Epoxide and fluorinated epoxide stabilizers for fluoroolefins

1. A composition comprising at least one fluoroolefin and an effective amount of a stabilizer comprising:

a. at least one compound selected from the group consisting of epoxides and fluorinated epoxides represented by Formula A, wherein each of R 2 through R 5 is H, alkyl of 1 to 6 carbon atoms or fluoroalkyl of 1 to 6 carbon atoms with the proviso that at least one of R 2 through R 5 is a fluoroalkyl group;

and

b. at least one butylated triphenylphosphorothionate.

2. The composition of claim 1 wherein:

the at least one butylated triphenylphosphorothionate is represented by formula B,

wherein each R is independently selected from H or tert-butyl.

3. The composition of claim 1 further comprising at least one refrigerant selected from the group consisting of fluoroolefins, hydrofluorocarbons, hydrocarbons, dimethyl ether, carbon dioxide, ammonia and mixtures thereof.

4. The composition of claim 1 further comprising a lubricant selected from the groups consisting of mineral oils, alkylbenzenes, polyalphaolefins, silicone oils, polyoxyalkylene glycol ethers, polyol esters, polyvinylethers and mixtures thereof.

5. The composition of claim 1 further comprising at least one additional stabilizer compound selected from the group consisting of phenols, phosphites, terpenes, terpenoids, and mixtures thereof.

6. The composition of claim 5 wherein:

a. the phenols are selected from the group consisting of 2,6-di-tert-butyl-4-methylphenol; 2,6-di-tert-butyl-4-ethylphenol; 2,4-dimethyl-6-tertbutylphenol; tocopherol; hydroquinone; t-butyl hydroquinone; 4,4′-thio-bis(2-methyl-6-tert-butylphenol); 4,4′-thiobis(3-methyl-6-tertbutylphenol); 2,2′-thiobis(4-methyl-6-tert-butylphenol); 4,4′-methylenebis(2,6-di-tert-butylphenol); 4,4′-bis(2,6-di-tert-butylphenol); 2,2′-methylenebis(4-ethyl-6-tertbutylphenol); 2,2′-methylenebis(4-methyl-6-tert-butylphenol); 4,4-butylidenebis(3-methyl-6-tert-butylphenol); 4,4-isopropylidenebis(2,6-di-tert-butylphenol); 2,2′-methyleenbis(4-methyl-6-nonylphenol); 2,2′-isobutylidenebis(4,6-dimethylphenol; 2,2′-methylenebis(4-methyl-6-cyclohexylphenol, 2,2′-methylenebis(4-ethyl-6-tert-butylphenol); butylated hydroxyl toluene (BHT); 2,6-di-tert-alpha-dimethylamino-p-cresol; 4,4-thiobis(6-tert-butyl-m-cresol; acylaminophenols; 2,6-di-tert-butyl-4(N,N′-dimethylaminomethylphenol); bis(3-methyl-4-hydroxy-5-tert-butylbenzyl)sulfide; bis(3,5-di-tert-butyl-4-hydroxybenzyl)sulfide and mixtures thereof;

b. the phosphites are selected from the group consisting of tris-(di-tert-butylphenyl)phosphite, di-n-octyl phosphite, iso-decyl diphenyl phosphite, and mixtures thereof;

c. the terpenes are selected from the group consisting of isoprene, myrcene, allo-cimene, beta-ocimene, terebene, d-limonene, retinal, pinene, menthol, geraniol, farnesol, phytol, Vitamin A, terpinene, delta-3-carene, terpinolene, phellandrene, fenchene, dipentene, lycopene, betacarotene, zeaxanthin, hepaxanthin, isotretinoin, and mixtures thereof; and

d. the terpenoids are selected from the group consisting of abietane, ambrosane, aristolane, atisane, beyerane, bisabolane, bornane, caryophyllane, cedrane, dammarane, drimane, eremophilane, eudesmane, fenchane, gammacerane, germacrane, gibbane, grayanotoxane, guaiane, himachalane, hopane, humulane, kaurane, labdane, lanostane, lupane, p-menthane, oleanane, ophiobolane, picrasane, pimarane, pinane, podocarpane, protostane, rosane, taxane, thujane, trichothecane, ursane; and mixtures thereof.

7. The composition of claim 1 wherein the epoxide or fluorinated epoxide is selected from the group consisting of 1,2-propylene oxide, 1,2-butylene oxide, butylphenylglycidy ether, pentylphenylglycidyl ether, hexylphenylglycidyl ether, heptylphenylglycidyl ether, octylphenylglycidyl ether, nonylphenylglycidyl ether, decylphenylglycidyl ether, glycidyl methylphenylether, 1,4-glycidyl phenyl diether, 4-methoxyphenylglycidyl ether, naphthyl glycidyl ether, 1,4-diglycidyl naphthyl diether, butylphenyl glycidyl ether, n-butyl glycidyl ether, isobutyl glycidyl ether, hexanediol diglycidyl ether, allyl glycidyl ether, polypropylene glycol diglycidyl ether, trifluoromethyloxirane, 1,1-bis(trifluoromethyl)oxirane, and mixtures thereof.

8. The composition of claim 1 wherein said fluoroolefin is at least one compound selected from the group consisting of:

(i) fluoroolefins of the formula E- or Z—R 1 CH═CHR 2 , wherein R 1 and R 2 are, independently, C 1 to C 6 perfluoroalkyl groups;

(ii) cyclic fluoroolefins of the formula cyclo-[CX═CY(CZW) n -], wherein X, Y, Z, and W, independently, are H or F, and n is an integer from 2 to 5; and

(iii) fluoroolefins selected from the group consisting of: 1,2,3,3,3-pentafluoro-1-propene (CHF═CFCF 3 ), 1,1,3,3,3-pentafluoro-1-propene (CF 2 ═CHCF 3 ), 1,1,2,3,3-pentafluoro-1-propene (CF 2 ═CFCHF 2 ), 1,2,3,3-tetrafluoro-1-propene (CHF═CFCHF 2 ), 2,3,3,3-tetrafluoro-1-propene (CH 2 ═CFCF 3 ), 1,3,3,3-tetrafluoro-1-propeneCHF═CHCF 3 ), 1,1,2,3-tetrafluoro-1-propene (CF 2 ═CFCH 2 F), 1,1,3,3-tetrafluoro-1-propene (CF 2 ═CHCHF 2 ), 1,2,3,3-tetrafluoro-1-propene (CHF═CFCHF 2 ), 3,3,3-trifluoro-1-propene (CH 2 ═CHCF 3 ), 2,3,3-trifluoro-1-propene (CHF 2 CF═CH 2 ); 1,1,2-trifluoro-1-propene (CH 3 CF═CF 2 ); 1,2,3-trifluoro-1-propene (CH 2 FCF═CF 2 ); 1,1,3-trifluoro-1-propene (CH 2 FCH═CF 2 ); 1,3,3-trifluoro-1-propene (CHF 2 CH═CHF); 1,1,1,2,3,4,4,4-octafluoro-2-butene (CF 3 CF═CFCF 3 ); 1,1,2,3,3,4,4,4-octafluoro-1-butene (CF 3 CF 2 CF═CF 2 ); 1,1,1,2,4,4,4-heptafluoro-2-butene (CF 3 CF═CHCF 3 ); 1,2,3,3,4,4,4-heptafluoro-1-butene (CHF═CFCF 2 CF 3 ); 1,1,1,2,3,4,4-heptafluoro-2-butene (CHF 2 CF═CFCF 3 ); 1,3,3,3-tetrafluoro-2-(trifluoromethyl)-1-propene ((CF 3 ) 2 C═CHF); 1,1,3,3,4,4,4-heptafluoro-1-butene (CF 2 ═CHCF 2 CF 3 ); 1,1,2,3,4,4,4-heptafluoro-1-butene (CF 2 ═CFCHFCF 3 ); 1,1,2,3,3,4,4-heptafluoro-1-butene (CF 2 ═CFCF 2 CHF 2 ); 2,3,3,4,4,4-hexafluoro-1-butene (CF 3 CF 2 CF═CH 2 ); 1,3,3,4,4,4-hexafluoro-1-butene (CHF═CHCF 2 CF 3 ); 1,2,3,4,4,4-hexafluoro-1-butene (CHF═CFCHFCF 3 ); 1,2,3,3,4,4-hexafluoro-1-butene (CHF═CFCF 2 CHF 2 ); 1,1,2,3,4,4-hexafluoro-2-butene (CHF 2 CF═CFCHF 2 ); 1,1,1,2,3,4-hexafluoro-2-butene (CH 2 FCF═CFCF 3 ); 1,1,1,2,4,4-hexafluoro-2-butene (CHF 2 CH═CFCF 3 ); 1,1,1,3,4,4-hexafluoro-2-butene (CF 3 CH═CFCHF 2 ); 1,1,2,3,3,4-hexafluoro-1-butene (CF 2 ═CFCF 2 CH 2 F); 1,1,2,3,4,4-hexafluoro-1-butene (CF 2 ═CFCHFCHF 2 ); 3,3,3-trifluoro-2-(trifluoromethyl)-1-propene (CH 2 ═C(CF 3 ) 2 ); 1,1,1,2,4-pentafluoro-2-butene (CH 2 FCH═CFCF 3 ); 1,1,1,3,4-pentafluoro-2-butene (CF 3 CH═CFCH 2 F); 3,3,4,4,4-pentafluoro-1-butene (CF 3 CF 2 CH═CH 2 ); 1,1,1,4,4-pentafluoro-2-butene (CHF 2 CH═CHCF 3 ); 1,1,1,2,3-pentafluoro-2-butene (CH 3 CF═CFCF 3 ); 2,3,3,4,4-pentafluoro-1-butene (CH 2 ═CFCF 2 CHF 2 ); 1,1,2,4,4-pentafluoro-2-butene (CHF 2 CF═CHCHF 2 ); 1,1,2,3,3-pentafluoro-1-butene (CH 3 CF 2 CF═CF 2 ); 1,1,2,3,4-pentafluoro-2-butene (CH 2 FCF═CFCHF 2 ); 1,1,3,3,3-pentafluoro-2-methyl-1-propene (CF 2 ═C(CF 3 )(CH 3 )); 2-(difluoromethyl)-3,3,3-trifluoro-1-propene (CH 2 ═C(CHF 2 )(CF 3 )); 2,3,4,4,4-pentafluoro-1-butene (CH 2 ═CFCHFCF 3 ); 1,2,4,4,4-pentafluoro-1-butene (CHF═CFCH 2 CF 3 ); 1,3,4,4,4-pentafluoro-1-butene (CHF═CHCHFCF 3 ); 1,3,3,4,4-pentafluoro-1-butene (CHF═CHCF 2 CHF 2 ); 1,2,3,4,4-pentafluoro-1-butene (CHF═CFCHFCHF 2 ); 3,3,4,4-tetrafluoro-1-butene (CH 2 ═CHCF 2 CHF 2 ); 1,1-difluoro-2-(difluoromethyl)-1-propene (CF 2 ═C(CHF 2 )(CH 3 )); 1,3,3,3-tetrafluoro-2-methyl-1-propene (CHF═C(CF 3 )(CH 3 )); 3,3-difluoro-2-(difluoromethyl)-1-propene (CH 2 ═C(CHF 2 ) 2 ); 1,1,1,2-tetrafluoro-2-butene (CF 3 CF═CHCH 3 ); 1,1,1,3-tetrafluoro-2-butene (CH 3 CF═CHCF 3 ); 1,1,1,2,3,4,4,5,5,5-decafluoro-2-pentene (CF 3 CF═CFCF 2 CF 3 ); 1,1,2,3,3,4,4,5,5,5-decafluoro-1-pentene (CF 2 ═CFCF 2 CF 2 CF 3 ); 1,1,1,4,4,4-hexafluoro-2-(trifluoromethyl)-2-butene ((CF 3 ) 2 C═CHCF 3 ); 1,1,1,2,4,4,5,5,5-nonafluoro-2-pentene (CF 3 CF═CHCF 2 CF 3 ); 1,1,1,3,4,4,5,5,5-nonafluoro-2-pentene (CF 3 CH═CFCF 2 CF 3 ); 1,2,3,3,4,4,5,5,5-nonafluoro-1-pentene (CHF═CFCF 2 CF 2 CF 3 ); 1,1,3,3,4,4,5,5,5-nonafluoro-1-pentene (CF 2 ═CHCF 2 CF 2 CF 3 ); 1,1,2,3,3,4,4,5,5-nonafluoro-1-pentene (CF 2 ═CFCF 2 CF 2 CHF 2 ); 1,1,2,3,4,4,5,5,5-nonafluoro-2-pentene (CHF 2 CF═CFCF 2 CF 3 ); 1,1,1,2,3,4,4,5,5-nonafluoro-2-pentene (CF 3 CF═CFCF 2 CHF 2 ); 1,1,1,2,3,4,5,5,5-nonafluoro-2-pentene (CF 3 CF═CFCHFCF 3 ); 1,2,3,4,4,4-hexafluoro-3-(trifluoromethyl)-1-butene (CHF═CFCF(CF 3 ) 2 ); 1,1,2,4,4,4-hexafluoro-3-(trifluoromethyl)-1-butene (CF 2 ═CFCH(CF 3 ) 2 ); 1,1,1,4,4,4-hexafluoro-2-(trifluoromethyl)-2-butene (CF 3 CH═C(CF 3 ) 2 ); 1,1,3,4,4,4-hexafluoro-3-(trifluoromethyl)-1-butene (CF 2 ═CHCF(CF 3 ) 2 ); 2,3,3,4,4,5,5,5-octafluoro-1-pentene (CH 2 ═CFCF 2 CF 2 CF 3 ); 1,2,3,3,4,4,5,5-octafluoro-1-pentene (CHF═CFCF 2 CF 2 CHF 2 ); 3,3,4,4,4-pentafluoro-2-(trifluoromethyl)-1-butene (CH 2 ═C(CF 3 )CF 2 CF 3 ); 1,1,4,4,4-pentafluoro-3-(trifluoromethyl)-1-butene (CF 2 ═CHCH(CF 3 ) 2 ); 1,3,4,4,4-pentafluoro-3-(trifluoromethyl)-1-butene (CHF═CHCF(CF 3 ) 2 ); 1,1,4,4,4-pentafluoro-2-(trifluoromethyl)-1-butene (CF 2 ═C(CF 3 )CH 2 CF 3 ); 3,4,4,4-tetrafluoro-3-(trifluoromethyl)-1-butene ((CF 3 ) 2 CFCH═CH 2 ); 3,3,4,4,5,5,5-heptafluoro-1-pentene (CF 3 CF 2 CF 2 CH═CH 2 ); 2,3,3,4,4,5,5-heptafluoro-1-pentene (CH 2 ═CFCF 2 CF 2 CHF 2 ); 1,1,3,3,5,5,5-heptafluoro-1-butene (CF 2 ═CHCF 2 CH 2 CF 3 ); 1,1,1,2,4,4,4-heptafluoro-3-methyl-2-butene (CF 3 CF═C(CF 3 )(CH 3 )); 2,4,4,4-tetrafluoro-3-(trifluoromethyl)-1-butene (CH 2 ═CFCH(CF 3 ) 2 ); 1,4,4,4-tetrafluoro-3-(trifluoromethyl)-1-butene (CHF═CHCH(CF 3 ) 2 ); 1,1,1,4-tetrafluoro-2-(trifluoromethyl)-2-butene (CH 2 FCH═C(CF 3 ) 2 ); 1,1,1,3-tetrafluoro-2-(trifluoromethyl)-2-butene (CH 3 CF═C(CF 3 ) 2 ); 1,1,1-trifluoro-2-(trifluoromethyl)-2-butene ((CF 3 ) 2 C═CHCH 3 ); 3,4,4,5,5,5-hexafluoro-2-pentene (CF 3 CF 2 CF═CHCH 3 ); 1,1,1,4,4,4-hexafluoro-2-methyl-2-butene (CF 3 C(CH 3 )═CHCF 3 ); 3,3,4,5,5,5-hexafluoro-1-pentene (CH 2 ═CHCF 2 CHFCF 3 ); 4,4,4-trifluoro-2-(trifluoromethyl)-1-butene (CH 2 ═C(CF 3 )CH 2 CF 3 ); 1,1,2,3,3,4,4,5,5,6,6,6-dodecafluoro-1-hexene (CF 3 (CF 2 ) 3 CF═CF 2 ); 1,1,1,2,2,3,4,5,5,6,6,6-dodecafluoro-3-hexene (CF 3 CF 2 CF═CFCF 2 CF 3 ); 1,1,1,4,4,4-hexafluoro-2,3-bis(trifluoromethyl)-2-butene ((CF 3 ) 2 C═C(CF 3 ) 2 ); 1,1,1,2,3,4,5,5,5-nonafluoro-4-(trifluoromethyl)-2-pentene ((CF 3 ) 2 CFCF═CFCF 3 ); 1,1,1,4,4,5,5,5-octafluoro-2-(trifluoromethyl)-2-pentene ((CF 3 ) 2 C═CHC 2 F 5 ); 1,1,1,3,4,5,5,5-octafluoro-4-(trifluoromethyl)-2-pentene ((CF 3 ) 2 CFCF═CHCF 3 ); 3,3,4,4,5,5,6,6,6-nonafluoro-1-hexene (CF 3 CF 2 CF 2 CF 2 CH═CH 2 ); 4,4,4-trifluoro-3,3-bis(trifluoromethyl)-1-butene (CH 2 ═CHC(CF 3 ) 3 ); 1,1,1,4,4,4-hexafluoro-3-methyl-2-(trifluoromethyl)-2-butene ((CF 3 ) 2 C═C(CH 3 )(CF 3 )); 2,3,3,5,5,5-hexafluoro-4-(trifluoromethyl)-1-pentene (CH 2 ═CFCF 2 CH(CF 3 ) 2 ); 1,1,1,2,4,4,5,5,5-nonafluoro-3-methyl-2-pentene (CF 3 CF═C(CH 3 )CF 2 CF 3 ); 1,1,1,5,5,5-hexafluoro-4-(trifluoromethyl)-2-pentene (CF 3 CH═CHCH(CF 3 ) 2 ); 3,4,4,5,5,6,6,6-octafluoro-2-hexene (CF 3 CF 2 CF 2 CF═CHCH 3 ); 3,3,4,4,5,5,6,6-octafluoro1-hexene (CH 2 ═CHCF 2 CF 2 CF 2 CHF 2 ); 1,1,1,4,4-pentafluoro-2-(trifluoromethyl)-2-pentene ((CF 3 ) 2 C═CHCF 2 CH 3 ); 4,4,5,5,5-pentafluoro-2-(trifluoromethyl)-1-pentene (CH 2 ═C(CF 3 )CH 2 C 2 F 5 ); 3,3,4,4,5,5,5-heptafluoro-2-methyl-1-pentene (CF 3 CF 2 CF 2 C(CH 3 )═CH 2 ); 4,4,5,5,6,6,6-heptafluoro-2-hexene (CF 3 CF 2 CF 2 CH═CHCH 3 ); 4,4,5,5,6,6,6-heptafluoro-1-hexene (CH 2 ═CHCH 2 CF 2 C 2 F 5 ); 1,1,1,2,2,3,4-heptafluoro-3-hexene (CF 3 CF 2 CF═CFC 2 H 5 ); 4,5,5,5-tetrafluoro-4-(trifluoromethyl)-1-pentene (CH 2 ═CHCH 2 CF(CF 3 ) 2 ); 1,1,1,2,5,5,5-heptafluoro-4-methyl-2-pentene (CF 3 CF═CHCH(CF 3 )(CH 3 )); 1,1,1,3-tetrafluoro-2-(trifluoromethyl)-2-pentene ((CF 3 ) 2 C═CFC 2 H 5 ); 1,1,1,2,3,4,4,5,5,6,6,7,7,7-tetradecafluoro-2-heptene (CF 3 CF═CFCF 2 CF 2 C 2 F 5 ); 1,1,1,2,2,3,4,5,5,6,6,7,7,7-tetradecafluoro-3-heptene (CF 3 CF 2 CF═CFCF 2 C 2 F 5 ); 1,1,1,3,4,4,5,5,6,6,7,7,7-tridecafluoro-2-heptene (CF 3 CH═CFCF 2 CF 2 C 2 F 5 ); 1,1,1,2,4,4,5,5,6,6,7,7,7-tridecafluoro-2-heptene (CF 3 CF═CHCF 2 CF 2 C 2 F 5 ); 1,1,1,2,2,4,5,5,6,6,7,7,7-tridecafluoro-3-heptene (CF 3 CF 2 CH═CFCF 2 C 2 F 5 ); and 1,1,1,2,2,3,5,5,6,6,7,7,7-tridecafluoro-3-heptene (CF 3 CF 2 CF═CHCF 2 C 2 F 5 ).

9. The composition of claim 1 further comprising at least one metal deactivator selected from the group consisting of areoxalyl bis(benzylidene)hydrazide; N,N′-bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamoylhydrazine); 2,2′-oxamidobis-ethyl-(3,5-d-tert-butyl-4-hydroxyhydorcinnamate); N,N′-(disalicyclidene)-1,2-propanediamine; ethyenediaminetetraacetic acid and salts thereof; triazoles; benzotriazole, 2-mercaptobenzothiazole, tolutriazole derivatives, N,N-disalicylidene-1,2-diaminopropane, and mixtures thereof.

10. A process for producing cooling comprising condensing the composition of claim 1 and thereafter evaporating said composition in the vicinity of a body to be cooled.

11. A process for producing heat comprising condensing the composition of claim 1 in the vicinity of a body to be heated, and thereafter evaporating said composition.

12. A method for stabilizing a composition comprising at least one fluoroolefin, said method comprising adding an effective amount of a stabilizer comprising at least one epoxide or fluorinated epoxide and at least one butylated triphenylphosphorothionate.

13. A method for reducing degradation of a composition comprising at least one fluoroolefin, wherein said degradation is caused by the presence of inadvertent air in a refrigeration, air-conditioning or heat pump system, said method comprising adding an effective amount of a stabilizer comprising at least one epoxide or fluorinated epoxide and at least one butylated triphenylphosphorothionate to the composition comprising at least one fluoroolefin.

14. A method for reducing reaction with oxygen for a composition comprising at least one fluoroolefin, said method comprising adding an effective amount of a stabilizer comprising at least one epoxide or fluorinated epoxide and at least one butylated triphenylphosphorothionate and mixtures thereof to the composition comprising at least one fluoroolefin.