| JP60072979 | FLUOROCHLOROHYDROCARBON COMPOSITION |
| JP2003064352 | MIXED WORKING FLUID AND FREEZING CYCLE DEVICE |
| JP02240186 | HALOGENATED HYDROCARBON MIXTURE |
MARHOLD, Michael (Carl-Rumpff-Str. 75, Leverkusen, 51373, DE)
EICHER, Johannes (Ratswinkel 6, Sehnde, 31319, DE)
MROSS, Stefan (Rue Seutin 43, Brussels, B-1030, BE)
SESEKE-KOYRO, Ulrich (Eichendorffstrasse 3F, Isernhagen, 30916, DE)
MEURER, Christoph (Eckerstrasse 9, Hannover, 30161, DE)
RIVA, Marcello (Plathnerstrasse 43, Hannover, 30173, DE)
FLOHR, Felix (Wildefüerstrasse 14, Hildesheim, 31134, DE)
FISCHER, Reiner (Poststrasse 5, Dettum, 38173, DE)
UENVEREN, Ercan (Kleestrasse 2, Hannover, 30265, DE)
MARHOLD, Michael (Carl-Rumpff-Str. 75, Leverkusen, 51373, DE)
EICHER, Johannes (Ratswinkel 6, Sehnde, 31319, DE)
MROSS, Stefan (Rue Seutin 43, Brussels, B-1030, BE)
SESEKE-KOYRO, Ulrich (Eichendorffstrasse 3F, Isernhagen, 30916, DE)
MEURER, Christoph (Eckerstrasse 9, Hannover, 30161, DE)
RIVA, Marcello (Plathnerstrasse 43, Hannover, 30173, DE)
FLOHR, Felix (Wildefüerstrasse 14, Hildesheim, 31134, DE)
FISCHER, Reiner (Poststrasse 5, Dettum, 38173, DE)
C L A I M S
1 - A method using compounds or compositions for useful applications such as foam blowing, solvent cleaning, refrigeration, as etching gas for semiconductor etching or chamber cleaning, heat transfer, fire extinguishing and production of aerosols comprising a step wherein
at least one compound is applied selected from Tables 1 or 2 of the specification, namely at least one compound selected from the groups consisting of
Fluorosubstituted ethers consisting of 3,3,4,4-tetrafluoro-tetrahydrofuran, 2,2,5, 5-tetrafluoro-2,5-dihydro-furan, methyl-(l , 1 ,2-trifluoro-ethyl)-ether, (1,1 ,2,3 ,3 ,3-hexafluoro-propyl)-methyl ether, (1,1 ,2,2-tetrafluoro-ethyl)-(2,2,2- trifluoro-ethyl)-ether, methyl-(βH-octafluoro-isobutyl)-ether, bis-(2,2,2-trifluoro- ethyl) ether, l,l,l,2,2-pentafluoro-3-methoxy-propane, 1,1,2,2-Tetrafluorethyl- fluormethylether, 1 -difluoromethoxy- 1 ,2,2-trifluoro-ethane, 1,1,1 ,2,2-pentafluoro- 3-fluoromethoxy-propane, 3,3,3-trifluoro-l-(l,l,2,2,3,3,3-heptafluoro-propoxy)- propyne, 1 , 1 ,2,2-Tetrafiuoroethyl- 1 ,2,2-trifluoroethylether, difluoro-(2,2,2- trifluoro- 1 -methoxy- 1 -trifluoromethyl-ethyl)-amine, 1 , 1 ,2,2,3 ,3 ,4-heptafluoro-4- methoxy-cyclo butane, 4-difluoromethoxy- 1,1,1 ,2,2,3,3-heptafluoro-butane, 1,1,1 ,3 ,3 ,3-hexafluoro-2-methoxymethyl-2-trifluoromethyl-propane, 2-difluoromethoxy- 1,1,1 -trifluoro-propane, 3 -difluoromethoxy- 1,1,1 ,2,2- pentafluoro-propane, 2-difluoromethoxy- 1,1, 2, 3, 3-pentafluoro-propane, 1 -difluoromethoxy- 1 , 1 ,2,3,3,3-hexafluoro-propane, 1,1,1 ,2,3,3-hexafluoro-3- fluoromethoxy-propane, 1,1,1 ,2,3 ,3 ,3-heptafluoro-2-(2,2,2-trifluoro- 1 - trifluoromethyl-ethoxy)-propane, methoxymethyl-bis-trifluoromethyl-amine, 1, 2,2,3, 3-Pentafluorpropyl-difluormethylether, perfluoro-3,6-dioxa-l-heptene, 1 , 1 ,2-trifluoro-2-[ 1 , 1 ,2,2-tetrafiuoro-2-( 1 , 1 ,2,2,2-pentafluoro-ethoxy)-ethoxy]- ethene, 1,1,1 ,3 ,3-pentafluoro-3-( 1 ,2,2,2-tetrafluoro- 1 -trifluoromethyl-ethoxy)- propan-2-one, Bis-(2-difluoramino-perfluorethyl)-ether, 2,2,3,4,4,5-hexafluoro- tetrahydro-furan, 2,3,3 ,4,4,5-hexafluoro-tetrahydro-furan, 1 , 1 ,2,2-tetrafluoro- 1 - (1,1 ,2,2-tetrafluoro-ethoxy)-ethane, 2,2,3,5 ,6, 6-hexafluoro-[l ,4]dioxane, 2,2,3, 5,5, 6-hexafluoro-[l,4]dioxane, 2-[(2,2-difluoro-vinyloxy)-difluoro- methoxy]- 1 , 1 -difluoro-ethene, 2,2,4,4-tetrakis-trifluoromethyl-[ 1 ,3]dioxolane, 1 , 1 ,2-trifluoro- 1 ,2-bis-trifluoromethoxy-ethane, heptafluoro-[ 1 ,4]dioxane, 1,1,1 -trifluoro-2-methoxy-ethane, methyl-( 1 , 1 ,2-trifluoro-ethyl)-ether, difluoromethyl-fluoromethyl ether, 1 , 1 ,2,2-tetrafluoro- 1 ,2-bis-trifluoromethoxy- ethane, 2,2,2-trifluoroethyl difluoromethyl ether, Perfluoropropylmethylether, 1 , 1 ,2,2-tetrafluoro- 1 -( 1 ,2,2,2-tetrafluoro-ethoxy)-ethane, 1,1,1 ,2,2-pentafluoro-2- (1,1 ,2,2-tetrafluoro-ethoxy)-ethane, 1 ,3-difluoro-l , 1 ,3,3-tetramethyl-disiloxane and 1,1,1 ,2,2,3-hexafluoro-3-trifluoromethoxy-propane,
N-containing compounds selected from the group consisting of 2,4,6-trifluoro- [l,3,5]triazine, 2,2,4,4,5, 5-hexafluoro-l,3-bis-trifluoromethyl-imidazolidine, 1 -isopropyl-3 ,3-bis-trifluoromethyl-diaziridine, 1 ,4-Bis(difluoramino)- 1 , 1 ',4,4'- tetrafluorbutene-2, 1 ,4-Bis(difluoramino) perfluorbut-2-ene, N,N-bis- trifluoromethyl-acetamide, bis-(l , 1 ,2,2-tetrafluoro-ethyl)-diazene, bis-(2,2,2- trifluoro- 1 -trifluoromethyl-ethylidene)-hydrazine, 1 , 1 ,2,2-tetrafluoro-N,N'-bis- trifluoromethyl-ethane-l,2-diamine, trifluoro-acetic acid difluoro- (trifluoromethyl-amino)-methyl ester, N,N'-bis-difluoromethyl-N,N'-bis- trifluoromethyl-hydrazine, Octafluoro-2,5-diaza- 1 ,5-hexadiene, cis- 1 ,2-Di-(bis- trifluoromethylamino)- 1 ,2-difluorethylen, Perfluor-bis-dimethylamino-acetylene, 3,3,3-Trifluor-N,N-bis-(trifluoromethyl)-propylamine, perfluoro-2,5-diazahexa- 2,4-diene, bis-trifluoromethyl-(3,3,3-trifluoro-propenyl)-amine, 4,4,5, 5-tetrafluoro-l,3-bis-trifluoromethyl-imidazolidin-2-one, Methyl-bis- trifluorsilyl-amine, N,N,N'-tris-trifluoromethyl-hydrazine, 1 ,2-Difluoramino 1,1,4,4 tetrafluorobut-3-ene, trifluorosilyldimethylamine, Perfluoro-diethylamine, Hexafluorotrimethylamine, tris-difluoromethyl-amine, bis-difluoromethyl- (1,1 ,2,2,2-pentafluoro-ethyl)-amine,
Fluorosubstituted alkenes and alkynes selected from the group consisting of
1 , 1 ,2,3,3-pentafluoro-3-iodo-propene, 1 , 1 ,2,3,3,4,4-heptafluoro-4-iodo-but-l-ene,
1,1, 2, 3,3,4,4, 5,6, 6-decafluoro-hexa-l,5-diene, 1,2,3,3,3-pentafluoro-l-iodo- propene, 1 , 1 ,3 ,3 ,5 ,5-hexafluoro-penta- 1 ,4-diene, 4,4,4-trifluoro-2-trifluoromethyl- but- 1 -ene, 1,1,1 ,5 ,5 ,5-hexafluoro-2,4-bis-trifluoromethyl-pent-2-ene,
1,1,1 ,3 ,5 ,5 ,5-heptafluoro-4-trifluoromethyl-pent-2-ene, 4H-tridecafluoro-hept-3- ene, trifluoromethyl-2-perfluorocyclopentene, 1 H:4H-hexafluorcyclopentene,
1,1, 2, 3,3,4,5, 6,6, 6-decafluoro-5-trifluoromethyl-hex-l-ene, l,2,3,3,4,6,6-heptafluoro-cyclohexa-l,4-diene, 1,2,3, 3, 4,4,5, 5,6, 6-decafluoro- cyclohexene, 1,1,1 ,2,3,4,4,5,5,6,6,6-dodecafluoro-hex-2-ene,
1,3,3, 4,4,5, 5-heptafluoro-2-trifluoromethyl-cyclopentene, 4-difluoromethylene-
3,3-difluoro-l,2-bis-trifluoromethyl-cyclobutene, 3, 3,4,4,5, 5-hexafluoro- cyclopentene, trifluoromethyl-3-perfluorocyclopentene, (E)-6H-undecafluoro- hex-2-ene, perfluoronorbornadiene, 1 ,2,3,4,5,5-hexafluoro-6-trifluoromethyl- bicyclo[2.2.0]hex-2-ene, l,2,3,5-tetrafluoro-4,6-bis-trifluoromethyl- bicyclo[2.2.0]hexa-2,5-diene, (Z)-l,2-difluoro-l-iodoethene, 1,1,1 ,4,4,4-hexafluoro-but-2-ene, 1 , 1 ,3 ,3-tetrafluoro-2-methyl-propene, 1,1,3, 3,5, 5-hexafluoro-penta-l,4-diene, octafluoro-cyclopentene ; perfluorocyclopentene, 1,1,1 ,2,4,4,4-heptafluoro-3-trifluoromethyl-but-2-ene, hexafluorocyclopentadiene, (E)-l,l,l,2,3,4,4,5,5,5-decafluoro-pent-2-ene, (Z)-1 , 1 ,1 ,3,4,4,5,5,5-nonafluoro-pent-2-ene and 1 ,1 , 1 ,5,5,5-hexafluoro-4,4-bis- trifluoromethyl-pent-2-yne,
Alkanes and iodoalkanes selected from the group consisting of l,l,l-trifluoro-2- iodo-ethane, nonafluoro-1-io do -butane (perfluorobutyl iodide), nonafluoro-2- iodo-butane, 1 , 1 ,2,3 ,3 ,4-hexafluoro-cyclo butane, 1 H,3H-cctafluorcyclopentane, 1 , 1 ,2,2,3-pentafluoro-3-iodo-cyclopropane, 1 , 1 ,2-trifluoro-2-trifluoromethyl- cyclopropane, cis- 1 , 1 ,2,3-tetrafluorocyclopropane,
Fluorinated compounds with a keto group selected from the group consisting of 1 , 1 ,1 ,3-tetrafluoro-propan-2-one, 3,3,4,4, 5,5, 5-heptafluoro-pentan-2-one, 1 ,3,3,4,4,4-hexafluoro-butan-2-one, decafluorocyclohexanone, 3,3,4,4-tetrafluoro- butan-2-one, 3 ,3 ,3-trifluoro-2-trifluoromethyl-propionaldehyde, Iodopentafluoroacetone, 3 ,4,4,4-tetrafluoro-butan-2-one, 1,1,1 -trifluoro-butan-2- one, 3,3,4,4,4-pentafluoro-butan-2-one, l,l,l,4,4,4-hexafluoro-2,3-butanedione, octafluoro-cyclopentanone, trifluoro-acetic acid 2,2,2-trifluoro-ethyl ester, perfluor-tert.-butyl perfluoracetate, hexafluor-2-buten-2,3-diol bis(trifluoroacetic acid) ester, trifluoro-acetic acid 2,2-difluoro-l-trifluoromethyl- vinyl ester, and trifluoro-acetic acid methyl ester,
Fluorinated alcohols selected from the group consisting of 1,1,1,3,3,3-hexafluoro- 2-propanol, l,l,l,3,3,3-hexafluoro-2-methyl-2-propanol and 2,2,3 ,3 ,4,4-hexafluoro- 1 -trifluoromethyl-cyclobutanol,
Fluorinated silanes selected from the group consisting of 3,3,3-trifluorpropyl- trifluorsilane, trifluoro-propyl-silane, trifluoro-(3,3,3-trifluoro-propyl)-silane, hexa-Si-fluoro-Si,Si'-methanediyl-bis-silane, and Tris-trifluorsilylmethane, and
Fluorinated phosphorous and sulfur compounds selected from the group consisting of 2,2,2-trifluoro-4,4,5 ,5-tetrakis-trifluoromethyl-2λ 5 - [1,3 ,2] dioxaphospho lane, methyl-bis-trifluoromethyl-phosphane, and 1 ,2-perfluoropropylene sulfate. 2 - The method according to claim 1 for cleaning a surface which comprises contacting said surface with a solvent comprising at least one compound described in Tables 1 or 2 of the specification.
3 - The method according to claim 2, wherein the compound is described in table 1.
4 - The method according to claim 2 or 3, wherein the compound is selected from compounds No. 1, 3, 5, 10, 23, 34, 39, 40, 53, 57, 60, 61, 73, 76, 83, 86, 94, 99 and 100 described in table 1, preferably from compounds No. 1, 5, 10, 23 and 53.
5 - The method according to anyone of claims 2 to 4 wherein the surface is dried.
6 - The method according to anyone of claims 2 to 4 wherein the surface is degreased.
7 - The method according to anyone of claims 2 to 5 wherein the solvent has a GWPioo less than 150.
8 - The method according to anyone of claims 2 to 6 wherein the solvent has an atmospheric boiling point from 30 0 C to 80 0 C.
9 - The method according to anyone of claims 2 to 7 wherein the solvent contains from 10 to about 100 % by weight of the compound.
10 - A method according to claim 1 for producing a polymer foam which comprises using a blowing agent comprising at least one compound described in Tables 1 or 2 of the specification.
11 - The method according to claim 10, wherein the compound is described in table 2.
12 - The method according to claim 11, wherein the compound is selected from compounds No. 4, 17, 25, 26, 28, 30, 38 and 39 described in table 2.
13 - The method according to anyone of claims 10 to 12 wherein the polymer foam is a thermoset foam. 14 - The method according to claim 13 wherein the polymer foam is an isocyanate-based foam.
15 - The method according to anyone of claims 10 to 12 wherein the polymer foam is a thermoplastic foam.
16 - The method according to claim 15 wherein the polymer foam is an alkenylaromatic foam, preferably a polystyrene foam.
17 - The method according to anyone of claims 10 to 16 wherein the foam blowing agent has a GWP 100 less than 150.
18 - The method according to anyone of claims 10 to 17 wherein the foam blowing agent has an atmospheric boiling point from 0 0 C to 45°C.
19 - The method according to anyone of claims 10 to 18 wherein the foam blowing agent contains from 10 to about 100 % by weight of the compound.
20 - Use of a fluorinated olefin having at least 4 carbon atoms and an atmospheric boiling point from 0 0 C to 100 0 C, preferably 10 to 80 0 C as constituent of a foam blowing agent, a solvent, a refrigerant, a heat transfer fluid, a fire extinguishing agent or an aerosol propellant.
21 - Use according to claim 20, wherein the fluorinated olefin is cyclic.
22 - Use according to claim 20 or 21, wherein the fluorinated olefin is a conjugated or non-conjugated diene.
23 - Use of a cyclic fluorinated ether having an atmospheric boiling point from 0 0 C to 100 0 C, preferably 10 to 80 0 C as constituent of a foam blowing agent, a solvent, a refrigerant, a heat transfer fluid, a fire extinguishing agent or an aerosol propellant.
24 - Use of a fluorinated N-heterocyclic compound having an atmospheric boiling point from 0 0 C to 100 0 C, preferably 10 to 80 0 C as constituent of a foam blowing agent, a solvent, a refrigerant, a heat transfer fluid, a fire extinguishing agent or an aerosol propellant. 25 - Use of a fluorinated unsaturated nitrogen containing compound having an atmospheric boiling point from 0 0 C to 100 0 C, preferably 10 to 80 0 C as constituent of a foam blowing agent, a solvent, a refrigerant, a heat transfer fluid, a fire extinguishing agent or an aerosol propellant.
26 - Use of a cyclic fluorinated ketone having an atmospheric boiling point from 0 0 C to 100 0 C, preferably 10 to 80 0 C as constituent of a foam blowing agent, a solvent, a refrigerant, a heat transfer fluid, a fire extinguishing agent or an aerosol propellant.
27 - Composition comprising a compound disclosed in table 1 or 2, a non fluoro organic solvent and optionally a hydrofluoroalkane.
28 - Composition comprising a fluorinated compound in accordance with anyone of claims 19 to 25, a non fluoro organic solvent and optionally a hydrofluoroalkane.
29 - Mixtures, preferably azeotropes and azeotrope like compositions, formed from the compound described under number 10 of table 1, (1,1,2,3,3,3- hexafluoro-propyl)-methyl ether, and ethanol or perfluoropoly ether available under GALDEN® HT 55.
30 - The azeotrope of claim 29 consisting of (1,1,2, 3,3, 3-hexafluoro- propyl)-methyl ether and ethanol, having a minimum boiling point of about 51.1 0 C at about 990 mbar and a composition of about 13 % by volume of ethanol and about 87 % by weight of (1,1, 2,3,3, 3-hexafluoro-propyl)-methyl ether.
31 - The azeotrope of claim 29 consisting of (1,1,2, 3,3, 3-hexafluoro- propyl)-methyl ether and GALDEN® HT 55 has a minimum boiling point of about 41.3°C at 977 mbar and a composition of about 50 % by weight of GALDEN® HT 55 and about 50 % by weight of (1,1,2,3,3,3-hexafluoro-propyl)- methyl ether. |
Methods of using a solvent or a foam blowing agent
The invention relates to methods using compounds or compositions for useful applications such as foam blowing, solvent cleaning, and refrigeration, as etching gas for semiconductor etching or chamber cleaning, heat transfer, fire extinguishing and production of aerosols, and to specific azeotropes which can be applied in at least one of these processes.
Halofluorocarbons and especially chlorofluorocarbons had been used for many technical applications, for example, as solvents, foam blowing agents, for refrigeration, heat transfer and for fire extinguishing. In view of regulations in view of ozone depletion and greenhouse potential, alternatives are considered necessary.
In its broadest aspect, the invention concerns a method using compounds or compositions for useful applications such as foam blowing, solvent cleaning, refrigeration, as etching gas for semiconductor etching or chamber cleaning, heat transfer, fire extinguishing and production of aerosols comprising a step wherein at least one compound is applied selected from Tables 1 or 2 of the specification, namely at least one compound selected from the groups consisting of Fluorosubstituted ethers consisting of 3,3,4,4-tetrafluoro-tetrahydrofuran, 2,2,5,5-tetrafluoro-2,5-dihydro-furan, methyl-(l , 1 ,2-trifluoro-ethyl)-ether, (1,1 ,2,3 ,3 ,3-hexafluoro-propyl)-methyl ether, (1,1 ,2,2-tetrafluoro-ethyl)-(2,2,2- trifluoro-ethyl)-ether, methyl-(βH-octafluoro-isobutyl)-ether, bis-(2,2,2-trifluoro- ethyl) ether, l,l,l,2,2-pentafluoro-3-methoxy-propane, 1,1,2,2-Tetrafluorethyl- fluormethylether, 1 -difluoromethoxy- 1 ,2,2-trifluoro-ethane, l,l,l,2,2-pentafluoro-3-fluoromethoxy-propane, 3,3,3-trifluoro-l-(l,l,2,2,3,3,3- heptafluoro-propoxy)-propyne, 1 , 1 ,2,2-Tetrafluoroethyl- 1 ,2,2-trifluoroethylether, difluoro-(2,2,2-trifluoro- 1 -methoxy- 1 -trifluoromethyl-ethyl)-amine,
1 , 1 ,2,2,3 ,3 ,4-heptafluoro-4-methoxy-cyclo butane, 4-difluoromethoxy-
1,1,1 ,2,2,3 ,3-heptafluoro-butane, 1,1,1 ,3 ,3 ,3-hexafluoro-2-methoxymethyl-2- trifluoromethyl-propane, 2-difluoromethoxy- 1,1,1 -trifluoro-propane,
3 -difluoromethoxy- 1,1,1 ,2,2-pentafluoro-propane, 2-difluoromethoxy- 1 , 1 ,2,3,3- pentafluoro-propane, 1 -difluoromethoxy- 1 , 1 ,2,3 ,3,3-hexafluoro-propane,
1 , 1 ,1 ,2,3,3-hexafluoro-3-fluoromethoxy-propane, 1 , 1 ,1 ,2,3,3,3-heptafluoro-2- (2,2,2-trifluoro- 1 -trifluoromethyl-ethoxy)-propane, methoxymethyl-bis-
trifluoromethyl-amine, 1 ,2,2,3, 3-Pentafluorpropyl-difluormethylether, perfluoro- 3 ,6-dioxa- 1 -heptene, 1 , 1 ,2-trifluoro-2-[ 1 , 1 ,2,2-tetrafluoro-2-( 1 , 1 ,2,2,2- pentafluoro-ethoxy)-ethoxy]-ethene, 1,1,1 ,3,3-pentafluoro-3-(l ,2,2,2-tetrafluoro- l-trifluoromethyl-ethoxy)-propan-2-one, Bis-(2-difluoramino-perfluorethyl)- ether, 2,2,3,4,4,5-hexafluoro-tetrahydro-furan, 2, 3,3,4,4, 5-hexafluoro-tetrahydro- furan, l,l,2,2-tetrafluoro-l-(l,l,2,2-tetrafluoro-ethoxy)-ethane, 2,2,3,5,6,6- hexafluoro-[l,4]dioxane, 2,2,3,5,5,6-hexafluoro-[l,4]dioxane, 2-[(2,2-difluoro- vinyloxy)-difluoro-methoxy]- 1 , 1 -difluoro-ethene, 2,2,4,4-tetrakis- trifluoromethyl-[ 1 ,3]dioxolane, 1 , 1 ,2-trifluoro- 1 ,2-bis-trifluoromethoxy-ethane, heptafluoro-[l,4]dioxane, l,l,l-trifluoro-2-methoxy-ethane, methyl-( 1,1,2- trifluoro-ethyl)-ether, difluoromethyl-fluoromethyl ether, l,l,2,2-tetrafluoro-l,2- bis-trifluoromethoxy-ethane, 2,2,2-trifluoroethyl difluoromethyl ether, Perfluoropropylmethylether, 1 , 1 ,2,2-tetrafluoro- 1 -( 1 ,2,2,2-tetrafluoro-ethoxy)- ethane, 1,1,1 ,2,2-pentafluoro-2-(l , 1 ,2,2-tetrafluoro-ethoxy)-ethane, 1 ,3-difluoro- 1,1,3,3-tetramethyl-disiloxane and 1,1, 1,2,2, 3-hexafluoro-3-trifluoromethoxy- propane,
N-containing compounds selected from the group consisting of 2,4,6-trifluoro- [l,3,5]triazine, 2,2,4,4,5, 5-hexafluoro-l,3-bis-trifluoromethyl-imidazolidine, 1 -isopropyl-3 ,3-bis-trifluoromethyl-diaziridine, 1 ,4-Bis(difluoramino)- 1 , 1 ',4,4'- tetrafluorbutene-2, 1 ,4-Bis(difluoramino) perfluorbut-2-ene, N,N-bis- trifluoromethyl-acetamide, bis-(l , 1 ,2,2-tetrafluoro-ethyl)-diazene, bis-(2,2,2- trifluoro- 1 -trifluoromethyl-ethylidene)-hydrazine, 1 , 1 ,2,2-tetrafluoro-N,N'-bis- trifluoromethyl-ethane-l,2-diamine, trifluoro-acetic acid difluoro- (trifluoromethyl-amino)-methyl ester, N,N'-bis-difluoromethyl-N,N'-bis- trifluoromethyl-hydrazine, Octafluoro-2,5-diaza-l,5-hexadiene, cis-l,2-Di-(bis- trifluoromethylamino)- 1 ,2-difluorethylen, Perfluor-bis-dimethylamino-acetylene, 3,3,3-Trifluor-N,N-bis-(trifluoromethyl)-propylamine, perfluoro-2,5-diazahexa- 2,4-diene, bis-trifluoromethyl-(3,3,3-trifluoro-propenyl)-amine, 4,4,5, 5-tetrafluoro-l,3-bis-trifluoromethyl-imidazolidin-2-one, Methyl-bis- trifluorsilyl-amine, N,N,N'-tris-trifluoromethyl-hydrazine, 1 ,2-Difluoramino 1,1,4,4 tetrafluorobut-3-ene, trifluorosilyldimethylamine, Perfluoro-diethylamine, Hexafluorotrimethylamine, tris-difluoromethyl-amine, bis-difluoromethyl-(l , 1 ,2,2,2-pentafluoro-ethyl)-amine, Fluorosubstituted alkenes and alkynes selected from the group consisting of 1,1 ,2,3,3-pentafluoro-3-iodo-propene, 1 , 1 ,2,3,3,4,4-heptafluoro-4-iodo-but-l- ene, 1,1, 2, 3,3,4,4, 5,6, 6-decafluoro-hexa-l,5-diene, 1,2,3,3,3-pentafluoro-l-iodo-
propene, l,l,3,3,5,5-hexafluoro-penta-l,4-diene, 4,4,4-trifluoro-2- trifluoromethyl-but- 1 -ene, 1,1,1 ,5 ,5 ,5-hexafluoro-2,4-bis-trifluoromethyl-pent-2- ene, 1,1,1 ,3 ,5 ,5 ,5-heptafluoro-4-trifluoromethyl-pent-2-ene, 4H-tridecafluoro- hept-3 -ene, trifluoromethyl-2-perfluorocyclopentene, lH:4H-hexafluorcyclopentene, l,l,2,3,3,4,5,6,6,6-decafluoro-5-trifluoromethyl- hex-1-ene, l,2,3,3,4,6,6-heptafluoro-cyclohexa-l,4-diene, 1,2,3,3,4,4,5,5,6,6-decafluoro-cyclohexene, 1,1, 1,2,3, 4,4,5, 5, 6,6,6-dodecafluoro- hex-2-ene, l,3,3,4,4,5,5-heptafluoro-2-trifluoromethyl-cyclopentene, 4-difluoromethylene-3,3-difluoro-l,2-bis-trifluoromethyl-cyc lobutene, 3, 3,4,4,5, 5-hexafluoro-cyclopentene, trifluoromethyl-S-perfluorocyclopentene, (E)-6H-undecafluoro-hex-2-ene, perfluoronorbornadiene, 1 ,2,3,4,5,5-hexafluoro- 6-trifluoromethyl-bicyclo[2.2.0]hex-2-ene, l,2,3,5-tetrafluoro-4,6-bis- trifluoromethyl-bicyclo[2.2.0]hexa-2,5-diene, (Z)-l,2-difluoro-l-iodoethene, 1,1,1 ,4,4,4-hexafluoro-but-2-ene, 1 , 1 ,3 ,3-tetrafluoro-2-methyl-propene, 1,1,3, 3,5, 5-hexafluoro-penta-l,4-diene, octafluoro-cyclopentene ; perfluorocyclopentene, 1,1,1 ,2,4,4,4-heptafluoro-3-trifluoromethyl-but-2-ene, hexafluorocyclopentadiene, (E)-l,l,l,2,3,4,4,5,5,5-decafluoro-pent-2-ene, (Z)- 1 , 1 ,1 ,3,4,4,5,5,5-nonafluoro-pent-2-ene and 1 ,1 ,1 ,5,5,5-hexafluoro-4,4-bis- trifluoromethyl-pent-2-yne, Alkanes and iodoalkanes selected from the group consisting of l,l,l-trifluoro-2- iodo-ethane, nonafluoro-1-io do -butane (perfluorobutyl iodide), nonafluoro-2- iodo-butane, 1 , 1 ,2,3 ,3 ,4-hexafluoro-cyclo butane, 1 H,3H-cctafluorcyclopentane, 1 , 1 ,2,2,3-pentafluoro-3-iodo-cyclopropane, 1 , 1 ,2-trifluoro-2-trifluoromethyl- cyclopropane, cis- 1 , 1 ,2,3-tetrafluorocyclopropane, Fluorinated compounds with a keto group selected from the group consisting of 1 , 1 ,1 ,3-tetrafluoro-propan-2-one, 3,3,4,4, 5,5, 5-heptafluoro-pentan-2-one, 1 ,3,3,4,4,4-hexafluoro-butan-2-one, decafluorocyclohexanone, 3 ,3 ,4,4-tetrafluoro-butan-2-one, 3 ,3 ,3-trifluoro-2-trifluoromethyl- propionaldehyde, Iodopentafluoroacetone, 3 ,4,4,4-tetrafluoro-butan-2-one, l,l,l-trifluoro-butan-2-one, 3,3,4,4,4-pentafluoro-butan-2-one,
1,1,1 ,4,4,4-hexafluoro-2,3-butanedione, octafluoro-cyclopentanone, trifluoro-acetic acid 2,2,2-trifluoro-ethyl ester, perfluor-tert. -butyl perfluoracetate, hexafluor-2-buten-2,3-diol bis(trifluoroacetic acid) ester, trifluoro-acetic acid 2,2-difluoro-l-trifluoromethyl-vinyl ester, and trifluoro-acetic acid methyl ester,
Fluorinated alcohols selected from the group consisting of 1 , 1 ,1 ,3,3,3-hexafluoro-2-propanol, 1 , 1 ,1 ,3,3,3-hexafluoro-2-methyl-2-propanol and 2,2,3 ,3 ,4,4-hexafluoro- 1 -trifluoromethyl-cyclobutanol, Fluorinated silanes selected from the group consisting of 3,3,3-trifluorpropyl- trifluorsilane, trifluoro-propyl-silane, trifluoro-(3,3,3-trifluoro-propyl)-silane, hexa-Si-fluoro-Si,Si'-methanediyl-bis-silane, and Tris-trifluorsilylmethane, and Fluorinated phosphorous and sulfur compounds selected from the group consisting of 2,2,2-trifluoro-4,4,5 ,5-tetrakis-trifluoromethyl-2λ 5 - [l,3,2]dioxaphospholane, methyl-bis-trifluoromethyl-phosphane, and 1 ,2-perfluoropropylene sulfate.
These compounds are environmentally advantageous, especially in view of low or zero ODP (ozone depletion potential) and GWP (global warming potential).
In a first aspect, the invention relates to a method for cleaning a surface which comprises contacting said surface with a solvent comprising at least one compound selected from the groups mentioned above.
The foregoing compounds are described in Tables 1 or 2 of this specification. The tables 1 and 2 of the specification also include information about the structure, the chemical formula, boiling point, a comment to the general type of the compound (ether, alkane, alkene etc) and literature where the respective compounds are cited. Said compounds are known and can be obtained for example according to certain methods described or referred to in the literature cited in the tables. In this first aspect, the compound is preferably selected from those described in table 1. More preferably, the compound is selected from compounds No. 1, 3, 5, 10, 23, 34, 39, 40, 53, 57, 60, 61, 73, 76,
83, 86, 94, 99 and 100 described in table 1, and most preferably from compounds No. 1, 5, 10, 23 and 53 described in table 1.
In the first aspect of the invention the solvent has generally a GWPioo of less than 150, preferably equal to or less than 120, more preferably equal to or less than 80 and most preferably equal to or less than 50.
In the first aspect of the invention the solvent has generally an atmospheric boiling point equal to or higher than 20 0 C, preferably equal to or higher than 30 0 C and more preferably equal to or higher than 35°C. In the first aspect of the invention the solvent has generally an atmospheric boiling point equal to or lower than 100 0 C, preferably equal to or lower than 80 0 C and more preferably equal to or lower than 60 0 C.
In the frame of the present invention, often the term "compound" is used. It is to be understood that, unless otherwise stated, of course, also two, three or more of the compounds mentioned in the tables can be present.
In the first aspect of the invention, the content of the compound described in Table 1 or 2 in the solvent is generally equal to our more than 1 % by weight relative to the weight of the solvent. Often this content is equal to or more than 10 % by weight, preferably equal to or more than 30 % by weight. In some embodiments of the first aspect of the invention, the content of the compound described in Table 1 or 2 in the solvent can be about 100 % by weight relative to the weight of the solvent. Other typical contents in these embodiments are, for example equal to or less than 99 % by weight, equal to or less than 98 % by weight or even equal to our lower than 75 % by weight.
In the first aspect of the invention, the solvent can consist or consist essentially of a compound described in Table 1 or 2. In the first aspect of the invention the solvent can for example comprise a non-fluoro organic solvent in addition to anyone of the fluorinated compounds described in Tables 1 and 2. The invention relates also to compositions of the compounds described in Tables 1 and 2 with a non-fluoro organic solvent in particular as described herein. Preferably, the content of the compound described in Table 1 or 2 in these compositions is as described before in relation to the content of the compound in the solvent. The remainder of the composition can consist of non-fluoro organic solvent.
Examples of non-fluoro organic solvents, are hydrocarbons, halogenated hydrocarbons in particular chlorohydrocarbons, alcohols, esters, ketones or ethers.
The hydrocarbons which can be used in the compositions according to the invention may be linear, branched or cyclic and generally contain 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12 carbon atoms. Hydrocarbons comprising at least 5 carbon atoms are suitable for use. The hydrocarbons preferably comprise at least 6 carbon atoms. Among the alkanes or alkenes, compounds comprising from 5 to
12 carbon atoms are preferred. n-Hexane, n- heptane and n-octane are suitable for use. Among the aromatic hydrocarbons which are preferred are those comprising at least one alkyl substituent on a benzene ring. Toluene, 1,2-xylene, 1,3-xylene, 1,4-xylene or mixtures thereof are most particularly preferred. The chlorohydrocarbons which can be used in the compositions according to the invention may be linear, branched or cyclic and generally contain 1, 2, 3,
4, 5, 6, 7, 8, 9 or 10 carbon atoms. Chlorohydrocarbons comprising 1, 2, 3 or 4 carbon atoms are suitable for use. The chlorohydrocarbons preferably comprise 1 or 2 carbon atoms. Among the chloroalkanes, dichloromethane, trichloromethane and 1 ,2-dichloroethane are preferred. Among the chloroalkenes, perchloroethylene and 1 ,2-dichloroethylene are preferred. Trans- 1 ,2-Dichloroethylene is most particularly preferred.
The alcohols which can be used in the compositions according to the invention may be linear, branched or cyclic and generally contain 1, 2, 3, 4, 5, 6,
7, 8, 9 or 10 carbon atoms. Alcohols comprising 1, 2, 3, 4 or 5 carbon atoms are suitable for use. The alcohols preferably comprise 1, 2, 3 or 4 carbon atoms.
Among the alkanols, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol and tert-butanol are preferred. Methanol, ethanol, isopropanol and isobutanol give good results. Methanol is most particularly preferred. Ethanol is also very suitable in the compositions according to the invention. The esters which can be used in the compositions according to the invention can be linear, branched or cyclic and generally contain 3, 4, 5, 6, 7, 8, 9 or 10 carbon atoms. Esters comprising 4, 5, 6, 7, 8 or 9 carbon atoms are suitable for use. Preferably, the esters are derivatives of a carboxylic acid comprising at least 2 carbon atoms. Preferably, the esters are derivatives of an alkanol, selected from the group consisting of methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol and tert-butanol. Ethyl acetate, ethyl butyrate and ethyl caproate are suitable for use.
The ketones which can be used in the compositions according to the invention can be linear, branched or cyclic and generally contain 3, 4, 5, 6, 7, 8, 9 or 10 carbon atoms. Ketones comprising 3, 4, 5, 6, 7 or 8 carbon atoms are suitable for use. Among the ketones, acetone, 2-butanone, 2- or 3-pentanone, methyl isobutyl ketone, diisopropyl ketone, cyclohexanone and acetophenone are preferred. Methyl isobutyl ketone is particularly preferred.
The ethers which can be used in the compositions according to the invention can be linear, branched or cyclic and generally contain 2, 3, 4, 5, 6, 7,
8, 9 or 10 carbon atoms. Ethers comprising 4, 5, 6, 7, 8 or 9 carbon atoms are suitable for use. Among the aliphatic or alicyclic ethers, diethyl ether, methyl isopropyl ether, diethylene glycol mono methyl ether, diethylene glycol dimethyl ether, tetrahydrofuran and 1 ,4 dioxane are preferred.
Nitrogen-containing non fluoro solvents such as nitroalkanes, amides, e.g. dimethylformamide, dimethylacetamide or N-methylpyrollidone or heterocycles such as pyridine can also be used.
Sulphur-containing non fluoro solvents such as dimethyl sulphoxide can also be used.
The content of non-fluoro organic solvents in the solvent is generally at equal to our more than 1 % by weight relative to the weight of the solvent. Often this content is equal to or more than 10 % by weight, preferably equal to or more than 25 % by weight. This content can be equal to or less than 99 % by weight equal to or less than 98 % by weight or even equal to our lower than 75 % by weight.
The compositions according to the invention may further comprise at least one additional fluorinated compound, having typically from 1 to 6 carbon atoms. In one aspect of this embodiment the additional fluorinated compound is a hydro fluoroalkane which is frequently selected from difluoromethane (HFC-32), 1,1-difiuoroethane (HFC-152a), 1,1,1-trifluoroethane (HFC-143a), 1,1,1,2-tetrafluoroethane (HFC- 134a), pentafluoroethane (HFC- 125), 1 , 1 ,1 ,3,3-pentafluoropropane (HFC-245fa), 1 , 1 ,1 ,3,3,3-hexafluoropropane (HFC-236fa), 1,1,1,2,3,3,3-heptafiuoropropane (HFC-227ea), 1,1,1,3,3-pentafiuorobutane (HFC-365mfc) and 1,1,1,2,3,4,4,5,5,5- decafluoropentane (HFC-43-lOmee).
In a first preferred aspect of this embodiment, the hydrofluoroalkane is 1 , 1 -difluoroethane.
In a second preferred aspect of this embodiment, the hydrofluoroalkane is 1,1,1 ,2-tetrafluoroethane (HFC- 134a).
In a third preferred aspect of this embodiment, the hydrofluoroalkane is 1,1,1 ,3,3-pentafluoropropane.
In a fourth preferred aspect of this embodiment, the hydrofluoroalkane is 1,1,1 ,3,3-pentafluorobutane. In a fifth preferred aspect of this embodiment, the hydrofluoroalkane is l,l,l,2,3,4,4,5,5,5-decafluoropentane (HFC-43-10mee).
In another aspect of this embodiment the additional fluorinated compound is a hydrofluoroether selected from 1,1,2,2-tetrafluoroethyl-methyl ether, perfluoropropylmethyl ether, perfluorobutylmethyl ether and perfluorobutylethyl ether.
In still another aspect of this embodiment, the additional compound is a perfluoropolyether or a mixture thereof. Particular examples are perfluoropoly ethers marketed by Solvay So lexis under the names GALDEN® and FOMBLIN®, especially the the perfluoropolyether GALDEN® HT55 which has a boiling point of about 57°C at 101.3 kPa and forms an azeotrope with (1,1,2, 3,3, 3-hexafluoro-propyl)-methyl ether (compound 10 in table 1) which will described below.
In still another aspect of this embodiment the additional fluorinated compound is a pentafluoropropene, in particular 1,1,1,2,3-pentafluoropropene. This compound can be present in the form of the (Z) isomer, the (E) isomer or mixtures thereof.
When an additional fluorinated compound is present in a composition according to the invention, its content is generally chosen so that the composition has a GWPioo as described in this specification for the solvent. In that case, the content of the additional fluorinated compound is generally equal to more than 1 % by weight relative to the total weight of the composition of compound disclosed in table 1 or 2, optional non fluoro solvent and additional fluorinated compound. Often, this content is equal to or more than 2 % by weight, preferably equal to or more than 10 % by weight. In that case, the content of the additional fluorinated compound is generally equal to or lower than 99 % by weight equal to or lower than 98 % by weight and preferably equal to or lower than 70 % by weight.
A first particular composition according to the invention comprises from 1-50 % by weight of trans- 1 ,2-dichloroethylene and from 50-99 % by weight of a compound disclosed in table 1 or 2. Non-limiting examples are the following compositions :
• 50 % by weight of 3,3,4,4-tetrafluoro-tetrahydro-furane and 50 % by weight of 1 ,2-trans-dichloroethylene
• 75 % by weight of 3,3,4,4-tetrafluoro-tetrahydro-furane and 25 % by weight of 1 ,2-trans-dichloroethylene
• 50 % by weight of 2,2,5,5-tetrafluoro-2,5-dihydro-furane and 50 % by weight of 1 ,2-trans-dichloroethylene
• 75 % by weight of 2,2,5,5-tetrafluoro-2,5-dihydro-furane and 25 % by weight of 1 ,2-trans-dichloroethylene • 50 % by weight of (l,l,2,3,3,3-hexafluoro-propyl)-methyl ether and 50 % by weight of 1 ,2-trans-dichloroethylene
• 75 % by weight of (1,1,2, 3,3, 3 -hexafluoro -propyl) -methyl ether and 25 % by weight of 1 ,2-trans-dichloroethylene
• 50 % by weight of 1,1,3, 3,5, 5-hexafluoro-penta-l,4-diene and 50 % by weight of 1 ,2-trans-dichloroethylene « 50 % by weight of 1,1,3, 3,5, 5-hexafluoro-penta-l,4-diene and 50 % by weight of 1 ,2-trans-dichloroethylene
• 50 % by weight of 1H:4H-Hexafluorcyclopentene and 50 % by weight of 1 ,2-trans-dichloroethylene
The mixtures described above are very suitable, for example, for degreasing metals.
A second particular composition according to the invention comprises from 1-50 % by weight of trans- 1 ,2-dichloroethylene and from 35-98 % by weight of a compound disclosed in table 1 or 2 and from 1-15 % by weight of a C1-C3 alcohol, in particular methanol or ethanol. Non- limiting examples are the following compositions :
• 50 % by weight of 3,3,4,4-tetrafluoro-tetrahydro-furane, 40 % by weight of 1 ,2-trans-dichloroethylene and 10 % by weight of methanol
• 55 % by weight of 3,3,4,4-tetrafluoro-tetrahydro-furane, 40 % by weight of 1 ,2-trans-dichloroethylene and 5 % by weight of ethanol • 75 % by weight of 3,3,4,4-tetrafluoro-tetrahydro-furane, 20 % by weight of 1 ,2-trans-dichloroethylene and 5 % by weight of methanol
• 50 % by weight of 2,2,5, 5-tetrafluoro-2,5-dihydro-furane, 40 % by weight of 1 ,2-trans-dichloroethylene and 10 % by weight of ethanol
• 50 % by weight of 2,2,5, 5-tetrafluoro-2,5-dihydro-furane, 40 % by weight of 1 ,2-trans-dichloroethylene and 10 % by weight of methanol
• 75 % by weight of 2,2,5, 5-tetrafluoro-2,5-dihydro-furane, 20 % by weight of 1 ,2-trans-dichloroethylene and 5 % by weight of methanol
• 75 % by weight of 2,2,5, 5-tetrafluoro-2,5-dihydro-furane, 20 % by weight of 1 ,2-trans-dichloroethylene and 5 % by weight of ethanol • 70 % by weight of 2,2,5, 5-tetrafluoro-2,5-dihydro-furane, 20 % by weight of 1 ,2-trans-dichloroethylene and 10 % by weight of methanol
• 50 % by weight of (1,1,2,3, 3, 3 -hexafluoro -propyl) -methyl ether, 45 % by weight of 1 ,2-trans-dichloroethylene and 5 % by weight of methanol
• 75 % by weight of (1,1,2, 3,3, 3 -hexafluoro -propyl) -methyl ether, 20 % by weight of 1 ,2-trans-dichloroethylene and 5 % by weight of methanol
• 50 % by weight of 1,1,3, 3,5, 5-hexafluoro-penta-l,4-diene, 45 % by weight of 1 ,2-trans-dichloroethylene and 5 % by weight of methanol
• 75 % by weight of 1,1,3, 3,5, 5-hexafluoro-penta-l,4-diene, 20 % by weight of 1 ,2-trans-dichloroethylene and 5 % by weight of ethanol • 50 % by weight of 1H:4H-Hexafluorcyclopentene, 45 % by weight of 1 ,2-trans-dichloroethylene and 5 % by weight of ethanol
The mixtures described above are very suitable, for example, for degreasing metals.
A third particular composition according to the invention which is useful as water displacement agent comprises from 80-99 %, preferably 90-99 % and most preferably about 95 % by weight of a compound disclosed in table 1 or 2 and from 1-15 %, preferably 1 to 10 % and most preferably about 5 % by weight of a C1-C3 alcohol, in particular methanol or ethanol. Non- limiting examples are the following compositions : • 80 % by weight of 3,3,4,4-tetrafluoro-tetrahydro-furane and 20 % by weight of methanol
• 85 % by weight of 3,3,4,4-tetrafluoro-tetrahydro-furane and 15 % by weight of ethanol
• 80 % by weight of 3,3,4,4-tetrafluoro-tetrahydro-furane, and 20 % by weight ofmethanol
• 80 % by weight of 2,2,5,5-tetrafluoro-2,5-dihydro-furane and 20 % by weight of ethanol
• 85 % by weight of 2,2,5, 5-tetrafluoro-2,5-dihydro-furane and 15 % by weight ofmethanol • 80 % by weight of (l,l,2,3,3,3-hexafiuoro-propyl)-methyl ether and 20 % by weight ofmethanol
• 85 % by weight of (1,1,2, 3,3, 3 -hexafluoro -propyl) -methyl ether and 15 % by weight ofmethanol
• 85 % by weight of (1,1,2, 3,3, 3 -hexafluoro -propyl) -methyl ether and 15 % by weight o f ethano 1
• 87 % by weight of (1,1,2, 3,3, 3 -hexafluoro -propyl) -methyl ether and 13 % by weight of ethanol which is azeotrope or near-azeotrope
• 88 % by weight of (l,l,2,3,3,3-hexafiuoro-propyl)-methyl ether and 12 % by weight of ethanol which is an azeotrope or near-azeotrope • 85 % by weight of 1,1,3, 3,5, 5-hexafluoro-penta-l,4-diene and 25 % by weight ofmethanol
• 85 % by weight of 1,1,3, 3,5, 5-hexafluoro-penta-l,4-diene and 25 % by weight of ethanol
The mixtures described above are very suitable, for example, for degreasing metals. Often, it can be advantageous to add the nitrogen-containing non fluoro solvents such as nitroalkanes, amides, e.g. dimethylformamide, dimethylacetamide or N-methylpyrollidone or hetero cycles such as pyridine or sulphur-containing non fluoro solvents such as dimethyl sulphoxide can as additional component to the binary and ternary compositions given above. For example, the resulting compositions can contain the mentioned nitrogen or sulfur compounds preferably in an amount from equal to or greater than 0.5 % by weight to equal to or lower than 15 % by weight.
If desired, the process according to the present invention can be one step in a process comprising several cleaning steps. For example, items can in a first step be treated by high boiling hydrocarbons, for example, n-octane, toluene or xylene, and in a further, preferably a second step, the method of the present is applied.
In a further embodiment of the first aspect of the method according to the invention, the surface is dried. In that case, the solvent functions as a drying agent. A drying agent is used, for example, in the electronics or electromechanical industry or optionally the cosmetic industry when it is desired to remove the water adsorbed onto a solid surface of an object after an aqueous treatment. The aqueous treatment can consist, for example, of a cleaning operation, optionally in the presence of a surfactant. Generally, after the aqueous treatment, the object is immersed in a drying agent in the boiling state comprising a surfactant, and the surfactant which adheres to the surface of the object is then removed in a washing bath. The compositions according to the invention comprising a surfactant are suitable for the drying operation. The compositions according to the invention which are free of surfactant are suitable for the washing bath intended to remove the surfactant.
A number of surfactants which can be used in this embodiment are described, for example, in Ullmann's Encyclopedia of Industrial Chemistry, 5th edition, 1987, vol. A8, pp. 338 350. Cationic, anionic, nonionic and amphoteric surfactants can be used. It is possible, for example, to use fatty acids, fatty esters, alkylbenzenesulphonates, alkanesulphonates, α-olefm sulphonates, α-sulphonated fatty acid esters (SES), alkyl sulphates, alkyl ether sulphates,
quaternary ammonium compounds, polyethylene glycol alkyl ethers, polyethylene glycol phenyl ethers, fatty acid alkanolamides, polyglycol fatty alkyl ethers, ethylene oxide and propylene oxide block copolymers, alkylbetaines, alkylsulphobetaines, tetraalkylammonium salts of mono or dialkylphosphoric acids or surfactants comprising at least one imidazoline group. It is also possible to use surfactants such as those described above containing at least one fluorine substituent. More specifically, surfactants comprising at least one polyfluoro alkyl chain or a polyfluoro aromatic substituent can be used.
A surfactant of alkylbenzenesulphonate type is particularly preferred. This surfactant often comprises an alkyl chain comprising from 4 to 22 and preferably from 10 to 14 carbon atoms. Dodecylbenzenesulphonate salts, in particular the salts of a quaternary amine, give good results. Isopropylammonium dodecylbenzenesulphonate is particularly preferred.
When a surfactant is present in a composition according to the invention, its content is generally at least 100 ppm (mg/kg). It is often at least 500 ppm. Preferably, it is at least 1000 ppm. Generally, the surfactant content is not more than 5000 ppm. It is often not more than 4000 ppm. Preferably, it is not more than 3000 ppm.
In a particular aspect, the solvent is used as a water displacement agent. In another embodiment of the first aspect of the invention, the surface is degreased. In this case, the solvent functions as a degreasing solvent.
A degreasing solvent is used, for example, in the electronics or electromechanical industry to remove the grease adsorbed in particular onto metal components machined with grease. Generally, a component to be degreased is immersed in a bath of boiling degreasing solvent. The compositions according to the invention comprising a non-fluoro organic solvent of high polarity, such as alkanols, in particular methanol or ethanol and/or those which comprise a chlorohydrocarbon, are particularly suitable as degreasing solvents.
In another embodiment of the first aspect of the invention, the solvent is used to remove flux residues. For example, flux residues of soldered electric components are defluxed.
A second aspect of the invention relates to a method for producing polymer foam which comprises using a blowing agent comprising at least one compound described in Tables 1 or 2 of the specification which are mentioned above with their chemical name. In this aspect, the compound is preferably selected from
those described in table 2. More preferably, the compound is selected from compounds No. 4, 17, 25, 26, 28, 30, 38 and 39 described in table 2.
In the second aspect of the invention the foam blowing agent has generally an atmospheric boiling point equal to or higher than 0 0 C, preferably equal to or higher than 20 0 C. In the second aspect of the invention the foam blowing agent has generally an atmospheric boiling point equal to or lower than 45 0 C, preferably equal to or lower than 40 0 C.
In the second aspect of the invention, the content of the compound described in Table 1 or 2 in the foam blowing agent is generally equal to or more than 10 % by weight relative to the weight of the foam blowing agent. Often this content is equal to or more than 30 % by weight and preferably equal to or more than 50 % by weight. In some embodiments of the second aspect of the invention, the content of compound described in Table 1 or 2 in the foam blowing agent can be equal to or lower than 90 % by weight relative to the weight of the foam blowing agent. Other typical contents in these embodiments are equal to or lower than 80 % by weight or even equal to or lower than 75 % by weight.
In the second aspect of the invention, the foam blowing agent can consist or consist essentially of compound described in Table 1 or 2. In the second aspect of the invention the foam blowing agent can for example comprise a non-fluoro organic co-blowing agent as described above for the first aspect of the invention in addition to anyone of the fluorinated compounds described in Tables 1 and 2. Preferably non fluoro organic co- blowing agents to be used in the foam blowing agent are selected from hydrocarbons and halogenated hydrocarbons. If in the second aspect of the invention the foam blowing agent comprises a hydrocarbon, then it is preferred to use a hydrocarbon, in particular an alkane having 3, 4, 5 or 6 carbon atoms. More particulary, cyclopentane, n-pentane and isopentane are preferred. Non- limiting examples of suitable mixtures are the following : • 65 % by weight of 1 , 1 , 1 ,4,4,4-hexafluoro-but-2-ene and 35 % by weight of cyclopentane
• 65 % by weight of N,N,N'-tris-trifluoromethyl- hydrazine and 35 % by weight of isopentane
• 65 % by weight of 1 , 1 , 1 ,2,4,4,4-heptafluoro-3-trifluoromethyl-but-2-ene and 35 % by weight of n-pentane
• 65 % by weight of octafluoro-cyclopentanone and 35 % by weight of n-pentane
• 65 % by weight of (preferably freshly cracked) hexafluoro-cyclopentadiene and 35 % by weight of cyclopentane « 65 % by weight of (Z)-I, l,l,3,4,4,5,5,5-nonafiuoro-pent-2-ene and 35 % by weight of isopentane
• 65 % by weight of 1 , 1 , 1 ,2,2-pentafluoro-2-( 1 , 1 ,2,2-tetrafluoro-ethoxy)-ethane and 35 % by weight of n-pentane
• 65 % by weight of 1 , 1 , 1 ,2,2,3-hexafluoro-3-trifluoromethoxy-propane and 35 % by weight of n-pentane
Other non- limiting examples of blowing agent mixtures include those wherein at least one compound of the group consisting of compounds No. 4, 17, 25, 26, 28, 30, 38 and 39 described in table 2, carbon dioxide and dichloromethane, n-pentane, isopentane or cyclopentane are comprised. In a first particular embodiment of the second aspect of the invention, the polymer foam is a thermoset foam. Thermoset foams which can be produced according to the method according to the invention include, for example, phenolic foams and, preferably, isocyanate-based foams.
The first particular embodiment of the second aspect of the invention relates consequently in particular to a process for producing foams based on polyisocyanates by reacting polyisocyanates, compounds having at least two hydrogen atoms reactive towards isocyanate groups, blowing agents and, if appropriate, further additives, which comprises using a blowing agent as described here above. Polyisocyanates suitable for the process according to the invention are the aliphatic, cyclo aliphatic and aromatic diisocyanates or polyisocyanates usual for this purpose. 2,4- and 2,6-toluyl diisocyanate, diphenylmethane diisocyanate, polymethylenepolyphenyl isocyanate and mixtures thereof are preferred. Polyisocyanates which contain carbodiimide groups, urethane groups, allophanate groups, isocyanurate groups, urea groups or biuret groups and which are termed "modified polyisocyanates" and "isocyanate prepolymers", can also be used.
The polyisocyanates are reacted with compounds which contain at least two hydrogen atoms reactive towards isocyanate groups, for example compounds containing hydroxyl groups and based on polyethers, polyesters and amines, and also compounds having amino groups and/or carboxyl groups and/or thiol
groups. As a rule, these compounds have 2-8 hydrogen atoms reactive towards isocyanates.
The catalysts used in this reaction are often tertiary amines which, if desired, can also contain hydrogen atoms active towards isocyanate groups, and/or organic metal compounds, preferably tin salts of carboxylic acids.
In addition, surface-active additives such as emulsifiers and foam stabilizers are in general also used. The emulsifiers are, for example, salts of fatty acids. Polyethersiloxanes are frequently used as foam stabilizers.
The blowing agent and the polyol component, optionally in the presence of phosphate or phosphonate-type flame retardants, can be present in a premix. Suitable phosphate type flame retardants are, for example, triethyl phosphate, tris-chloropropyl phosphate and tris-chloroethyl phosphate. Suitable phosphonate-type flame retardants are, for example, the diethyl esters of methyl or ethyl phosphonate and the dimethyl esters of methyl or ethyl phosphonate. In a second particular embodiment of the second aspect of the invention, the polymer foam is a thermoplastic foam. In this embodiment the polymer foam is often a polyalkenylaromatic foam, preferably a polystyrene foam and most preferably an extruded polystyrene foam. The polymer foam can also be an expanded polystyrene foam or a thermoplastic polyurethane foam. In a third aspect, the invention relates to the use of a fluorinated olefin having at least 4 carbon atoms and an atmospheric boiling point from 0 0 C to 100 0 C, preferably 10 to 80 0 C as constituent of a foam blowing agent, a solvent, a refrigerant, a heat transfer fluid, a fire extinguishing agent, an etching gas, in particular for semiconductor etching or chamber cleaning or an aerosol propellant. The fluorinated olefin can be cyclic. In that case it often comprises a 3-, 4-, 5-, 6-, or 7-membered ring, preferably a 5-, or 6-membered ring. In a particular embodiment, said fluorinated olefin is a conjugated or non-conjugated diene.
The fluorinated olefin of the third aspect can be combined with non fluoro organic solvents and/or additional fluorinated compounds, as described in the first aspect of the invention, to form compositions having typically the same GWPioo as the solvent in the first aspect of the invention. The invention also concerns these compositions. In said compositions the content of the fluorinated olefin often corresponds to the content of compounds described in Table 1 or 2 in the compositions according to the first aspect of the invention. In this aspect, the olefine l,l,3,3,5,5-hexafluoro-penta-l,4-diene cited under numbers 23 of table 1
and 15 of table 2 and lH:4H-hexafluorcyclopenten cited under number 53 of table 1 and the olefins cited under numbers 4, 25 and 30 in table 2, 1,1,1 ,4,4,4-hexafluoro-but-2-ene, 1,1,1 ,2,4,4,4-heptafluoro-3-trifTuoromethyl- but-2-ene and (Z)-1, 1,1, 3,4,4, 5,5, 5-nonafluoro-pent-2-ene are preferred. Often, the compositions described above are preferred compositions in this third aspect. In a fourth aspect, the invention relates to use of a cyclic fluorinated ether having an atmospheric boiling point from 0 0 C to 100 0 C, preferably 10 to 80 0 C as constituent of a foam blowing agent, a solvent, a refrigerant, a heat transfer fluid, a fire extinguishing agent, an etching gas, in particular for semiconductor etching or chamber cleaning or an aerosol propellant. The cyclic ether often comprises a 3-, A-, 5-, 6-, or 7-membered ring, preferably a 5-, or 6-membered ring. The compounds cited under numbers 1 and 5 described in table 1 are preferred. The cyclic ether of the fourth aspect can be combined with non fluoro organic solvents and/or additional fluorinated compounds, as described in the first aspect of the invention, to form compositions having typically the same GWPioo as the solvent in the first aspect of the invention. The invention also concerns these compositions. In said compositions the content of the cyclic ether often corresponds to the content of compounds described in Table 1 or 2 in the compositions according to the first aspect of the invention. The compounds cited under numbers 1 and 5 described in table 1 are preferred.
In a fifth aspect, the invention relates to the use of a fluorinated N- heterocyclic compound having an atmospheric boiling point from 0 0 C to 100 0 C, preferably 10 to 80 0 C as constituent of a foam blowing agent, a solvent, a refrigerant, a heat transfer fluid, a fire extinguishing agent an etching gas, in particular for semiconductor etching or chamber cleaning or an aerosol propellant. The N-heterocycle is often a 3-, 4-, 5-, 6-, or 7-membered ring, preferably a 5-, or 6-membered ring.
The fluorinated N-heterocyclic compound of the fifth aspect can be combined with non fluoro organic solvents and/or additional fluorinated compounds, as described in the first aspect of the invention, to form compositions having typically the same GWP ioo as the solvent in the first aspect of the invention. The invention also concerns these compositions. In said compositions the content of the fluorinated N-heterocyclic compound often corresponds to the content of compounds described in Table 1 or 2 in the compositions according to the first aspect of the invention.
In a sixth aspect, the invention relates to use of a fluorinated unsaturated nitrogen containing compound having an atmospheric boiling point from 0 0 C to 100 0 C, preferably 10 to 80 0 C as constituent of a foam blowing agent, a solvent, a refrigerant, a heat transfer fluid, a fire extinguishing agent an etching gas, in particular for semiconductor etching or chamber cleaning or an aerosol propellant.
The fluorinated unsaturated nitrogen containing compound of the sixth aspect can be combined with non fluoro organic solvents and/or additional fluorinated compounds, as described in the first aspect of the invention, to form compositions having typically the same GWP 100 as the solvent in the first aspect of the invention. The invention also concerns these compositions. In said compositions the content of the unsaturated nitrogen containing compound often corresponds to the content of compounds described in Table 1 or 2 in the compositions according to the first aspect of the invention. In a seventh aspect, the invention relates to use of a cyclic fluorinated ketone having an atmospheric boiling point from 0 0 C to 100 0 C, preferably 10 to 80 0 C as constituent of a foam blowing agent, a solvent, a refrigerant, a heat transfer fluid, a fire extinguishing agent, an etching gas, in particular for semiconductor etching or chamber cleaning or an aerosol propellant. The cyclic fluorinated ketone of the seventh aspect can be combined with non fluoro organic solvents and/or additional fluorinated compounds, as described in the first aspect of the invention, to form compositions having typically the same GWP 100 as the solvent in the first aspect of the invention. The invention also concerns these compositions. In said compositions the content of the cyclic fluorinated ketone often corresponds to the content of compounds described in Table 1 or 2 in the compositions according to the first aspect of the invention.
In an eight aspect, the invention relates to use of a compound disclosed in table 1 or 2 as etching gas, in particular for semiconductor etching or chamber cleaning. In this embodiment, in particular silicon-free compounds are used. More preferably the atmospheric boiling point of the compound is equal to or lower than 30 0 C.
In an ninth aspect, the invention relates to the use of a compound disclosed in table 1 or 2 as carrier fluid to depose layers of material, for example organic materials and in particular greases on a surface.
A tenth aspect of the present invention concerns mixtures of (1,1,2,3, 3,3- hexafluoro-propyl)-methyl ether, and ethanol or perfluoropoly ether available under GALDEN® HT 55 available from Solvay Solexis. The preferred binary mixtures of (1,1, 2,3,3, 3-hexafluoro-propyl)-methyl ether, and ethanol consist of 1.6 to 50 % by volume ethanol, preferably 6.3 % by volume to 38.8 % by volume, the remainder to 100 % by volume is (1,1,2, 3,3, 3-hexafluoro-propyl)- methyl ether. The preferred binary mixtures of (1,1, 2,3,3, 3-hexafluoro-propyl)- methyl ether, and GALDEN® HT 55 consist of 1.5 to 75 % by weight GALDEN® HT 55, preferably 10 to 70 % by weight, the remainder to 100 % by weight is (l,l,2,3,3,3-hexafluoro-propyl)-methyl ether. The advantage of these mixtures is their unexpected low boiling point which is lower than the lower- boiling component. To these mixtures, further solvents, foam blowing agents, propellants or other components and additives can be added.
The following tables list the boiling points for specific mixtures :
It was observed that the mixtures of mixtures of (1,1,2, 3,3, 3-hexafluoro- propyl)-methyl ether, and ethanol or perfluoropoly ether include azeotropes and azeotrope like compositions formed from the compound described under number 10 of table 1, (1, 1,2,3, 3,3-hexafluoro-propyl)-methyl ether, and ethanol or perfluoropoly ether available under GALDEN® HT 55 available from Solvay Solexis. An azeotrope-like mixture in the frame of the present invention is a mixture of two or more fluids having a vapor composition substantially equal to
that of the liquid and which undergoes phase changes without substantially modifying its composition and temperature. According to the present invention, a mixture is azeotrope-like when, after evaporation at a constant temperature of 50 % of the initial liquid mass, the per cent variation of the vapor pressure between that of the initial mixture and that of the final mixture results lower than about 10 %. See on the matter the paper of D. A. Didion and D. B. Bivens in Int. J. of Refrigeration 13 (1990), pages 163 to 175.
The binary azeotrope formed from (l,l,2,3,3,3-hexafluoro-propyl)-methyl ether and ethanol has a minimum boiling point of about 51.1 0 C at about 990 mbar. The composition is about 13 % by volume of ethanol and about 87 % by volume of (1,1,2, 3,3, 3-hexafluoro-propyl)-methyl ether.
The binary azeotrope formed from (l,l,2,3,3,3-hexafluoro-propyl)-methyl ether and GALDEN® HT 55 has a minimum boiling point of about 41.3°C at 977 mbar. The minimum boiling point appears at range of the composition at about 50 to about 55 mol- % of GALDEN® HT 55 and the remainder to 100 mol % of (1,1,2, 3,3, 3-hexafluoro-propyl)-methyl ether.
These binary azeotropes and respective near azeotropes are suitable, for example, as foam blowing agents or solvents. When used as solvents, they may contain further solvents, e.g. 1 ,2-trans-dichloroethylene, or additives, e.g. surfactants, for example, surfactants as those described above. When used as foam blowing agents, they may contain further blowing agents, e.g. one or more of those mentioned above, e.g. carbon dioxide, cyclopentane, n-pentane and/or isopentane.
Here after table 1 and 2 describe compounds which are useful in this invention.
TABLE 1
TABLE 2
The following examples are intended to explain the invention in further detail without intending to limit it. Examples concerning solvent uses : Example 1 : Solvents for degreasing
Example 1.1 : An azeotropic mixture was prepared from (l,l,2,3,3,3-hexafiuoro-propyl)-methyl ether and GALDEN® TH55 by mixing them in a molar ratio of 1 : 1. To the resulting mixture, 1 ,2-trans-dichloroethylene is added in an amount that, in the resulting mixture, it is contained in an amount of about 25 % by weight. The resulting mixture is used for degreasing metal parts by immersing the metal parts into the mixture, lifting the parts out of the mixture, removing adhering liquid and drying the parts.
Example 1.2 : Example 1.1 is repeated, but this time, ethanol is added in an amount that it is contained in the resulting mixture in an amount of 10 % by weight. The resulting mixture is used for removal of water adhering to metal parts by immersing the metal parts into the mixture, lifting the parts out of the mixture, removing adhering liquid and drying the parts.
Example 1.3 : An azeotropic mixture was prepared from (1,1,2, 3,3, 3-hexafluoro-propyl)-methyl ether and ethanol by mixing them in a volume ratio of 87: 13. The resulting mixture is used for removal of water adhering to metal parts by immersing the metal parts into the mixture, lifting the parts out of the mixture, removing adhering liquid and drying the parts.
Example 1.4 : Example 1.3 is repeated. To the resulting azeotropic mixture, 1 ,2-trans-dichloroethylene is added in an amount that, in the resulting mixture, it is contained in an amount of about 25 % by weight. The resulting mixture is used for degreasing metal parts by immersing the metal parts into the mixture, lifting the parts out of the mixture, removing adhering liquid and drying the parts.
Example 1.5 : 3,3,4,4-tetrafluoro-tetrahydro-furane and 1,2-trans- dichloroethylene are mixed in a weight ratio of 1 : 1. The resulting mixture is used for degreasing metal parts by immersing the metal parts into the mixture, lifting the parts out of the mixture, removing adhering liquid and drying the parts.
Example 1.6 : Example 1.5 is repeated, but this time, methanol is added in such an amount that the resulting mixture contains 10 % by weight of methanol. The resulting mixture is used for removal of water adhering to metal parts by immersing the metal parts into the mixture, lifting the parts out of the mixture, removing adhering liquid and drying the parts.
Example 1.7 : Example 1.6 is repeated, but this time, a Isopropylammonium dodecylbenzenesulphonate is added as surfactant in such an amount that it is contained in the resulting mixture in an amount of 1 % by weight. The resulting mixture is used for degreasing metal parts by immersing the metal parts into the mixture, lifting the parts out of the mixture, removing adhering liquid and drying the parts.
Example 1.8 : Example 1.6 is repeated, but this time, N-methylpyrollidone is added in such an amount that in the resulting mixture, it is contained in an amount of 5 % by weight. The resulting mixture is used for degreasing metal parts by immersing the metal parts into the mixture, lifting the parts out of the mixture, removing adhering liquid and drying the parts. Example 2 : Use as foam blowing agents :
Example 2.1 : Preparation of a thermoplastic foam
200 kg of Polystyrol (melt index 3.0 to 110) are mixed with 2 kg talcum as nucleating agent. The resulting mixture is filled into a conventional extruder apparatus and molten therein. Into the melt, l,l,l,2,4,4,4-heptafluoro-3- trifluoromethyl-but-2-ene is injected such that this blowing agent is contained in an amount of about 8.5 % by weight in the resulting mixture. The resulting mixture is extruded via an extruder die to provide a closed cell foam.
Example 2.2 : Preparation of a polyurethane foam
2.2.1. Preparation of a premix : A mixture containg 80 % ny weight of polyetherpolyol (Tercarol A350), 10 % by weight of 1,1,1, 2,4,4,4-heptafluoro-3- trifluoromethyl-but-2-ene and 10 % by weight of triethylphosphatejs prepared by mixing the respective compounds.
2.2.2. Foaming : The premix of 2.2.1. is mixed with diphenylmethane diisocyanate ; the latter is applied in an amount which was 10 % higher than stoechiometrically needed. The extrusion is then performed in a low pressure extruder to provide a closed cell polyurethane foam.
Example 3 : Use as etching agent
Etching can be performed in an Inductive Coupled Plasma Source (ICP) etch reactor or in a Capacitively Coupled Plasma Source (CCP) reactor which is available from Applied Materials. A self-aligned contact (SAC) is formed as described in FIG. 1 and page 3 of WO 2000/302168. A polysilicon gate layer, a tungsten suicide barrier and glue layer, and a silicon nitride cap layer are deposited and photolithographically formed into two closely related spaced gate structures having a gap there between. Then, a silicon nitride layer is deposited
via CVD on the structure, and dopant ions are implanted. A dielectric SiC> 2 layer is deposited over the structure, a photoresist layer is deposited over the over the oxide layer and photographically defined using light with a wavelength of 193 nm into a mask. Then, using l,l,3,3-tetrafluoro-2-methyl-propene and argon, delivered in a weight ratio of 1 :4 into the plasma reactor, the SiC> 2 layer is etched.
Example 3 can be repeated using low-k dielectric layers or ultra-low-k dielectric layers instead of SiC> 2 layers.
Example 3 is repeated using l,l,3,3,5,5-hexafluoro-penta-l,4-diene.
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