only
- C07C 41/22: by introduction of halogens; by substitution of halogen atoms by other halogen atoms
- C07C 41/24: by elimination of halogens, e.g. elimination of HCl
- C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS

## Abstract

A process for preparing fluorovinylethers having general formula: RfO—CF═CF2 (IA) wherein Rf is a fluorinated or perfluorinated alkyl or cycloalkyl substituent; comprising the following reaction steps: 1) reaction of a hypofluorite; 2) dehalogenation or dehydrohalogenation of the fluorohalogenethers obtained in step 1) and obtainment of vinyl ethers; 3) fluorination with fluorine of the vinyl ethers and obtainment of fluorohalogenethers; and 4) dehydrohalogenation of the fluorohalogenethers and obtainment of the fluorovinylethers of formula (IV). The compounds of formula (IA) can be used, for example, in the preparation of various polymers, such as fluorinated elastomers and fluorinated thermoprocessable semicrystalline polymers.

## Claims

### Claim 1

A process for preparing perfluoroalkylvinylethers having the general formula:
RfO—CF═CF2 (IA)
wherein Rf is a C1-C3, perfluorinated substituent;
comprising the following steps:
1) reaction of a hypofluorite of formula RfOF, wherein Rf is as above, with an olefin selected from the group consisting of: trichloroethylene; 1,2-dichloroethylene; and 1,1-dichloroethylene;
2) dehalogenation or dehydrohalogenation of the fluorohalogenethers obtained in step 1) and obtainment of vinyl ethers of formula:
RfO—CYI═CYIIF (IV)
wherein YI and YII are selected from the group consisting of H, Cl, and Br with the proviso that one of YI and YII is H;
3) fluorination with fluorine of the vinyl ethers (IV) and obtainment of fluorohalogenethers of formula:
RfO—CFY1—CF2YII (I)
wherein YI, YII and Rf are as above; and
4) dehydrohalogenation of the fluorohalogenethers of formula (I) and obtainment of vinyl ethers of formula:
RfO—CF═CF2 (IA).

### Claim 2 (depends on 1)

A process according to claim 1, wherein step 1) is carried out in liquid phase at temperatures from −130° C. to 0° C., optionally in the presence of organic solvents.

### Claim 3 (depends on 1)

A process according to claim 1 wherein in step 2), the dehalogenation is carried out with transition metals or with metal couples, in the presence of solvents selected from the group consisting of: hydrogenated protics, hydrogenated ethers, and dipolar aprotic solvents.

### Claim 4 (depends on 1)

A process according to claim 1, wherein in step 2) the dehydrohalogenation is carried out with an inorganic or an organic base.

### Claim 5 (depends on 4)

A process according to claim 4, wherein the dehydrohalogenation is carried out in the presence of a quaternary ammonium or phosphonium salt selected from the group consisting of: ammonium tetrabutyl, ammonium trioctyl benzyl, phosphonium tetrabutyl and phosphonium trioctyl benzyl.

### Claim 6 (depends on 1)

A process according to claim 1, wherein step 2) occurs at temperatures in the range of 0°-150° C.

### Claim 7 (depends on 1)

A process according to claim 1, wherein in step 3) the reaction is carried out by addition of gaseous fluorine, optionally in the presence of an inert diluent, to the compounds of formula (IV), liquid at the reaction temperature, by optionally using a solvent or a mixture of inert solvents being at the liquid state under the conditions in which step 3) is carried out.

### Claim 8 (depends on 1)

A process according to claim 1, wherein step 3) occurs temperatures between −120° C. and 0° C.

### Claim 9 (depends on 1)

A process according to claim 1, wherein in steps 1) and 3), solvents may optionally be used, wherein the solvents are selected from the group consisting of: (per)fluoropolyethers, (per)fluoroalkanes, HFC, HCFC, CFC, perfluoroamines, hydrofluoroethers or hydrofluoropolyethers, and mixtures thereof.

### Claim 10 (depends on 1)

A process according to claim 1, wherein in step 4) the dehydrohalogenation is carried out with an inorganic or organic base.

### Claim 11 (depends on 10)

A process according to claim 10, wherein the dehydrohalogenation is carried out in the presence of a quaternary ammonium or phosphonium salt selected from the group consisting of: ammonium tetrabutyl, ammonium trioctyl benzyl, phosphonium tetrabutyl and phosphonium trioctyl benzyl.

### Claim 12 (depends on 1)

A process according to claim 1, wherein step 4) occurs at temperatures in the range 0°-150° C.

### Claim 13 (depends on 1)

A process according to claim 1, carried out in a discontinuous, semicontinuous or continuous way.