CN109971431A - Composition comprising fluoroolefin - Google Patents
Composition comprising fluoroolefin Download PDFInfo
- Publication number
- CN109971431A CN109971431A CN201910001475.5A CN201910001475A CN109971431A CN 109971431 A CN109971431 A CN 109971431A CN 201910001475 A CN201910001475 A CN 201910001475A CN 109971431 A CN109971431 A CN 109971431A
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- China
- Prior art keywords
- hfc
- composition
- butane
- dimethyl ether
- temperature
- Prior art date
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- Pending
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- 239000000203 mixture Substances 0.000 title claims abstract description 288
- 238000000034 method Methods 0.000 claims abstract description 65
- 238000004378 air conditioning Methods 0.000 claims abstract description 54
- 239000000126 substance Substances 0.000 claims abstract description 32
- 239000003380 propellant Substances 0.000 claims abstract description 6
- 239000004088 foaming agent Substances 0.000 claims abstract description 5
- 239000003507 refrigerant Substances 0.000 claims description 95
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 claims description 76
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 75
- 238000005057 refrigeration Methods 0.000 claims description 70
- -1 2- methybutane Chemical compound 0.000 claims description 58
- 229910052799 carbon Inorganic materials 0.000 claims description 57
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 55
- NPNPZTNLOVBDOC-UHFFFAOYSA-N 1,1-difluoroethane Chemical compound CC(F)F NPNPZTNLOVBDOC-UHFFFAOYSA-N 0.000 claims description 50
- 150000001875 compounds Chemical class 0.000 claims description 44
- IJDNQMDRQITEOD-UHFFFAOYSA-N sec-butylidene Natural products CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims description 42
- 239000000314 lubricant Substances 0.000 claims description 41
- 239000000463 material Substances 0.000 claims description 41
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 40
- YFMFNYKEUDLDTL-UHFFFAOYSA-N 1,1,1,2,3,3,3-heptafluoropropane Chemical compound FC(F)(F)C(F)C(F)(F)F YFMFNYKEUDLDTL-UHFFFAOYSA-N 0.000 claims description 39
- 239000001282 iso-butane Substances 0.000 claims description 38
- 235000013847 iso-butane Nutrition 0.000 claims description 38
- WXGNWUVNYMJENI-UHFFFAOYSA-N 1,1,2,2-tetrafluoroethane Chemical compound FC(F)C(F)F WXGNWUVNYMJENI-UHFFFAOYSA-N 0.000 claims description 36
- LVGUZGTVOIAKKC-UHFFFAOYSA-N 1,1,1,2-tetrafluoroethane Chemical compound FCC(F)(F)F LVGUZGTVOIAKKC-UHFFFAOYSA-N 0.000 claims description 34
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 33
- 229910052739 hydrogen Inorganic materials 0.000 claims description 30
- 239000001257 hydrogen Substances 0.000 claims description 29
- VPAYJEUHKVESSD-UHFFFAOYSA-N trifluoroiodomethane Chemical compound FC(F)(F)I VPAYJEUHKVESSD-UHFFFAOYSA-N 0.000 claims description 29
- 239000002904 solvent Substances 0.000 claims description 28
- 125000004432 carbon atom Chemical group C* 0.000 claims description 25
- RWRIWBAIICGTTQ-UHFFFAOYSA-N difluoromethane Chemical compound FCF RWRIWBAIICGTTQ-UHFFFAOYSA-N 0.000 claims description 25
- 239000004215 Carbon black (E152) Substances 0.000 claims description 23
- 125000001931 aliphatic group Chemical group 0.000 claims description 22
- 229930195733 hydrocarbon Natural products 0.000 claims description 22
- 150000002576 ketones Chemical class 0.000 claims description 21
- 150000002596 lactones Chemical class 0.000 claims description 21
- 125000000217 alkyl group Chemical group 0.000 claims description 20
- 239000000975 dye Substances 0.000 claims description 20
- MSSNHSVIGIHOJA-UHFFFAOYSA-N pentafluoropropane Chemical compound FC(F)CC(F)(F)F MSSNHSVIGIHOJA-UHFFFAOYSA-N 0.000 claims description 20
- 239000001294 propane Substances 0.000 claims description 20
- 239000003153 chemical reaction reagent Substances 0.000 claims description 17
- 239000003795 chemical substances by application Substances 0.000 claims description 17
- 150000002825 nitriles Chemical class 0.000 claims description 17
- UJMWVICAENGCRF-UHFFFAOYSA-N oxygen difluoride Chemical compound FOF UJMWVICAENGCRF-UHFFFAOYSA-N 0.000 claims description 17
- NSGXIBWMJZWTPY-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropane Chemical compound FC(F)(F)CC(F)(F)F NSGXIBWMJZWTPY-UHFFFAOYSA-N 0.000 claims description 16
- 150000002148 esters Chemical class 0.000 claims description 16
- 125000002723 alicyclic group Chemical group 0.000 claims description 15
- 150000001408 amides Chemical class 0.000 claims description 15
- 150000002430 hydrocarbons Chemical class 0.000 claims description 15
- 239000000700 radioactive tracer Substances 0.000 claims description 15
- FYIRUPZTYPILDH-UHFFFAOYSA-N 1,1,1,2,3,3-hexafluoropropane Chemical compound FC(F)C(F)C(F)(F)F FYIRUPZTYPILDH-UHFFFAOYSA-N 0.000 claims description 14
- 239000013529 heat transfer fluid Substances 0.000 claims description 14
- 150000008378 aryl ethers Chemical class 0.000 claims description 13
- 238000004880 explosion Methods 0.000 claims description 13
- 239000002480 mineral oil Substances 0.000 claims description 13
- GTLACDSXYULKMZ-UHFFFAOYSA-N pentafluoroethane Chemical compound FC(F)C(F)(F)F GTLACDSXYULKMZ-UHFFFAOYSA-N 0.000 claims description 13
- UJPMYEOUBPIPHQ-UHFFFAOYSA-N 1,1,1-trifluoroethane Chemical compound CC(F)(F)F UJPMYEOUBPIPHQ-UHFFFAOYSA-N 0.000 claims description 12
- 239000011737 fluorine Chemical group 0.000 claims description 12
- 229910052731 fluorine Chemical group 0.000 claims description 12
- 235000010446 mineral oil Nutrition 0.000 claims description 12
- 150000005846 sugar alcohols Polymers 0.000 claims description 12
- WZLFPVPRZGTCKP-UHFFFAOYSA-N 1,1,1,3,3-pentafluorobutane Chemical compound CC(F)(F)CC(F)(F)F WZLFPVPRZGTCKP-UHFFFAOYSA-N 0.000 claims description 11
- 239000000460 chlorine Chemical group 0.000 claims description 11
- 229910052801 chlorine Inorganic materials 0.000 claims description 11
- UHCBBWUQDAVSMS-UHFFFAOYSA-N fluoroethane Chemical compound CCF UHCBBWUQDAVSMS-UHFFFAOYSA-N 0.000 claims description 11
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 10
- 150000001336 alkenes Chemical class 0.000 claims description 10
- HZIVRQOIUMAXID-UHFFFAOYSA-N oxocane Chemical compound C1CCCOCCC1 HZIVRQOIUMAXID-UHFFFAOYSA-N 0.000 claims description 10
- 125000003118 aryl group Chemical group 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical class CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 150000004996 alkyl benzenes Chemical class 0.000 claims description 8
- 239000006260 foam Substances 0.000 claims description 8
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical group [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 7
- 230000015572 biosynthetic process Effects 0.000 claims description 7
- 125000004122 cyclic group Chemical group 0.000 claims description 7
- 238000001704 evaporation Methods 0.000 claims description 7
- 229920005862 polyol Polymers 0.000 claims description 7
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical class [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 claims description 6
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 claims description 6
- 239000002131 composite material Substances 0.000 claims description 6
- 150000001924 cycloalkanes Chemical class 0.000 claims description 6
- 239000012188 paraffin wax Substances 0.000 claims description 6
- 239000002516 radical scavenger Substances 0.000 claims description 6
- 238000006467 substitution reaction Methods 0.000 claims description 6
- 238000003786 synthesis reaction Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000000443 aerosol Substances 0.000 claims description 5
- 239000012530 fluid Substances 0.000 claims description 5
- 239000003205 fragrance Substances 0.000 claims description 5
- UFWIBTONFRDIAS-UHFFFAOYSA-N naphthalene-acid Natural products C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 5
- 229920001515 polyalkylene glycol Polymers 0.000 claims description 5
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 4
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 4
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 claims description 4
- 239000000470 constituent Substances 0.000 claims description 4
- 230000008020 evaporation Effects 0.000 claims description 4
- CBOIHMRHGLHBPB-UHFFFAOYSA-N hydroxymethyl Chemical compound O[CH2] CBOIHMRHGLHBPB-UHFFFAOYSA-N 0.000 claims description 4
- 230000000873 masking effect Effects 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- VWCLQNINSPFHFV-UHFFFAOYSA-N 10-oxapentacyclo[12.8.0.02,11.04,9.015,20]docosa-1(14),2(11),4,6,8,12,15,17,19,21-decaene Chemical compound C1=CC=C2C3=CC=C4OC5=CC=CC=C5CC4=C3C=CC2=C1 VWCLQNINSPFHFV-UHFFFAOYSA-N 0.000 claims description 3
- GJCOSYZMQJWQCA-UHFFFAOYSA-N 9H-xanthene Chemical compound C1=CC=C2CC3=CC=CC=C3OC2=C1 GJCOSYZMQJWQCA-UHFFFAOYSA-N 0.000 claims description 3
- PQMOXTJVIYEOQL-UHFFFAOYSA-N Cumarin Natural products CC(C)=CCC1=C(O)C(C(=O)C(C)CC)=C(O)C2=C1OC(=O)C=C2CCC PQMOXTJVIYEOQL-UHFFFAOYSA-N 0.000 claims description 3
- FSOGIJPGPZWNGO-UHFFFAOYSA-N Meomammein Natural products CCC(C)C(=O)C1=C(O)C(CC=C(C)C)=C(O)C2=C1OC(=O)C=C2CCC FSOGIJPGPZWNGO-UHFFFAOYSA-N 0.000 claims description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 3
- XJHABGPPCLHLLV-UHFFFAOYSA-N benzo[de]isoquinoline-1,3-dione Chemical compound C1=CC(C(=O)NC2=O)=C3C2=CC=CC3=C1 XJHABGPPCLHLLV-UHFFFAOYSA-N 0.000 claims description 3
- ZYGHJZDHTFUPRJ-UHFFFAOYSA-N coumarin Chemical compound C1=CC=C2OC(=O)C=CC2=C1 ZYGHJZDHTFUPRJ-UHFFFAOYSA-N 0.000 claims description 3
- GNBHRKFJIUUOQI-UHFFFAOYSA-N fluorescein Chemical compound O1C(=O)C2=CC=CC=C2C21C1=CC=C(O)C=C1OC1=CC(O)=CC=C21 GNBHRKFJIUUOQI-UHFFFAOYSA-N 0.000 claims description 3
- QDLAGTHXVHQKRE-UHFFFAOYSA-N lichenxanthone Natural products COC1=CC(O)=C2C(=O)C3=C(C)C=C(OC)C=C3OC2=C1 QDLAGTHXVHQKRE-UHFFFAOYSA-N 0.000 claims description 3
- 239000001272 nitrous oxide Chemical class 0.000 claims description 3
- 150000003077 polyols Chemical class 0.000 claims description 3
- 239000003381 stabilizer Substances 0.000 claims description 3
- PQJUJGAVDBINPI-UHFFFAOYSA-N 9H-thioxanthene Chemical compound C1=CC=C2CC3=CC=CC=C3SC2=C1 PQJUJGAVDBINPI-UHFFFAOYSA-N 0.000 claims description 2
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 claims description 2
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 claims description 2
- 150000001299 aldehydes Chemical class 0.000 claims description 2
- 238000013461 design Methods 0.000 claims description 2
- 230000002401 inhibitory effect Effects 0.000 claims description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 claims description 2
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims description 2
- 150000002431 hydrogen Chemical group 0.000 claims 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims 3
- QIROQPWSJUXOJC-UHFFFAOYSA-N 1,1,2,2,3,3,4,4,5,5,6-undecafluoro-6-(trifluoromethyl)cyclohexane Chemical compound FC(F)(F)C1(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C1(F)F QIROQPWSJUXOJC-UHFFFAOYSA-N 0.000 claims 2
- MEBONNVPKOBPEA-UHFFFAOYSA-N 1,1,2-trimethylcyclohexane Chemical compound CC1CCCCC1(C)C MEBONNVPKOBPEA-UHFFFAOYSA-N 0.000 claims 2
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 claims 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical group FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims 2
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 claims 2
- 235000019441 ethanol Nutrition 0.000 claims 2
- ATUOYWHBWRKTHZ-AUOAYUKBSA-N 1,1,1,2,2,3,3,3-octadeuteriopropane Chemical compound [2H]C([2H])([2H])C([2H])([2H])C([2H])([2H])[2H] ATUOYWHBWRKTHZ-AUOAYUKBSA-N 0.000 claims 1
- SUAMPXQALWYDBK-UHFFFAOYSA-N 1,1,1,2,2,3-hexafluoropropane Chemical compound FCC(F)(F)C(F)(F)F SUAMPXQALWYDBK-UHFFFAOYSA-N 0.000 claims 1
- CMBKOSTZCGEKQA-UHFFFAOYSA-N 1,1,2,2,3,3,4,5,6,7-decafluoroindene Chemical compound FC1=C(F)C(F)=C2C(F)(F)C(F)(F)C(F)(F)C2=C1F CMBKOSTZCGEKQA-UHFFFAOYSA-N 0.000 claims 1
- PAAZPARNPHGIKF-UHFFFAOYSA-N 1,2-dibromoethane Chemical compound BrCCBr PAAZPARNPHGIKF-UHFFFAOYSA-N 0.000 claims 1
- XPDWGBQVDMORPB-UHFFFAOYSA-N Fluoroform Chemical compound FC(F)F XPDWGBQVDMORPB-UHFFFAOYSA-N 0.000 claims 1
- 125000002252 acyl group Chemical group 0.000 claims 1
- 150000001412 amines Chemical class 0.000 claims 1
- DIKBFYAXUHHXCS-UHFFFAOYSA-N bromoform Chemical compound BrC(Br)Br DIKBFYAXUHHXCS-UHFFFAOYSA-N 0.000 claims 1
- GZUXJHMPEANEGY-UHFFFAOYSA-N bromomethane Chemical compound BrC GZUXJHMPEANEGY-UHFFFAOYSA-N 0.000 claims 1
- 238000009833 condensation Methods 0.000 claims 1
- 230000005494 condensation Effects 0.000 claims 1
- YSLFMGDEEXOKHF-UHFFFAOYSA-N difluoro(iodo)methane Chemical compound FC(F)I YSLFMGDEEXOKHF-UHFFFAOYSA-N 0.000 claims 1
- AQYSYJUIMQTRMV-UHFFFAOYSA-N hypofluorous acid Chemical compound FO AQYSYJUIMQTRMV-UHFFFAOYSA-N 0.000 claims 1
- LYGJENNIWJXYER-BJUDXGSMSA-N nitromethane Chemical group [11CH3][N+]([O-])=O LYGJENNIWJXYER-BJUDXGSMSA-N 0.000 claims 1
- 229950011087 perflunafene Drugs 0.000 claims 1
- LOQGSOTUHASIHI-UHFFFAOYSA-N perfluoro-1,3-dimethylcyclohexane Chemical compound FC(F)(F)C1(F)C(F)(F)C(F)(F)C(F)(F)C(F)(C(F)(F)F)C1(F)F LOQGSOTUHASIHI-UHFFFAOYSA-N 0.000 claims 1
- UWEYRJFJVCLAGH-IJWZVTFUSA-N perfluorodecalin Chemical compound FC1(F)C(F)(F)C(F)(F)C(F)(F)[C@@]2(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)[C@@]21F UWEYRJFJVCLAGH-IJWZVTFUSA-N 0.000 claims 1
- 229920001289 polyvinyl ether Polymers 0.000 claims 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims 1
- JRHMNRMPVRXNOS-UHFFFAOYSA-N trifluoro(methoxy)methane Chemical compound COC(F)(F)F JRHMNRMPVRXNOS-UHFFFAOYSA-N 0.000 claims 1
- OCEBOBGSOQRMQZ-UHFFFAOYSA-N trifluoromethylcyclopentane Chemical compound FC(F)(F)C1CCCC1 OCEBOBGSOQRMQZ-UHFFFAOYSA-N 0.000 claims 1
- 239000007788 liquid Substances 0.000 abstract description 11
- 238000010438 heat treatment Methods 0.000 abstract description 6
- 230000001629 suppression Effects 0.000 abstract description 6
- 238000007710 freezing Methods 0.000 abstract description 4
- 230000008014 freezing Effects 0.000 abstract description 4
- 238000000889 atomisation Methods 0.000 abstract description 2
- 238000012546 transfer Methods 0.000 abstract description 2
- 150000001721 carbon Chemical group 0.000 description 41
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 20
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 19
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 19
- 229910002092 carbon dioxide Inorganic materials 0.000 description 18
- 239000007850 fluorescent dye Substances 0.000 description 17
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 15
- FXRLMCRCYDHQFW-UHFFFAOYSA-N 2,3,3,3-tetrafluoropropene Chemical compound FC(=C)C(F)(F)F FXRLMCRCYDHQFW-UHFFFAOYSA-N 0.000 description 14
- 238000001816 cooling Methods 0.000 description 13
- VOPWNXZWBYDODV-UHFFFAOYSA-N Chlorodifluoromethane Chemical compound FC(F)Cl VOPWNXZWBYDODV-UHFFFAOYSA-N 0.000 description 11
- 239000000654 additive Substances 0.000 description 11
- 239000003921 oil Substances 0.000 description 11
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical group [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 10
- 238000009835 boiling Methods 0.000 description 10
- 238000007906 compression Methods 0.000 description 10
- 238000001514 detection method Methods 0.000 description 10
- 230000006835 compression Effects 0.000 description 9
- 229910052760 oxygen Inorganic materials 0.000 description 9
- 125000001424 substituent group Chemical group 0.000 description 9
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 8
- 239000001301 oxygen Substances 0.000 description 8
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 7
- 238000010792 warming Methods 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 230000000996 additive effect Effects 0.000 description 6
- 238000004821 distillation Methods 0.000 description 6
- 125000005842 heteroatom Chemical group 0.000 description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 5
- 125000002947 alkylene group Chemical group 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 5
- PXBRQCKWGAHEHS-UHFFFAOYSA-N dichlorodifluoromethane Chemical compound FC(F)(Cl)Cl PXBRQCKWGAHEHS-UHFFFAOYSA-N 0.000 description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 230000005764 inhibitory process Effects 0.000 description 5
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 5
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 5
- GRVDJDISBSALJP-UHFFFAOYSA-N methyloxidanyl Chemical compound [O]C GRVDJDISBSALJP-UHFFFAOYSA-N 0.000 description 5
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 5
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 125000005702 oxyalkylene group Chemical group 0.000 description 5
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Chemical group CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 4
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 4
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 description 4
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 4
- 125000004429 atom Chemical group 0.000 description 4
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- 150000002513 isocyanates Chemical class 0.000 description 1
- 238000009533 lab test Methods 0.000 description 1
- 150000003951 lactams Chemical class 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 230000004807 localization Effects 0.000 description 1
- 238000002483 medication Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- ZSUUCLLIOSUIFH-UHFFFAOYSA-N n,n-di(propan-2-yl)acetamide Chemical compound CC(C)N(C(C)C)C(C)=O ZSUUCLLIOSUIFH-UHFFFAOYSA-N 0.000 description 1
- NZMAJUHVSZBJHL-UHFFFAOYSA-N n,n-dibutylformamide Chemical compound CCCCN(C=O)CCCC NZMAJUHVSZBJHL-UHFFFAOYSA-N 0.000 description 1
- PZYDAVFRVJXFHS-UHFFFAOYSA-N n-cyclohexyl-2-pyrrolidone Chemical compound O=C1CCCN1C1CCCCC1 PZYDAVFRVJXFHS-UHFFFAOYSA-N 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 1
- VKCYHJWLYTUGCC-UHFFFAOYSA-N nonan-2-one Chemical compound CCCCCCCC(C)=O VKCYHJWLYTUGCC-UHFFFAOYSA-N 0.000 description 1
- WSGCRAOTEDLMFQ-UHFFFAOYSA-N nonan-5-one Chemical compound CCCCC(=O)CCCC WSGCRAOTEDLMFQ-UHFFFAOYSA-N 0.000 description 1
- PLZZPPHAMDJOSR-UHFFFAOYSA-N nonanenitrile Chemical compound CCCCCCCCC#N PLZZPPHAMDJOSR-UHFFFAOYSA-N 0.000 description 1
- YSIMAPNUZAVQER-UHFFFAOYSA-N octanenitrile Chemical compound CCCCCCCC#N YSIMAPNUZAVQER-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 150000002905 orthoesters Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 150000002924 oxiranes Chemical class 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- DLRJIFUOBPOJNS-UHFFFAOYSA-N phenetole Chemical compound CCOC1=CC=CC=C1 DLRJIFUOBPOJNS-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 150000008301 phosphite esters Chemical class 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- MCSINKKTEDDPNK-UHFFFAOYSA-N propyl propionate Chemical compound CCCOC(=O)CC MCSINKKTEDDPNK-UHFFFAOYSA-N 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000008521 reorganization Effects 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- 125000000446 sulfanediyl group Chemical group *S* 0.000 description 1
- WMOVHXAZOJBABW-UHFFFAOYSA-N tert-butyl acetate Chemical compound CC(=O)OC(C)(C)C WMOVHXAZOJBABW-UHFFFAOYSA-N 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- CYRMSUTZVYGINF-UHFFFAOYSA-N trichlorofluoromethane Chemical compound FC(Cl)(Cl)Cl CYRMSUTZVYGINF-UHFFFAOYSA-N 0.000 description 1
- CYIFVRUOHKNECG-UHFFFAOYSA-N tridecan-2-one Chemical compound CCCCCCCCCCCC(C)=O CYIFVRUOHKNECG-UHFFFAOYSA-N 0.000 description 1
- ULIAPOFMBCCSPE-UHFFFAOYSA-N tridecan-7-one Chemical compound CCCCCCC(=O)CCCCCC ULIAPOFMBCCSPE-UHFFFAOYSA-N 0.000 description 1
- WKJHMKQSIBMURP-UHFFFAOYSA-N tridecanenitrile Chemical compound CCCCCCCCCCCCC#N WKJHMKQSIBMURP-UHFFFAOYSA-N 0.000 description 1
- OFHCXWMZXQBQMH-UHFFFAOYSA-N trifluoro(trifluoromethylsulfanyl)methane Chemical class FC(F)(F)SC(F)(F)F OFHCXWMZXQBQMH-UHFFFAOYSA-N 0.000 description 1
- SZKKNEOUHLFYNA-UHFFFAOYSA-N undecanenitrile Chemical compound CCCCCCCCCCC#N SZKKNEOUHLFYNA-UHFFFAOYSA-N 0.000 description 1
- 125000004417 unsaturated alkyl group Chemical group 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
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- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
- C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
- C08J9/149—Mixtures of blowing agents covered by more than one of the groups C08J9/141 - C08J9/143
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- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D1/00—Fire-extinguishing compositions; Use of chemical substances in extinguishing fires
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- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/02—Materials undergoing a change of physical state when used
- C09K5/04—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa
- C09K5/041—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems
- C09K5/044—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems comprising halogenated compounds
- C09K5/045—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems comprising halogenated compounds containing only fluorine as halogen
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M171/00—Lubricating compositions characterised by purely physical criteria, e.g. containing as base-material, thickener or additive, ingredients which are characterised exclusively by their numerically specified physical properties, i.e. containing ingredients which are physically well-defined but for which the chemical nature is either unspecified or only very vaguely indicated
- C10M171/008—Lubricant compositions compatible with refrigerants
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- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/12—Organic compounds only containing carbon, hydrogen and oxygen atoms, e.g. ketone or alcohol
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- C08J2203/00—Foams characterized by the expanding agent
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- C08J2203/142—Halogenated saturated hydrocarbons, e.g. H3C-CF3
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- C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
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- C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
- C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
- C10M2203/1006—Petroleum or coal fractions, e.g. tars, solvents, bitumen used as base material
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- C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
- C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
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- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
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- C10M2207/283—Esters of polyhydroxy compounds
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- C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2209/04—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an alcohol or ester thereof; bound to an aldehyde, ketonic, ether, ketal or acetal radical
- C10M2209/043—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an alcohol or ester thereof; bound to an aldehyde, ketonic, ether, ketal or acetal radical used as base material
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- C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
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Abstract
Composition comprising fluoroolefin.The present invention relates to for freezing, the composition of air-conditioning and heat pump system, wherein the composition include fluoroolefin and at least one other component.Composition of the invention can be used for freezing or heating method, is used as heat transfer liquids, foaming agent, atomization propellant and suppression fire and extinguishing chemical.
Description
The information of related application
The application is the divisional application of Chinese patent application 201510623155.5, aforementioned Chinese patent application
201510623155.5 be again international application no be PCT/US2006/008164, international filing date be on March 3rd, 2006, invention
The divisional application original application of the application for a patent for invention of entitled " including the composition of fluoroolefin " enters National Phase in China and obtains
The national application number obtained is 2006800154380.
This application claims the U.S. Provisional Application submitted on March 4th, 2005 on August 23rd, 60/658,543,2005 to mention
The priority for the U.S. Provisional Application 60/732,769 that the U.S. Provisional Application 60/710,439 and 2005 year of friendship was submitted at November 1
Equity.
Technical field
The present invention relates to for freezing, the composition of air-conditioning and heat pump system, wherein the composition include fluoroolefin
With at least one other component.Composition of the invention can be used for freezing or heating method, is used as heat-transfer fluid, foaming agent, gas
Aerosol propellant and flame-out and extinguishing chemical.
Background technique
Refrigeration industry had made great efforts the chlorofluorocarbons (CFC) and hydrochlorofluorocarbons of finding consumption ozone in decades in the past
(HCFC) substitute refrigerants of (they require phased out use due to Montreal Agreement).Most of refrigerant producers
Solution be by hydrofluorocarbon (hydrofluorocarbon) (HFC) refrigerant industrialize.(HFC-134a is mesh to new HFC refrigerant
It is preceding most widely used) there is zero ozone depletion potential and therefore not mandatory by current regulation as defined in Montreal Agreement
It is required that the influence tapered off.
The whole world that other legislationss of environmental protection can eventually lead to certain HFC refrigerant tapers off use.Currently, automobile
Industry faces the limitation of the regulation related with global warming potential for the refrigerant used in mobile air conditioner.Therefore,
It is highly desirable to the new refrigerant for determining and reducing global warming potential at present for mobile air conditioner market.If the regulation it is following more
It is widely applicable in, even more there is an urgent need to can be in refrigerant used in all spectra of refrigeration and air-conditioning industry.
The refrigerant of the substitution HFC-134a suggested at present includes HFC-152a, pure hydrocarbon such as butane or propane, or " natural "
Refrigerant such as CO2.Many in these substitutes suggested be it is toxic, it is inflammable, and/or with low energy efficiency.Cause
This, is seeking new substitute refrigerants.
The object of the present invention is to provide novel refrigerant compositions and heat-transfer fluid composition, they provide unique
Characteristic is to meet low or zero ozone depletion potential requirement and provide the lower global warming potential compared with current refrigerant.
General introduction of the invention
The present invention relates to the compositions comprising HFC-1225ye and at least one compound selected from following substance:
HFC-1234ze、HFC-1234yf、HFC-1234ye、HFC-1243zf、HFC-32、HFC-125、HFC-134、
HFC-134a、HFC-143a、HFC-152a、HFC-161、HFC-227ea、HFC-236ea、HFC-236fa、HFC-245fa、
HFC-365mfc, propane, normal butane, iso-butane, 2- methybutane, pentane, pentamethylene, dimethyl ether, CF3SCF3、CO2With
CF3I。
The invention further relates to the compositions comprising HFC-1234ze and at least one compound selected from following substance:
HFC-1234yf、HFC-1234ye、HFC-1243zf、HFC-32、HFC-125、HFC-134、HFC-134a、HFC-143a、
HFC-152a, HFC-161, HFC-227ea, HFC-236ea, HFC-236fa, HFC-245fa, HFC-365mfc, propane, positive fourth
Alkane, iso-butane, 2- methybutane, pentane, pentamethylene, dimethyl ether, CF3SCF3、CO2And CF3I。
The invention further relates to the compositions comprising HFC-1234yf and at least one compound selected from following substance:
HFC-1234ye、HFC-1243zf、HFC-32、HFC-125、HFC-134、HFC-134a、HFC-143a、HFC-152a、HFC-
161, HFC-227ea, HFC-236ea, HFC-236fa, HFC-245fa, HFC-365mfc, propane, normal butane, iso-butane, 2-
Methybutane, pentane, pentamethylene, dimethyl ether, CF3SCF3、CO2And CF3I。
The invention further relates to the compositions comprising HFC-1234ye and at least one compound selected from following substance:
HFC-1243zf、HFC-32、HFC-125、HFC-134、HFC-134a、HFC-143a、HFC-152a、HFC-161、HFC-
227ea, HFC-236ea, HFC-236fa, HFC-245fa, HFC-365mfc, propane, normal butane, iso-butane, 2- methybutane,
Pentane, pentamethylene, dimethyl ether, CF3SCF3、CO2And CF3I。
The invention further relates to the compositions comprising HFC-1243zf and at least one compound selected from following substance:
HFC-32、HFC-125、HFC-134、HFC-134a、HFC-143a、HFC-152a、HFC-161、HFC-227ea、HFC-
236ea, HFC-236fa, HFC-245fa, HFC-365mfc, propane, normal butane, iso-butane, 2- methybutane, pentane, ring
Pentane, dimethyl ether, CF3SCF3、CO2And CF3I。
The invention further relates to the compositions comprising following substance:
(a) at least one to be selected from polyol ester, polyalkylene glycol, polyvingl ether, mineral oil, alkylbenzene, compound stone
Wax, the lubricant for synthesizing cycloalkane and poly- (α) alkene;With
(b) it is selected from the composition of group constituted by the following substances:
About 1wt%- about 99wt%HFC1225ye and about 99wt%- about 1wt%HFC-152a;
About 1wt%- about 99wt%HFC1225ye and about 99wt%- about 1wt%HFC-1234yf;
The trans- HFC-1234ze of about 1wt%- about 99wt%HFC1225ye and about 99wt%- about 1wt%;
About 1wt%- about 99wt%HFC-1225ye and about 99wt%- about 1wt%HFC-1243zf;
About 1wt%- about 99wt% trans- HFC-1234ze and about 99wt%- about 1wwt%HFC-134a;
About 1wt%- about 99wt% trans- HFC-1234ze and about 99wt%- about 1wt%HFC-152a;
About 1wt%- about 99wt% trans- HFC-1234ze and about 99wt%- about 1wt%HFC-227ea;With
About 1wt%- about 99wt% trans- HFC-1234ze and about 99wt%- about 1wt%CF3I。
The invention further relates to the compositions comprising following substance:
A) refrigerant or heat-transfer fluid composition, the composition are selected from:
About 1wt%- about 99wt%HFC1225ye and about 99wt%- about 1wt%HFC-152a:
About 1wt%- about 99wt%HFC1225ye and about 99wt%- about 1wt%HFC-1234yf;
The trans- HFC-1234ze of about 1wt%- about 99wt%HFC-1225ye and about 99wt%- about 1wt%;
About 1wt%- about 99wt%HFC-1225ye and about 99wt%- about 1wt%HFC-1243zf;
About 1wt%- about 99wt% trans- HFC-1234ze and about 99wt%- about 1wt%HFC-134a;
About 1wt%- about 99wt% trans- HFC-1234ze and about 99wt%- about 1wt%HFC-152a;
About 1wt%- about 99wt% trans- HFC-1234ze and about 99wt%- about 1wt%HFC-227ea;Add
About 1wt%- about 99wt% trans- HFC-1234ze and about 99wt%- about 1wt%CF3I;With
Expanding material selected from following substance:
I) by general formula R1[(OR2)xOR3] y indicate polyoxyalkylene glycol ether, in which: x is the integer of 1-3;Y is 1-4
Integer;R1Aliphatic hydrocarbyl selected from hydrogen and containing 1-6 carbon atom and y bonded positions;R2Selected from the rouge containing 2-4 carbon atom
Race's alkylene;R3Aliphatic series and alicyclic alkyl selected from hydrogen and containing 1-6 carbon atom;R1And R3In at least one be selected from the hydrocarbon
Base;And wherein the polyoxyalkylene glycol ether has the molecular weight of about 300 atomic mass unit of about 100-;
Ii) by general formula R1C(O)NR2R3With ring-[R4CON(R5The amide that) -] indicates, wherein R1、R2、R3And R5Independently select
The aliphatic series and alicyclic alkyl of self-contained 1-12 carbon atom, and an at most aromatic group containing 6-12 carbon atom;R4Selected from containing
The aliphatic hydrocarbylene of 3-12 carbon atom;And wherein the amide has point of about 300 atomic mass unit of about 100-
Son amount;
Iii) by general formula R1C(O)R2The ketone of expression, wherein R1And R2Independently selected from the aliphatic series containing 1-12 carbon atom, rouge
Ring race and Arylalkvl, and wherein the ketone has the molecular weight of about 300 atomic mass unit of about 70-;
Iv) by general formula R1The nitrile that CN is indicated, wherein R1Selected from aliphatic, the alicyclic or Arylalkvl containing 5-12 carbon atom,
And wherein the nitrile has the molecular weight of about 200 atomic mass unit of about 90-;
V) chlorohydrocarbon indicated by general formula R Clx, in which: x is 1 or 2;R is selected from aliphatic series and alicyclic ring containing 1-12 carbon atom
Race's alkyl;And wherein the chlorohydrocarbon has the molecular weight of about 200 atomic mass unit of about 100-;
Vi) by general formula R1OR2The aryl ether of expression, in which: R1Selected from the Arylalkvl containing 6-12 carbon atom;R2It is selected from
Aliphatic hydrocarbyl containing 1-4 carbon atom;And wherein the aryl ether has point of about 150 atomic mass unit of about 100-
Son amount;
Vii) by general formula CF3R11,1, the 1- trifluoroalkanes indicated, wherein R1Selected from about 15 carbon atoms Han about 5-
Aliphatic series and alicyclic alkyl;
Viii) by general formula R1OCF2CF2The fluoro-ether that H is indicated, wherein R1Rouge selected from about 15 carbon atoms Han about 5-
Race, alicyclic and aromatic hydrocarbyl;Or in which the fluoro-ether is derived from fluoroolefin and polyalcohol, wherein the fluoroolefin
With CF2=CXY pattern, wherein X is hydrogen, chlorine or fluorine, and Y is chlorine, fluorine, CF3Or ORf, wherein RfIt is CF3、C2F5Or C3F7;And institute
Stating polyalcohol is linear or branching, wherein the polyalcohols have HOCH2(CHOH)x(CRR′)yCH2OH pattern, wherein
R and R ' is hydrogen, CH3Or C2H5, x is the integer of 0-4, and y is the integer of 0-3, and z is that 0 or 1 and the Branched polyol have C
(OH)t(R)u(CH2OH)v[(CH2)mCH2OH] w pattern, wherein R can be hydrogen, CH3Or C2H5, m is the integer of 0-3, and t and u are
0 or 1, v and w are the integers of 0-4, furthermore wherein t+u+v+w=4;With
Ix) the lactone indicated by structure [B], [C] and [D]:
Wherein, R1-R8Independently selected from hydrogen, linearly, branching is cyclic annular, two rings, saturation and undersaturated alkyl;And molecule
Amount is about 100 to about 300 atomic mass units;With
X) by general formula R1CO2R2The ester of expression, wherein R1And R2Independently selected from linear and cyclic annular, saturation and unsaturated,
Alkyl and aryl;And wherein the ester has the molecular weight of from about 80 to about 550 atomic mass units.
The invention further relates to the compositions comprising following substance:
(a) at least one UV fluorescent dye, is selected from naphthalimide, cumarin, anthracene is luxuriant and rich with fragrance, xanthene, thiophene
Ton, naphthoxanthene, fluorescein, the derivative and their combination of the dyestuff;With
(b) it is selected from the composition of group constituted by the following substances:
About 1wt%- about 99wt%HFC1225ye and about 99wt%- about 1wt%HFC-152a;
About 1wt%- about 99wt%HFC1225ye and about 99wt%- about 1wt%HFC-1234yf;
The trans- HFC-1234ze of about 1wt%- about 99wt%HFC1225ye and about 99wt%- about 1wt%;
About 1wt%- about 99wt%HFC-1225ye and about 99wt%- about 1wt%HFC-1243zf;
About 1wt%- about 99wt% trans- HFC-1234ze and about 99wt%- about 1wt%HFC-134a;
About 1wt%- about 99wt% trans- HFC-1234ze and about 99wt%- about 1wt%HFC-152a;
About 1wt%- about 99wt% trans- HFC-1234ze and about 99wt%- about 1wt%HFC-227ea;With
About 1wt%- about 99wt% trans- HFC-1234ze and about 99wt%- about 1wt%CF3I。
The invention further relates to selected from mineral oil, alkylbenzene, synthesis paraffin, synthesis cycloalkane and poly- (α) alkene
By the method for refrigerant or heat-transfer fluid composition solubilising in refrigeration lubricant, wherein the method includes in a effective amount of increasing
Contact the lubricant with the refrigerant or heat-transfer fluid composition in the presence of appearance agent, wherein the refrigerant or heat pass
Baffle includes composition selected from the following:
About 1wt%- about 99wt%HFC-1225ye and about 99wt%- about 1wt%HFC-152a:
About 1wt%- about 99wt%HFC-1225ye and about 99wt%- about 1wt%HFC-1234yf;
The trans- HFC-1234ze of about 1wt%- about 99wt%HFC-1225ye and about 99wt%- about 1wt%;
About 1wt%- about 99wt%HFC-1225ye and about 99wt%- about 1wt%HFC-1243zf;
About 1wt%- about 99wt% trans- HFC-1234ze and about 99wt%- about 1wt%HFC-134a;
About 1wt%- about 99wt% trans- HFC-1234ze and about 99wt%- about 1wt%HFC-152a;
About 1wt%- about 99wt% trans- HFC-1234ze and about 99wt%- about 1wt%HFC-227ea;With
About 1wt%- about 99wt% trans- HFC-1234ze and about 99wt%- about 1wt%CF3I;
And wherein the expanding material is selected from:
A) by general formula R1[(OR2)xOR3] y indicate polyoxyalkylene glycol ether, in which: x is the integer of 1-3;Y is 1-4
Integer;R1Aliphatic hydrocarbyl selected from hydrogen and containing 1-6 carbon atom and y bonded positions;R2Selected from the rouge containing 2-4 carbon atom
Race's alkylene;R3 is selected from hydrogen and aliphatic series and alicyclic alkyl containing 1-6 carbon atom;R1And R3In at least one be selected from the hydrocarbon
Base;And wherein the polyoxyalkylene glycol ether has the molecular weight of about 300 atomic mass unit of about 100-;
B) by general formula R1C(O)NR2R3With ring-[R4CON(R5The amide that) -] indicates, wherein R1、R2、R3And R5Independently select
The aliphatic series and alicyclic alkyl of self-contained 1-12 carbon atom, and an at most aromatic group containing 6-12 carbon atom;R4Selected from containing
The aliphatic hydrocarbylene of 3-12 carbon atom;And wherein the amide has point of about 300 atomic mass unit of about 100-
Son amount;
C) by general formula R1C(O)R2The ketone of expression, wherein R1And R2Independently selected from the aliphatic series containing 1-12 carbon atom, alicyclic ring
Race and Arylalkvl, and wherein the ketone has the molecular weight of about 300 atomic mass unit of about 70-;
D) by general formula R1The nitrile that CN is indicated, wherein R1Selected from aliphatic, the alicyclic or Arylalkvl containing 5-12 carbon atom,
And wherein the nitrile has the molecular weight of about 200 atomic mass unit of about 90-;
E) chlorohydrocarbon indicated by general formula R Clx, in which: x is 1 or 2;R is selected from aliphatic series and alicyclic ring containing 1-12 carbon atom
Race's alkyl;And wherein the chlorohydrocarbon has the molecular weight of about 200 atomic mass unit of about 100-;
F) by general formula R1OR2The aryl ether of expression, in which: R1Selected from the Arylalkvl containing 6-12 carbon atom;R2Selected from containing
The aliphatic hydrocarbyl of 1-4 carbon atom;And wherein the aryl ether has the molecule of about 150 atomic mass unit of about 100-
Amount;
G) by general formula CF3R11,1, the 1- trifluoroalkanes indicated, wherein R1Rouge selected from about 15 carbon atoms Han about 5-
Race and alicyclic alkyl;
H) by general formula R1OCF2CF2The fluoro-ether that H is indicated, wherein R1Aliphatic series selected from about 15 carbon atoms Han about 5-
And alicyclic alkyl;Or in which the fluoro-ether is derived from fluoroolefin and polyalcohol, wherein the fluoroolefin has CF2=
CXY pattern, wherein X is hydrogen, chlorine or fluorine, and Y is chlorine, fluorine, CF3Or ORf, wherein RfIt is CF3、C2F5Or C3F7;With the linear multiple
Alcohol has HOCH2CRR′(CH2)z(CHOH)xCH2(CH2OH) y pattern, wherein R and R ' is hydrogen, CH3Or C2H5, x is the whole of 0-4
Number, y is the integer of 0-3, and z is 0 or 1;With
I) lactone indicated by structure [B], [C] and [D]:
Wherein, R1-R8Independently selected from hydrogen, linearly, branching is cyclic annular, two rings, saturation and undersaturated alkyl;And molecule
Amount is about 100 to about 300 atomic mass units;With
J) by general formula R1CO2R2The ester of expression, wherein R1And R2Independently selected from linear and cyclic annular, saturation and unsaturated,
Alkyl and aryl;And wherein the ester has the molecular weight of from about 80 to about 550 atomic mass units.
The invention further relates to the methods of high GWP refrigerant in substitution refrigeration, air-conditioning or heat-pump apparatus, wherein the height
GWP refrigerant be selected from R134a, R22, R123, R11, R245fa, R114, R236fa, R124, R12, R410A, R407C,
R417A, R422A, R507A, R502 and R404A, the method includes by composition selected from the following
About 1wt%- about 99wt%HFC-1225ye and about 99wt%- about 1wt%HFC-152a;
About 1wt%- about 99wt%HFC1225ye and about 99wt%- about 1wt%HFC-1234yf;
The trans- HFC-1234ze of about 1wt%- about 99wt%HFC-1225ye and about 99wt%- about 1wt%;
About 1wt%- about 99wt%HFC-1225ye and about 99wt%- about 1wt%HFC-1243zf;
About 1wt%- about 99wt% trans- HFC-1234ze and about 99wt%- about 1wt%HFC-134a;
About 1wt%- about 99wt% trans- HFC-1234ze and about 99wt%- about 1wt%HFC-152a;
About 1wt%- about 99wt% trans- HFC-1234ze and about 99wt%- about 1wt%HFC-227ea;With
About 1wt%- about 99wt% trans- HFC-1234ze and about 99wt%- about 1wt%CF3I;
It is supplied to use, is used to or is designed to set using the refrigeration, air-conditioning or the heat pump of the high GWP refrigerant
It is standby.
The invention further relates to the method for coolant leaks in early detection refrigeration, air-conditioning or heat-pump apparatus, the sides
Method includes in the apparatus using the reduction of non-azeotropic compositions and monitoring cooling performance.
Detailed description of the invention
The present invention relates to the compositions comprising at least one fluoroolefin.Composition of the invention further includes at least one
Kind additional component, the component can be the second fluoroolefin, hydrofluorocarbon (HFC), hydrocarbon, dimethyl ether, bis- (trifluoromethyl) thioethers,
CF3I or CO2.The fluoroolefin compounds of the present composition and other components are listed in Table 1 below.
Table 1
The each component being listed in Table 1 below can be prepared by method as known in the art.
Fluoroolefin compounds used in the present composition (HFC-1225ye, HFC-1234ze and HFC-1234ye)
The isomers or stereoisomer that can be used as various configuration exist.The present invention is intended to include all single configuration isomers, list
One stereoisomer or any combination of them or mixture.For example, 1,3,3,3- tetrafluoropropene (HFC-1234ze) means
Indicate any combination or mixture that any ratio is pressed along isomers, trans isomer or both isomers.Another example is
HFC-1225ye, it is taken over any combination or mixture table of what ratio by suitable isomers, trans isomer or both isomers
Show.
Composition of the invention include the following: HFC-1225ye and at least one compound selected from following substance: HFC-
1234ze、HFC-1234yf、HFC-1234ye、HFC-1243zf、HFC-32、HFC-125、HFC-134、HFC-134a、HFC-
143a, HFC-152a, HFC-16l, HFC-227ea, HFC-236ea, HFC-236fa, HFC-245fa, HFC-365mfc, third
Alkane, normal butane, iso-butane, 2- methybutane, pentane, pentamethylene, dimethyl ether, CF3SCF3、CO2And CF3I;
HFC-1234ze and at least one compound selected from following substance: HFC-1225ye, HFC-1234yf, HFC-
1234ye、HFC-1243zf、HFC-32、HFC-125、HFC-134、HFC-134a、HFC-143a、HFC-152a、HFC-161、
HFC-227ea, HFC-236ea, HFC-236fa, HFC-245fa, HFC-365mfc, propane, normal butane, iso-butane, 2- methyl
Butane, pentane, pentamethylene, dimethyl ether, CF3SCF3、CO2And CF3I;
HFC-1234yf and at least one compound selected from following substance: HFC-1234ye, HFC-1243zf, HFC-
32、HFC-125、HFC-134、HFC-134a、HFC-143a、HFC-152a、HFC-161、HFC-227ea、HFC-236ea、
HFC-236fa, HFC-245fa, HFC-365mfc, propane, normal butane, iso-butane, 2- methybutane, pentane, pentamethylene, two
Methyl ether, CF3SCF3、CO2And CF3I;With
HFC-1243zf and at least one compound selected from following substance: HFC-1234ye, HFC-32, HFC-125,
HFC-134、HFC-134a、HFC-143a、HFC-152a、HFC-161、HFC-227ea、HFC-236ea、HFC-236fa、HFC-
245fa, HFC-365mfc, propane, normal butane, iso-butane, 2- methybutane, pentane, pentamethylene, dimethyl ether, CF3SCF3、
CO2And CF3I;With
HFC-1234ye and at least one compound selected from following substance: HFC-32, HFC-125, HFC-134, HFC-
134a、HFC-143a、HFC-152a、HFC-161、HFC-227ea、HFC-236ea、HFC-236fa、HFC-245fa、HFC-
365mfc, propane, normal butane, iso-butane, 2- methybutane, pentane, pentamethylene, dimethyl ether, CF3SCF3、CO2And CF3I。
When the fluoroolefin is with about 1wt%- about 99wt%, preferably approximately 20wt%- about 99wt%, more preferably
In the presence of the concentration of about 40wt%- about 99wt%, still more preferably 50wt%- about 99wt%, composition of the invention is logical
It often may be useful.
The present invention further provides the compositions being listed in Table 2 below.
Table 2
In the presence of each component is with the concentration of such as listed +/- 2wt%, of the invention being listed in Table 2 below is most preferred
Composition is generally expected to performance and function needed for maintaining.Work as CO2In the presence of the listed +/- 0.2wt% of concentration, contain CO2's
Composition maintains required performance and function for expected.
Composition of the invention can be azeotropic or the composition close to azeotropic.So-called Azeotrope compositions, which refer to, to be shown as
The constant boiling point mixture of two or more substances of single substance.A kind of method for characterizing Azeotrope compositions is by liquid
The steam that part is evaporated or distillation generates evaporates or distills liquid composition having the same certainly with it, i.e. the mixture is not having
Distillation/reflux in the case where composition variation.Constant boiling point composition is characterized as Azeotrope compositions, because of them and the same compound
The boiling point of zeotrope is compared to display maximum or the smallest boiling point.Azeotrope compositions will not in operation refrigeration or
Fractionation in air-conditioning system, this may be decreased the efficiency of the system.In addition, Azeotrope compositions will not be in leakage from refrigeration or air-conditioning
System fractionation.In the case that a kind of component is combustible components in the mixture, fractionation may be in the system in leakage process
Flammable compositions are generated outside the interior or system.
Composition (also usually referred to as " Azeotrope-like compositions ") close to azeotropic is substantially behaved as single substance
The liquid mixture of the generally constant boiling point of two or more substances.A kind of method of characterization close to the composition of azeotropic is logical
The steam that the part evaporation or distillation for crossing liquid generate, which evaporates or distill liquid certainly with it, has substantially the same composition, i.e.,
Mixture distillation/reflux in the case where no significantly composition variation.Characterize another method close to the composition of azeotropic
Be the composition at a certain temperature bubble point vapor pressure and dew point vapor pressure it is substantially the same.Here, if being combined removing
After the 50wt% of object (such as by evaporating or boiling removing), original composition and 50wt% original composition is being removed
The vapour pressure difference between remaining composition is less than about 10% later, then the composition is proximate to azeotropic.
Azeotrope compositions of the invention are shown in table 3 at the specified temperature.
Table 3
Further, it is found that the ternary azeotropic compositions as listed by table 4.
Table 4
The composition of the invention close to azeotropic is listed in Table 5 below at the specified temperature.
Table 5
Ternary and higher order as listed by table 6 comprising fluoroolefin have also been determined close to Azeotrope compositions.
Table 6
Certain compositions of the invention are non-azeotropic compositions.Belong to the preferred scope of table 2, but connecing in table 5 and table 6
Those compositions of the invention except nearly azeotropic range may be considered non-azeotrope.
Non-azeotropic compositions can have it is certain better than azeotropic or close to azeotropic mixture the advantages of.Non-azeotropic compositions is
Show as mixture rather than the mixture of two or more substances of single substance.Characterize a kind of side of non-azeotropic compositions
Method is that have to evaporate or distill the dramatically different group of liquid certainly with it by the steam of part evaporation or the distillation generation of liquid
At i.e. mixture distillation/reflux under the variation of sizable composition.Another method for characterizing non-azeotropic compositions is in spy
The bubble point vapor pressure and dew point vapor pressure for determining the composition at temperature are dramatically different.Here, if removing composition
After 50wt% (such as by evaporating or boiling removing), original composition and after having removed 50wt% original composition
Vapour pressure difference between remaining composition is greater than about 10%, then the composition is non-azeotrope.
Composition of the invention can be mixed the desired amount of each component to prepare by any suitable method.Preferred side
Method is the amount of component needed for weighing, and later mixes these components in suitable container.If necessary, it can be used and stir
It mixes.
The replacement means for preparing the present composition can be the method for preparing refrigerant blend composition, wherein described
Refrigerant blend composition includes compositions disclosed herein, which comprises (i) is returned from least one cryogen vessel
A large amount of one or more components of refrigerant compositions are received, (ii) removes impurity to being enough to make one or more recycling
Component can reuse, (iii) and optionally, by the component of all or part of yields and at least one additional refrigeration
Agent composition or component mixing.
Cryogen vessel can be any container, wherein storing once for refrigeration equipment, air-conditioning equipment or heat-pump apparatus
Refrigerant blend composition.The cryogen vessel can be wherein using the refrigerant blend refrigeration equipment,
Air-conditioning equipment or heat-pump apparatus.In addition, cryogen vessel can be the storage for collecting recycled refrigerant blend component
Storage, including but not limited to pressurized cylinder.
Residual refrigerant refers to any amount of refrigerant blend or refrigerant blend component, can be by any
Become known for transmitting refrigerant blend or the method for refrigerant blend component is discharged from cryogen vessel.
Impurity can be any use due to it in refrigeration equipment, air-conditioning equipment or heat-pump apparatus and be total in refrigerant
Component in mixed object or refrigerant blend component.These impurity include but is not limited to refrigeration lubricant, they are previous herein
Those of description, the including but not limited to particle of metal, metal salt or elastomer particles, they may be from refrigeration equipment, sky
Adjust the impurity of equipment or heat-pump apparatus and any other performance that may negatively affect refrigerant blend composition.
Can by these impurity except go to be enough to allow to reuse refrigerant blend or refrigerant blend component without
The refrigerant blend or refrigerant blend component can be negatively affected will be in the performance of the device wherein used.
In order to generate the composition in accordance with specification needed for given product, additional refrigerant blend or refrigerant are blended
Object component is supplied to residual refrigerant blend or refrigerant blend component and may be necessary.For example, if refrigerant is total
Mixed object has 3 kinds of components in specified weight percent ranges, then adds one or more components so that the group by specified rate
It closes object and is restored in specification limitation and may be necessary.
Composition of the invention has zero or low ozone depleting potential and low global warming potential (GWP).In addition, this
The composition of invention by have than at present the low global warming potential of many hydrofluorocarbon refrigerant.A side of the invention
Face is to provide refrigerant of the global warming potential less than 1000, less than 500, less than 150, less than 100 or less than 50.Of the invention
It is to reduce the net GWP of refrigerant mixture by adding fluoroolefin to the mixture on the other hand.
The present composition may be used as low global warming potential (GWP) sub of refrigerant used at present, described
Refrigerant used at present includes but is not limited to: R134a (or HFC-134a, HFA 134a), R22 (or HCFC-
22, F-22), R123 (or HFC-123,2,2- bis- chloro- 1,1,1- trifluoroethane), R11 (CFC-11, a fluorine trichlorine
Methane), R12 (CFC-12, dicholorodifluoromethane), R245fa (or HFC-245fa, 1,1,1,3,3- pentafluoropropane), R114 (or
CFC-114,1,2- bis- chloro- 1,1,2,2- tetrafluoroethane), R236fa (or HFC-236fa, 1,1,1,3,3,3- hexafluoropropane),
R124 (or the chloro- HFA 134a of HCFC-124,2-), R407C (52wt%R134a, 25wt%R125 (pentafluoroethane)
Named with the ASHRAE of the blend of 23wt%R32 (difluoromethane)), the R410A (blending of 50wt%R125 and 50wt%R32
The ASHRAE of object is named), R417A (blend of 46.6wt%R125,50.0wt%R134a and 3.4wt% normal butane
ASHRAE name), (ASHRAE of the blend of 85.1wt%R125,11.5wt%R134a and 3.4wt% iso-butane is ordered R422A
Name), R404A (blend of 44wt%R125,52wt%R143a (1,1,1- trifluoroethane) and 4.0wt%R134a
ASHRAE name) and R507A (ASHRAE of the blend of 50wt%R125 and 50wt%R143a is named).In addition, of the invention
Composition may be used as R12 (CFC-12, dicholorodifluoromethane) or R502 (51.2wt%CFC-115 (chloropentafluoroethane) and
The ASHRAE of the blend of 48.8wt%HCFC-22 is named) sub.
In general, sub refrigerant is most if can be used in the original chiller designed for different refrigerant
Useful.Composition of the invention may be used as the sub of the above-mentioned refrigerant in primitive apparatus.In addition, combination of the invention
Object may be used as design and use the sub of the above-mentioned refrigerant in the device of above-mentioned refrigerant.
The present composition can further include lubricant.
Lubricant of the invention includes refrigeration lubricant, i.e., suitable for those of refrigeration, air-conditioning or heat-pump apparatus lubrication
Agent.These lubricants include those of common in the compression refrigeration equipment using fluorochlorohydrocarbon refrigerant.These lubricants and it
Performance in 1990ASHRAEH Handbook, Refrigeration Systems and Applications, the 8th chapter is entitled
" Lubricants in Refrigeration Systems " is discussed in page 8.1 to 8.21.Lubricant of the invention
It may include compressing in refrigeration lubrication field commonly referred to as those of " mineral oil ".Mineral oil includes paraffin (i.e. straight chain and branching
Carbochain, saturated hydrocarbons), naphthalene (i.e. cyclic paraffins) and aromatic compounds (be the alternately ring of double bond containing one or more features
Unsaturated cyclic hydrocarbon).It is commonly referred to as those of " synthetic oil " that lubricant of the invention, which further comprises in compression refrigeration lubrication field,.
Synthetic oil includes alkyl aryl compound (i.e. linear and branched-alkyl alkylbenzene), synthesis paraffin and cycloalkane and poly- (alhpa olefin).
Representative conventional lubricantss of the invention are commercially available BVM 100N (paraffinic mineral oils sold by BVA Oils),3GS and5GS (naphthenic mineral oil sold by Crompton Co.),372LT (by
The naphthenic mineral oil of Pennzoil sale),RO-30 (the naphthenic mineral sold by Calumet Lubricants
Oil),75、150 Hes500 (linear alkyl benzenes sold by Shrieve Chemicals) and
HAB22 (the branched-alkyl benzene sold by Nippon Oil).
Lubricant of the invention further comprises having designed to be used together with hydrofluorocarbon refrigerant and in compression refrigeration, sky
Adjust or the operating condition of heat-pump apparatus under can be those of with refrigerant mixing of the present invention.These lubricants and their performance exist
" Synthetic Lubricants and High-Performance Fluids ", R.L.Shubkin, editor, Marcel
Dekker is discussed in 1993.These lubricants include but is not limited to that polyol ester (POE) is for example100
(Castrol, United Kingdom), polyalkylene glycol (PAG) for example derived from Dow (Dow Chemical, Midland,
Michigan RL-488A and polyvingl ether (PVE)).These lubricants can be obtained easily from various commercial sources.
Lubricant of the invention pass through by the requirement of given compressor and lubricant into contact with environment take in
To select.Lubricant of the invention is preferably at 40 DEG C with the dynamic viscosity of at least about 5cs (centistoke).
As needed, common refrigerating system additive can be optionally added in composition of the invention, to improve
Lubricity and system stability.These additives are known in refrigeration compressor lubricating area, and including wear-resistant
Agent, limit lubricant, corrosion and oxidation retarder, metal surface deactivators, free radical scavenger, blistering and defoaming control
Agent, leak detectants etc..In general, these additives only exist in a small amount relative to total lubricant compositions.Typically, with from low
Them are used to the concentration for being up to about 3% each additive in about 0.1%.These additives are according to respective system requirements
To select.Some representative instances of these additives may include, but be not limited to, lubrication enhancing additive, such as phosphoric acid and thio
The alkyl or aryl ester of phosphate.In addition, dialkyl dithiophosphoric acid metal salt (such as zinc dialkyl dithiophosphate or
ZDDP, Lubrizol1375) and other members of this kind of chemicals can be used in composition of the invention.Other wear-resistant additions
Agent includes natural products oil and asymmetric polyhydroxy lubricating additive, such as Synergol TMS (International
Lubricants).Similarly, stabilizer such as antioxidant, free radical scavenger and water scavenger can use.In this one kind
Compound in class may include, but be not limited to, butylated hydroxytoluene (BHT) and epoxides.
Composition of the invention can further include about 0.01wt% to about 5wt% additive, for example, stablizing
Agent, free radical scavenger and/or antioxidant.These additives include but is not limited to nitromethane, hindered phenol, azanol, mercaptan,
Phosphite ester or lactone.Single additive or combination can be used.
The water scavenger that composition of the invention can further include about 0.01wt% to about 5wt% is (dry to use
Compound).These water scavengers may include ortho esters such as trimethyl-, triethyl group-or tripropyl orthoformate.
Composition of the invention can further include tracer, be selected from hydrofluorocarbon (HFC), deuteroparaffin, hydrogen deuteride fluorine
Carbon, perfluoroparaffin, fluoro-ether, brominated compound, iodinated compounds, alcohol, aldehyde, ketone, nitrous oxide (N2) and their combination O.
Tracer compounds are added in composition by predetermined quantities with allow any dilution of detection combination object, pollution or its
It changes, as described in 2 months 2005 U.S. Patent Application Serial Numbers 11/062044 submitted for 18th.
Typical tracer compounds for the present composition are shown in Table 7.
Table 7
The compound being shown in Table 7 is commercially available (chemically commercially available from product supplier) or can be by as known in the art
Method preparation.
Single tracer compounds and refrigerating/heating combination of fluids can be used in the present compositions or can be with
Multitracer compound is mixed to serve as tracer blend in any proportion.Tracer blend may include from phase
The multitracer compound of generic compound or multitracer compound from different classes of compound.For example, showing
Track agent blend may include two or more deuterate hydrofluorocarbon or a kind of deuterate hydrofluorocarbon and one kind in combination or more
Kind perfluoroparaffin.
In addition, some compounds in table 7 exist as multiple isomers (constitutional isomer or optical isomer).It is identical
The individual isomer of compound or multiple isomers can be used in any proportion to prepare tracer compounds.In addition, given
The single or multiple isomers of compound can serve as tracer blend in conjunction with many other compounds in any proportion.
Tracer compounds or tracer blend can be by about 50 parts by weight/mono- million parts by weight (ppm)-about
The total concentration of 1000ppm is present in composition.Preferably, tracer compounds or tracer blend are big with about 50ppm-
The total concentration of about 500ppm exists, most preferably, tracer compounds or tracer blend with about 100ppm- about
The total concentration of 300ppm exists.
Composition of the invention can be further included selected from polyoxyalkylene glycol ether, amide, nitrile, ketone, chlorohydrocarbon,
Ester, lactone, aryl ether, fluoro-ether and 1, the expanding material of 1,1- trifluoroalkanes.The expanding material is used to improve hydrofluorocarbon refrigerant
Dissolubility in conventional refrigerant lubricant.Refrigeration lubricant is needed to lubricate refrigeration, air-conditioning or the compressor of heat-pump apparatus.Profit
Lubrication prescription must be mobile with refrigerant in whole equipment, and particularly, it must be from uncompressed machine area back to compressor to continue
Super fatting agent acts on and avoids compressor failure.
Hydrofluorocarbon refrigerant usually not with conventional refrigerant lubricant for example mineral oil, alkylbenzene, synthesis paraffin, synthesis cycloalkane
It is compatible with poly- (α) alkene.Many sub lubricants have been proposed, it is suggested, however, that be used together with hydrofluorocarbon refrigerant
Polyalkylene glycol, polyol ester and polyvingl ether are expensive and are easy water suction.In refrigeration, air-conditioning system or heat pump
Water can cause corrosion and particle formation, the particle may block other apertures in capillary and system, thus most
Lead to thrashing eventually.In addition, needing time-consuming and expensive cleaning procedure to be made according to new lubricant in existing equipment and changing
Become.Therefore, it is desirable for continuing to use original lubricant if possible.
Expanding material of the invention improve dissolubility of the hydrofluorocarbon refrigerant in conventional refrigerant lubricant and therefore improve to
The oil return of compressor.
Polyoxyalkylene glycol ether expanding material of the invention is by general formula R1[(OR2)xOR3] y expression, in which: x is the whole of 1-3
Number;Y is the integer of 1-4;R1Aliphatic hydrocarbyl selected from hydrogen and containing 1-6 carbon atom and y bonded positions;R2Selected from containing 2-4 carbon
The aliphatic hydrocarbylene of atom;R3Aliphatic series and alicyclic alkyl selected from hydrogen and containing 1-6 carbon atom;R1And R3In at least one choosing
From the alkyl;And wherein the polyoxyalkylene glycol ether has the molecule of about 300 atomic mass unit of about 100-
Amount.Bonded position used herein refers to the position that can be used to that covalent bond is formed with other groups.Alkylene refers to divalent
Alkyl.In the present invention, it is preferred to polyoxyalkylene glycol ether expanding material by general formula R1[(OR2)xOR3] y expression, x is preferably 1-
2;Y is preferably 1;R1And R3Preferably independently it is selected from hydrogen and the aliphatic hydrocarbyl containing 1-4 carbon atom;R2It is preferably selected from containing 2 or 3
Carbon atom, the aliphatic hydrocarbylene of most preferably 3 carbon atoms;The polyoxyalkylene glycol ether molecular weight preferably about 100- is big
About 250 atomic mass units, about 250 atomic mass unit of most preferably about 125-.R containing 1-6 carbon atom1And R3Hydrocarbon
Base can be linear, branching or cricoid.Representative R1 and R3 alkyl includes methyl, ethyl, propyl, isopropyl, and butyl is different
Butyl, sec-butyl, tert-butyl, amyl, isopentyl, neopentyl, tertiary pentyl, cyclopenta and cyclohexyl.When in the polyoxyalkylene
Free hydroxyl group on glycol ethers expanding material may with certain compression refrigeration equipment structural materials (such as) it is incompatible when,
R1And R3Preferably contain 1 to 4 carbon atoms, the aliphatic hydrocarbyl of most preferably 1 carbon atom.R containing 2-4 carbon atom2Aliphatic is sub-
Alkyl forms duplicate oxyalkylene group-(OR2) x-, the latter includes oxygen ethylene group, oxygen propylidene group and oxygen
Butylene.That in a polyoxyalkylene glycol ether increase-volume agent molecule includes R2Oxyalkylene group can be phase
A same or molecule may include different R2Alkylidene oxide.Polyoxyalkylene glycol ether expanding material of the invention is preferred
Include at least one oxygen propylidene group.Work as R1It is aliphatic or alicyclic hydrocarbon group containing 1-6 carbon atom and y bonded positions
When, which can be linearly branching or cricoid.Representative R containing two bonded positions1Aliphatic hydrocarbyl includes, for example, sub-
Ethyl, propylidene, butylidene, pentylidene, hexylidene, cyclopentylene and sub- cyclohexyl.Representativeness containing 3 or 4 bonded positions
R1Aliphatic hydrocarbyl includes from polyalcohol, such as trimethylolpropane, glycerol, pentaerythrite, 1,2,3- trihydroxy hexamethylene and 13,
5- trihydroxy hexamethylene, by removing residue derived from their hydroxyl.
Representative polyoxyalkylene glycol ether expanding material includes but is not limited to: CH3OCH2CH(CH3) O (H or CH3) (third
Glycol methyl (or dimethyl) ether), CH3O[CH2CH(CH3)O]2(H or CH3) (dipropylene glycol methyl (or dimethyl) ether), CH3O
[CH2CH(CH3)O]3(H or CH3) (tripropylene glycol methyl (or dimethyl) ether), C2H5OCH2CH(CH3) O (H or C2H5) (the third two
Alcohol ethyl (or diethyl) ether), C2H5O[CH2CH(CH3)O]2(H or C2H5) (dipropylene glycol ethyl (or diethyl) ether), C2H5O
[CH2CH(CH3)O]3(H or C2H5) (tripropylene glycol ethyl (or diethyl) ether), C3H7OCH2CH(CH3) O (H or C3H7) (the third two
Alcohol n-propyl (or diη-propyl) ether), C3H7O[CH2CH(CH3)O]2(H or C3H7) (dipropylene glycol n-propyl (or diη-propyl)
Ether), C3H7O[CH2CH(CH3)O]3(H or C3H7) (tripropylene glycol n-propyl (or diη-propyl) ether), C4H9OCH2CH(CH3)OH
(propylene glycol n-butyl ether), C4H9O[CH2CH(CH3)O]2(H or C4H9) (dipropylene glycol normal-butyl (or di-n-butyl) ether), C4H9O
[CH2CH(CH3)O]3(H or C4H9) (tripropylene glycol normal-butyl (or di-n-butyl) ether), (CH3)3COCH2CH(CH3) OH (the third two
Alcohol tertbutyl ether), (CH3)3CO[CH2CH(CH3)O]2(H or (CH3)3) (dipropylene glycol tert-butyl (or di-t-butyl) ether),
(CH3)3CO[CH2CH(CH3)O]3(H or (CH3)3) (tripropylene glycol tert-butyl (or di-t-butyl) ether), C5H11OCH2CH(CH3)
OH (propylene glycol n-pentyl ether), C4H9OCH2CH(C2H5) OH (butanediol n-butyl ether), C4H9O[CH2CH(C2H5)O]2H (two fourths two
Alcohol n-butyl ether), trimethylolpropane tris n-butyl ether (C2H5C(CH2O(CH2)3CH3)3) and trimethylolpropane di-n-butyl ether
(C2H5C(CH2OC(CH2)3CH3)2CH2OH)。
Amide expanding material of the invention includes by general formula R1C(O)NR2R3With ring-[R4C(O)N(R5Those of)] indicate,
In: R1、R2、R3And R5Independently selected from aliphatic series and alicyclic alkyl containing 1-12 carbon atom;R4Selected from containing 3-12 carbon atom
Aliphatic hydrocarbylene;And wherein the amide has the molecular weight of about 300 atomic mass unit of about 100-.The amide
About 250 atomic mass unit of molecular weight preferably about 160-.R1, R2, R3And R5Substituted hydrocarbon can be optionally included
Base, that is, contain the group selected from halogen (such as fluorine, chlorine) and the substituents of alkoxy (such as methoxyl group).R1, R2, R3With
R5The substituted alkyl of hetero atom-can be optionally included, that is, contain Nitrogen Atom in the group chain being in addition made of carbon atom
(azepine -), the group of oxygen (oxa- -) or sulphur (thia -).Typically in R1-3In every 10 carbon atoms will be present and be no more than
Three substituents and hetero atom, and preferably more than one, and must be taken into consideration and appoint when being applicable in the limitation of above-mentioned molecular weight
What these substituents and heteroatomic presence.Preferred amide expanding material is made of carbon, hydrogen, nitrogen and oxygen.Representative R1,
R2, R3And R5Aliphatic series and alicyclic alkyl include methyl, ethyl, propyl, isopropyl, butyl, isobutyl group, sec-butyl, tert-butyl,
Amyl, isopentyl, neopentyl, tertiary pentyl, cyclopenta, cyclohexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl
With their configurational isomer.One preferred embodiment of Amide solubilizing agents is wherein in above-mentioned general formula ring-[R4C(O)N
(R5R in) -]4It can be by alkylene (CR6R7Those of) n expression, in other words, general formula: ring-[(CR6R7)nC(O)N(R5) -],
Wherein: equally applicable for the described value before molecular weight;N is the integer of 3-5;R5It is the saturation containing 1-12 carbon atom
Hydrocarbyl group;R6And R7By being previously used for defining R1-3Rule be selected independently (for each n).By general formula: ring-[(CR6R7)
nC(O)N(R5In the lactams that) -] indicates, whole R6And R7Preferably hydrogen, or containing single among n methylene units
Saturated hydrocarbons group, R5It is the saturated hydrocarbons group containing 3-12 carbon atom.For example, 1- (saturated hydrocarbyl) -5- methylpyrrolidin- 2-
Ketone.
Representative Amide solubilizing agents include but is not limited to: 1- octyl pyrrolidin-2-one, 1- decyl pyrrolidine -2- ketone, 1-
Octyl -5- methylpyrrolidin- 2- ketone, 1- butyl caprolactam, 1- cyclohexyl pyrrolidin-2-one, 1- butyl -5- methyl piperidine -
2- ketone, 1- amyl-5- methyl piperidine-2- ketone, 1- hexyl caprolactam, 1- hexyl-5- methylpyrrolidin- 2- ketone, 5- methyl-1-
Amyl piperidine -2- ketone, 1,3- lupetidine -2- ketone, 1- methyl caprolactam, 1- Butyl-pyrrol alkane -2- ketone, 1,5- diformazan
Phenylpiperidines -2- ketone, 1- decyl -5- methylpyrrolidin- 2- ketone, 1- dodecyl pyrrolidine -2- ketone, N, N- dibutyl formamide and
N, N- diisopropyl acetamide.
Ketone expanding material of the invention includes by general formula R1C(O)R2The ketone of expression, wherein R1And R2Independently selected from containing 1-12
Aliphatic, the alicyclic and Arylalkvl of a carbon atom, and wherein the ketone has about 300 atomic mass unit of about 70-
Molecular weight.R in the ketone1And R2Preferably independently it is selected from aliphatic series and alicyclic alkyl containing 1-9 carbon atom.The ketone
Molecular weight preferably about 100-200 atomic mass unit.R1And R2It can be formed together alkylene, which connects simultaneously
Form five, six or heptatomic ring cyclic ketones, such as cyclopentanone, cyclohexanone and cycloheptanone.R1, R2, R3And R5It can optionally include and take
The alkyl in generation, that is, contain the group selected from halogen (such as fluorine, chlorine) and the substituents of alkoxy (such as methoxyl group).R1
And R2The alkyl of hetero atom substitution can be optionally included, that is, contain Nitrogen Atom in the group chain being in addition made of carbon atom
(azepine -), the group of oxygen (ketone-, oxa- -) or sulphur (thia -).Typically in R1And R2In every 10 carbon atoms will be present
No more than three substituents and hetero atom, and preferably more than one, and it is necessary when being applicable in the limitation of above-mentioned molecular weight
Consider any of these substituents and heteroatomic presence.In general formula R1COR2In representative R1And R2Aliphatic, alicyclic ring
Race and Arylalkvl group include methyl, ethyl, propyl, isopropyl, butyl, isobutyl group, sec-butyl, tert-butyl, amyl, isoamyl
Base, neopentyl, tertiary pentyl, cyclopenta, cyclohexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl and they
Configurational isomer and phenyl, benzyl, cumenyl, 2,4,6- trimethylphenyls, tolyl, 3,5-dimethylphenyl and phenethyl.
Representative ketone solubilizer includes but is not limited to: 2- butanone, 2 pentanone, acetophenone, butyrophenone, amyl phenyl ketone, hexamethylene
Ketone, cycloheptanone, 2-HEPTANONE, 3- heptanone, 5 methy 12 hexanone, methyl hexyl ketone (methyln-hexyl ketone), 3- octanone, diisobutyl ketone,
4- ethyl cyclohexanone, methyl n-heptyl ketone, butyl ketone, 2- decanone, 4- decanone, 2- decalone, methyl n-undecyl ketone, dihexyl ketone and two hexamethylenes
Base ketone.
Nitrile expanding material of the invention includes by general formula R1The nitrile that CN is indicated, wherein R1Selected from containing 5-12 carbon atom aliphatic series,
Alicyclic or Arylalkvl, and wherein the nitrile has the molecular weight of about 200 atomic mass unit of about 90-.Described
R in nitrile expanding material1It is preferably selected from aliphatic series and alicyclic alkyl containing 8-10 carbon atom.The molecular weight of the nitrile expanding material is excellent
It is selected as about 140 atomic mass unit of about 120-.R1Substituted alkyl can be optionally included, that is, containing selected from halogen (example
Such as fluorine, chlorine) and alkoxy (such as methoxyl group) substituents group.R1The hydrocarbon of hetero atom substitution can be optionally included
Base, that is, contain Nitrogen Atom (azepine -), oxygen (ketone-, oxa- -) or sulphur (thia -) in the group chain being in addition made of carbon atom
Group.Typically in R1In every 10 carbon atoms will be present no more than three substituents and hetero atom, and preferably
No more than one, and any of these substituents must be taken into consideration when being applicable in the limitation of above-mentioned molecular weight and heteroatomic deposit
?.In general formula R1Representative R in CN1Aliphatic series, alicyclic and Arylalkvl group includes amyl, and isopentyl, neopentyl, uncle penta
Base, cyclopenta, cyclohexyl, heptyl, octyl, nonyl, decyl, undecyl, the configurational isomer of dodecyl and they, and
Phenyl, benzyl, cumenyl, 2,4,6- trimethylphenyls, tolyl, 3,5-dimethylphenyl and phenethyl.
Representative nitrile expanding material includes but is not limited to: 1- cyanopentane, 2,2- dimethyl -4- cyanopentanes, 1- cyano
Hexane, 1- cyanoheptane, 1- cyanooctane, 2- cyanooctane, 1- cyanononane, 1- cyanodecane, 2- cyanodecane, 1- cyano
Hendecane and 1- cyanododecane.
Chloro hydrocarbon compatibilizer of the invention includes the chlorohydrocarbon indicated by general formula R Clx, in which: x is selected from an integer of 1 or 2;R
Selected from aliphatic series and alicyclic alkyl containing 1-12 carbon atom;And wherein the chlorohydrocarbon has about 100- about 200 former
The molecular weight of protonatomic mass unit.The molecular weight of the chloro hydrocarbon compatibilizer preferably about 120-150 atomic mass unit.Logical
Representative R aliphatic series and alicyclic alkyl in formula RClx include methyl, ethyl, propyl, isopropyl, butyl, isobutyl group, Zhong Ding
Base, tert-butyl, amyl, isopentyl, neopentyl, tertiary pentyl, cyclopenta, cyclohexyl, heptyl, octyl, nonyl, decyl, hendecane
Base, the configurational isomer of dodecyl and they.
Representative chloro hydrocarbon compatibilizer includes but is not limited to: 3- (chloromethyl) pentane, the chloro- 3- methylpentane of 3-, 1- chlorine
Hexane, 1,6- dichloro hexane, 1- chloroheptane, 1- chloro-octane, 1- chlorononane, 1- chlorodecane and 1,1,1- trichlorodecane.
Ester expanding material of the invention includes by general formula R1CO2R2The ester of expression, wherein R1And R2Independently selected from linear and ring
Shape, saturation and unsaturated alkyl and aryl.Preferred ester is mainly made of Elements C, H and O, has about 550 atom of about 80-
The molecular weight of mass unit.
Representative ester includes but is not limited to: (CH3)2CHCH2OOC(CH2)2-4OCOCH2CH(CH3)2(two isobutyl of binary acid
Base ester), ethyl hexanoate, cognac oil, n-butyl propionate, propionic acid n-propyl ester, ethyl benzoate, phthalic acid diη-propyl
Ester, benzoic acid ethoxymethyl ethyl ester, dipropyl carbonate, " Exxate 700 " (commodity acetic acid C7Arrcostab), " Exxate 800 "
(commodity acetic acid C8Arrcostab), dibutyl phthalate and tert-butyl acetate.
Lactone expanding material of the invention includes the lactone indicated by structure [A], [B] and [C]:
These lactones contain the ring (A) in six atoms, or the functional group-CO in the ring (B) of preferably five atoms2,
In for structure [A] and [B], R1To R8Independently selected from hydrogen or linear, branching, ring-type, two rings, saturation and undersaturated alkyl.
R1To R8Each of can be with R1To R8In another be connected to form ring.The lactone can have outside the ring in structure [C]
Alkylidene radical, wherein R1To R6Independently selected from hydrogen or linear, branching, ring-type, two rings, saturation and undersaturated alkyl.R1To R6In
Each can be with R1To R6In another be connected to form ring.The lactone expanding material has about 300 atom matter of about 80-
Measure unit, the molecular weight of about 200 atomic mass unit of preferably approximately 80-.
Representative lactone expanding material includes but is not limited to the compound listed in table 8.
Table 8
Lactone expanding material has the dynamic viscosity lower than about 7 centistokes generally at 40 DEG C.For example, at 40 DEG C, γ-ten
One alkanoic acid lactone has the dynamic viscosity of 5.4 centistokes, has the viscous of 4.5 centistokes along (3- hexyl -5- methyl) dihydrofuran -2- ketone
Degree.Lactone expanding material can be as described in the commercially available or U.S. Patent application 10/910,495 by submitting for 3rd such as August in 2004
Method preparation, the document is hereby incorporated by reference.
Aryl ether expanding material of the invention further comprises by general formula R1OR2The aryl ether of expression, in which: R1Selected from containing 6-
The aryl hydrocarbon of 12 carbon atoms;R2Selected from the aliphatic hydrocarbyl containing 1-4 carbon atom;And wherein the aryl ether has about
The molecular weight of about 150 atomic mass unit of 100-.In general formula R1OR2In representative R1Aryl includes phenyl, xenyl,
Cumenyl, 2,4,6- trimethylphenyls, tolyl, 3,5-dimethylphenyl, naphthalene and pyridyl group.In general formula R1OR2In representative R2
Aliphatic hydrocarbyl includes methyl, ethyl, propyl, isopropyl, butyl, isobutyl group, sec-butyl and tert-butyl.Representative aromatic oxide increases
Solvent includes but is not limited to: methyl phenyl ether (anisole), 1,3- dimethoxy benzene, ethylphenyl ether and butyl phenylate.
Fluoro-ether expanding material of the invention includes by general formula R1OCF2CF2H those of indicates, wherein R1Selected from containing about 5-
Aliphatic, the alicyclic and aromatic hydrocarbyl of about 15 carbon atoms, preferably primary, linear, saturated alkyl.Representative fluoro-ether increase-volume
Agent includes but is not limited to: C8H17OCF2CF2H and C6H13OCF2CF2H.It should be noted that if the refrigerant is fluoro-ether,
The expanding material can not be identical fluoro-ether.
Fluoro-ether expanding material may further include the ether derived from fluoroolefin and polyalcohol.The fluoroolefin can be with
With CF2=CXY pattern, wherein X is hydrogen, chlorine or fluorine, and Y is chlorine, fluorine, CF3Or ORf, wherein RfIt is CF3、C2F5Or C3F7.It represents
The fluoroolefin of property is tetrafluoroethene, chloro trifluoro ethylene, hexafluoropropene and perfluoro methyl vinyl ether.The polyalcohol can be with
It is linear or branching.Polyalcohols can have HOCH2(CHOH)x(CRR′)yCH2OH pattern, wherein R and R ' be hydrogen,
CH3Or C2H5And wherein x is the integer of 0-4, and y is the integer of 0-4.Branched polyol has C (OH) t (R) u (CH2OH)v
[(CH2)mCH2OH] w pattern, wherein R can be hydrogen, CH3Or C2H5, m is the integer of 0-3, and t and u can be 0 or 1, and v and w are 0-
4 integer, furthermore wherein t+u+v+w=4.Representative polyalcohol is trimethylolpropane, pentaerythrite, butanediol and second two
Alcohol.
Of the invention 1,1,1- trifluoroalkanes expanding material include by general formula CF3R11,1, the 1- trifluoroalkanes indicated, wherein R1
Aliphatic series and alicyclic alkyl selected from about 15 carbon atoms Han about 5-, preferably primary, linear, saturated alkyl.Representative 1,
1,1- trifluoroalkanes expanding material includes but is not limited to: 1,1,1- trifluorohexane and 1,1,1- trifluorododecane.
The effective quantity of expanding material refer to cause lubricant in the composition effective solubilization and therefore provide enough oil returns with
Optimization refrigeration, air-conditioning or heat-pump apparatus operation expanding material amount.
Composition of the invention, which will generally comprise, accounts for the present composition about 0.1- about 40wt%, preferably approximately 0.2-
The expanding material of about 20wt%, most preferably from about 0.3- about 10wt%.
The invention further relates to refrigerant or the solubilization method of heat-transfer fluid composition, the composition is included in and is selected from
Mineral oil alkylbenzene, synthesizes paraffin, synthesizes the present composition in the refrigeration lubricant of cycloalkane and poly- (α) alkene, wherein
The method includes contacting the lubricant with the composition in the presence of effective quantity expanding material, wherein the expanding material selects
From polyoxyalkylene glycol ethers, amide, nitrile, ketone, chlorocarbon, ester, lactone, aryl ether, fluoro-ether and 1,1,1- trifluoroalkanes.
It is described the invention further relates to the method improved in compression refrigeration, air-conditioning or heat-pump apparatus to compressor oil return
Method includes using the composition comprising expanding material in the apparatus.
Composition of the invention can further include ultraviolet light (UV) dyestuff and optional solubilizer.The UV dyestuff is
Allow people in the leakage point of refrigeration, air-conditioning or heat-pump apparatus or observes in composition dye fluorescence near the equipment to examine
Survey the useful constituent of the leakage of the composition.People can observe the fluorescence of dyestuff under ultraviolet light.Solubilizer is desirable
, due to the dissolubility of difference of such UV dyestuff in some compositions.
" ultraviolet light " dyestuff refers to the UV that the light in the ultraviolet light of electromagnetic spectrum or " close " ultraviolet range can be absorbed
Fluorescent composition.By photograph of the UV fluorescent dye in UV light for launching the radiation with any wavelength from 10 nanometers -750 nanometers
The fluorescence for penetrating lower generation may detect that.Therefore, if the composition containing such UV fluorescent dye is in refrigeration, air-conditioning or warm
It is leaked on the set point of pumping unit, then the fluorescence can be detected in the leakage point.Such UV fluorescent dye includes but is not limited to
Naphthalimide, cumarin, anthracene is luxuriant and rich with fragrance, xanthene, thioxanthene, naphthoxanthene, fluorescein and their derivative or group
It closes.
Solubilizer of the invention may include at least one selected from hydrocarbon, hydrocarbyl ether, polyoxyalkylene glycol ether, amide, nitrile,
Ketone, chlorocarbon, ester, lactone, aryl hydrocarbon, fluoro-ether and 1, the compound of 1,1- trifluoroalkanes.The polyoxyalkylene glycol ether, acyl
Amine, nitrile, ketone, chlorocarbon, ester, lactone, aryl ether, fluoro-ether and 1,1,1- Trifluoroalkane solubilizing agents be defined herein before this for
In the expanding material of conventional refrigerant lubricant.
Hydrocarbon solubilizer of the invention includes hydrocarbon comprising containing 5 or less carbon atoms and only has hydrogen but not other
Straight chain, branch or the cyclic-paraffins or alkene of functional group.Representative hydrocarbon solubilizer includes propane, propylene, cyclopropane, positive fourth
Alkane, iso-butane, 2- methybutane and pentane.It should be noted that the solubilizer can be with if the composition includes hydrocarbon
It is not identical hydrocarbon.
Hydrocarbon ether solubilizing agents of the invention include the ether only containing carbon, hydrogen and oxygen, such as dimethyl ether (DME).
Solubilizer of the invention can be used as single compound presence, or can be used as the mixture of more than one solubilizer
In the presence of.The mixture of solubilizer can be containing belonging to two kinds of solubilizer in same category compound, such as two kinds of lactones, or
The two kinds of solubilizer to belong to a different category in compound, such as lactone and polyoxyalkylene glycol ether.
In the present invention combination comprising refrigerant and UV Fluorescence Fluorescence dyestuff or comprising heat-transfer fluid and UV fluorescent dye
In object, the about 0.001wt%- about 1.0wt% of the composition be UV dyestuff, preferably approximately 0.005wt%- about
0.5wt%, most preferably 0.01wt%- about 0.25wt%.
Solubilizer such as ketone has unfavorable smell, it can be covered by the addition of odor masking agent or fragrance.Smell
The representative instance of screening agent or fragrance may include evergreen (Evergreen), Fresh Lemon, cherry, cortex cinnamomi, peppermint, Hua Huo
Orange peel, their all commercially available and carvenes and firpene.Such odor masking agent can be by based on odor masking agent and solubilizer
The concentration that the about 0.001wt%- of total weight is up to about 15wt% uses.
These dissolubilities of UV fluorescent dye in the compositions of the present invention may be difference.Therefore, these dyestuffs are introduced
Be to the method in refrigeration, air-conditioning or heat-pump apparatus it is clumsy, it is expensive and time-consuming.U.S. Patent number RE36,951 is described
A kind of method, it uses dye powder, solid grain or the dyestuff being inserted into the component of refrigeration, air-conditioning or heat-pump apparatus
Slurry.When refrigerant and lubricant recycle in the device, which dissolves or disperses and spread whole equipment.In the literature
Describe many other methods dyestuff being introduced into refrigeration or air-conditioning equipment.
It is desirable that the UV fluorescent dye may be dissolved in refrigerant itself, therefore it is not required to be introduced into refrigeration, air-conditioning
Any ad hoc approach in equipment or heat pump.The present invention relates to the compositions including UV fluorescent dye, it can be used as in refrigeration
Solution in agent is introduced in system.Composition of the invention can be while keeping the dyestuff under dissolved state even
Allow to contain the composition storage and conveying of dyestuff at low temperatures.
Comprising refrigerant, UV fluorescent dye and solubilizer or comprising heat-transfer fluid and UV fluorescent dye and solubilizer
In the present composition, about 1- about 50wt%, preferably approximately the 2- about 25wt%, most preferably from about 5- of total composition are big
About 15wt% is solubilizer.In the present compositions, the UV fluorescent dye with about 0.001wt%- about
The concentration of 1.0wt%, preferably 0.005wt%- about 0.5wt%, most preferably 0.01wt%- about 0.25wt% exist.
The invention further relates in refrigeration, air-conditioning or heat-pump apparatus using further including UV fluorescent dye,
With the method for the composition of optional solubilizer.This method includes introducing the composition in refrigeration, air-conditioning or heat-pump apparatus.
This can by the presence of solubilizer by UV fluorescent dye be dissolved in the composition and by the combination be introduced into the equipment come
It realizes.Alternatively, this can be by being introduced into solubilizer and UV fluorescent dye in conjunction with and by the combination containing refrigerant and/or heat
It conducts in the refrigeration or air-conditioning equipment of fluid and realizes.Resulting composition can be used for refrigeration, air-conditioning or heat-pump apparatus.
The invention further relates to the methods for using the combination analyte detection leakage comprising UV fluorescent dye.The dyestuff exists
Presence permission in composition detects the refrigerant leaked in refrigeration, air-conditioning or heat-pump apparatus.Leak detection facilitates
Tackle, solve or prevent the operating of the inefficiency of the equipment or system or failure of apparatus.Leak detection also helps it to contain in device
Operating used in chemicals.
This method includes providing into refrigeration, air-conditioning or heat-pump apparatus comprising refrigerant, ultraviolet fluorescent described here
The composition of dyestuff and non-essential solubilizer described here, and using for refrigerant of the detection containing UV fluorescent dye
Appropriate device.The suitable equipment of detection dyestuff includes, but are not limited to ultraviolet radiator, usually referred to as " black light " or " blue light ".These
Ultraviolet radiator can be commercially available from many sources of supply specially designed for this purpose.Once the composition containing UV fluorescent dye
It has been incorporated into the refrigeration, air-conditioning or heat-pump apparatus and it is allowed to cycle through the system, by irradiating the ultraviolet radiator
The fluorescence of the dyestuff is observed on the device and near any breakthrough it can be found that leakage.
The invention further relates to the methods of high GWP refrigerant in substitution refrigeration, air-conditioning or heat-pump apparatus, wherein the height
GWP refrigerant is selected from R134a, R22, R245fa, R114, R236fa, R124, R410A, R407C, R417A, R422A, R507A
And R404A, the method includes composition of the invention is supplied to use, is used to or is designed to cause using the high GWP
The refrigeration, air-conditioning or the heat-pump apparatus of cryogen.Vapor compression refrigeration, air-conditioning or heat pump system include evaporator, and compressor is cold
Condenser and expansion device.Vapor-compression cycle reuses refrigerant in multiple steps, to generate cooling in one step
Effect generates heating effect in different steps.The circulation can easily describe as follows.Liquid refrigerant passes through expansion dress
It sets and enters evaporator, then boiling forms gas and generates cooling effect the liquid refrigerant at low temperature in evaporator.It should
Low-pressure gas enters in compressor, its pressure and temperature is increased after wherein gas is compressed.Elevated pressures (compression) gas
State refrigerant condenses in wherein refrigerant subsequently into condenser and its heat is discharged in environment.The refrigerant returns to
In the expansion device, it is expanded into evaporator by the liquid after the device from higher-pressure level within the condenser
Low voltage level, therefore repeat the circulation.
Movement refrigeration equipment used herein or movement air-conditioning equipment, which refer to, is integrated to road, track, ocean or sky
Delivery unit in any refrigeration or air-conditioning equipment.In addition, being used to as the system independent of any mobile vehicle (referred to as
" through transport (intermodal) " system) offer is freezed or the equipment of air-conditioning is also included in the present invention.Such intermodal system includes
" container " (in conjunction with ocean/land transport) and " permutoid " (in conjunction with road and railway transportation).Present invention is particularly useful for roads
Road transport refrigeration or air-conditioning equipment, such as air conditioning equipment of car or the road transporting tool of refrigeration.
The invention further relates to refrigerating method, including evaporating composition of the invention near body to be cooled, and
The composition is condensed later.
The invention further relates to the methods for generating heat, including in the condensed around combination of the invention of body to be heated
Object, and later evaporate the composition.
The invention further relates to the refrigeration comprising the present composition, air-conditioning or heat-pump apparatus, wherein the composition
Include at least one fluoroolefin.
The invention further relates to the movement air-conditioning equipments comprising the present composition, wherein the composition includes at least
A kind of fluoroolefin.
The invention further relates to the method for coolant leaks in early detection refrigeration, air-conditioning or heat-pump apparatus, the sides
Method includes in the apparatus using the reduction of non-azeotropic compositions and monitoring cooling performance.The non-azeotropic compositions will let out
When leakage from refrigeration, air-conditioning or heat-pump apparatus be fractionated and will be first from the equipment leakage compared with the component of low boiling point (higher vapor pressure)
Out.When it happens, if the more low-boiling component in the composition provides most of refrigerating capacity, there is refrigeration energy
Power significantly reduces simultaneously the therefore significant decrease of equipment performance.Passenger in automotive air-conditioning system, such as in automobile will test
To the reduction of system cooling capacity.This reduction of cooling capacity can be construed to refer to that refrigerant is leaking and the system
It needs to repair.
The invention further relates to use composition of the invention as the method for heat-transfer fluid composition, the method
Including the composition is transported to radiator from heat source.
Heat-transfer fluid is utilized to through radiation, conduction or convection current, by heat from a space, position, object or machine
Different spaces, position, object or body are shifted, migrate or separated in body.Heat-transfer fluid can be by providing from remote
Refrigeration (or heating) system carry out the transfer equipment of cooling (or heating) and be used as secondary coolant.In some systems, institute
Steady state (that is, do not evaporate or condense) can be maintained in the whole process by stating heat-transfer fluid.Alternatively, evaporation cooling procedure
Heat-transfer fluid can similarly be utilized.
Heat source can be defined as any space for wishing therefrom to shift, migrate or separate heat, position, object or body.
The example of heat source can be the space (open or closed) for needing refrigeration or cooling, such as the refrigerator or refrigerator at the supermarket
Cabinet, needs the space of air-conditioning, or needs the seating compartment of the automobile of air-conditioning.Radiator can be defined as that heat can be absorbed
Any space, position, object or body.Vapor compression refrigeration system is an example of such radiator.
In another embodiment, the present invention relates to the foaming agent for being used to prepare foam, it includes retouch herein
The composition containing fluoroolefin stated.In other embodiments, the present invention provides foamable composite, preferably polyurethane and more
Isocyanate foams composition, and the method for preparing foam.In these foam embodiments, including one or more present invention
The composition containing fluoroolefin as the foaming agent in foamable composite, which preferably includes a kind of or more
Kind can be reacted under proper condition and be foamed to form the annexing ingredient of foam or honeycomb structure.Foam according to the present invention
Embodiment, any method well known in the art, such as " Polyurethanes Chemistry and Technology ", the
I and II volumes, described in Saunders and Frisch, 1962, John Wiley and Sons, New York, N.Y. that
(document is hereby incorporated by reference) can be used or use through reorganization a bit.
The invention further relates to the forming methods of foam, comprising: (a) adds the composition of the invention containing fluoroolefin
It is added in foamable composite;(b) foamable composite is reacted.
Another embodiment of the invention is related to the composition described herein containing fluoroolefin in Sprayable composition
In be used as the purposes of propellant.In addition, the present invention relates to sprayable group comprising the composition described herein containing fluoroolefin
Close object.Active constituent and inert component to be sprayed, solvent and other materials can also exist in Sprayable composition.It is excellent
Selection of land, the Sprayable composition are aerosols.Suitable active material to be sprayed includes but is not limited to cosmetic material, such as
Deodorant, aromatic, hair spray, detergent and polishing agent and for example anti-asthma of medicinal materials and anti-halitosis medications.
The invention further relates to the preparation methods of aerosol product, comprising steps of containing fluoroolefin for described herein
Composition be added in the active constituent in aerosol container, wherein the composition plays propellant.
The method for inhibiting flame is provided on the other hand, the method includes making flame and comprising the disclosure of invention
The fluid of composition containing fluoroolefin contacts.Any suitable side for contacting the flame with the present composition can be used
Method.For example, can by the composition containing fluoroolefin of the disclosure of invention by being sprayed, toppling over, etc. in modes to flame,
Or at least part of flame can be immersed in the flame suppressant composition.In view of teaching herein, the skill of this field
Art personnel will easily vary various conventional equipments and the method for suppression for the disclosure of invention.
Another embodiment, which is provided, puts out or inhibits the method for fire by total flooding (total-flood) applying mode,
It include: that the reagent of the composition containing fluoroolefin comprising the disclosure of invention is provided;The reagent is arranged in pressurization row
In place system;It is discharged into a region with by the reagent to put out or inhibit the fire in that region.Another is implemented
Scheme provides the method for making islands inert to prevent fire or explosion, comprising: provides fluorine-containing comprising the disclosure of invention
For the reagent of the composition of alkene;The reagent is arranged in pressurized discharge system;The region is discharged by the reagent
In with prevent fire or explosion occur.
Term " putting out ", which is conventionally used to indicate, completely eliminates fire;And " inhibition " is conventionally used to indicate reduction, and not necessarily
Completely eliminate fire or explosion.Term as used herein " putting out " and " inhibition " will be interchangeably used.It is general there are four kinds
The halocarbon fire and explosion proof applications of type.(1) in total flooding fire suppression and/or inhibition application, the reagent is discharged into
To obtain the concentration for being enough to put out or inhibit existing fire in space.Total flooding purposes includes protecting sky that is closed, may occupying
Between, such as computer room and dedicated, usually idle space such as cabin in aero-engine gondola and carrier.(2) it is spraying
It penetrates in (streaming) application, the reagent is applied directly in the region on fire or to fire.This is usually using artificial
The wheel or mancarried device of operation are realized.The second method for including as spray application uses " localization
(localized) " system discharges reagent towards fire by one or more fixed nozzles.Localizing system can manually or from
Start dynamicly.(3) in explosion suppression, the composition containing fluoroolefin of the disclosure of invention is discharged to inhibit to be drawn
The explosion of hair.Term " inhibition " is generally used in this application, because explosion is usually self limiting.However, this art
The use of language is not necessarily mean that the reagent does not put out explosion.In this application, detector derives from quick-fried commonly used to detection
Fried expansion fireball, and discharge the reagent promptly to inhibit to explode.Explosion suppression is main but is not only used for defence application.
(4) in deactivation, the composition containing fluoroolefin of the disclosure of invention is discharged into space to prevent explosion or fire
Calamity is initiated.In general, using the system similar or identical used with total flooding fire suppression or inhibition.In general, detection is dangerous
The presence of condition (for example, flammable or explosive gas dangerous concentrations), then discharge the disclosure of invention containing fluoroolefin
Composition is to prevent explosion or fire from occurring until that can remedy the condition.
It can carry out putting out method by the enclosed area for introducing the composition around fire.What be can be used is any
Known introducing method, as long as being spaced suitable by the proper amount of metered enclosed area of composition.For example, can
To introduce composition as follows: injection is for example using Conventional portable (or fixed) fire-extinguishing apparatus;Atomization;Or flood
(flooding), the closing of corral a fire such as by composition release (using suitable pipeline, valve and controller) is arrived
Qu Zhong.The composition can optionally with inert propellant, such as nitrogen, argon gas, Glycidyl azide polymer
Decomposition product or carbon dioxide combine, to improve the rate that the composition is discharged from the injection used or flood device.
Preferably, putting out method includes to be enough to stamp out a fire or the amount of flame is by the alkene containing fluoro of the disclosure of invention
The composition of hydrocarbon is introduced into fire or flame.Those skilled in the art will recognize that the fire inhibitor for putting out that specific fire needs
Amount will depend on the property and degree of harm.When that will introduce fire inhibitor by flood, cup burner test data can
For determining the amount or concentration of putting out fire inhibitor required for the fire of specific type and scale.
When combination is put out or inhibits fire in a manner of total flooding application or fire deactivation, can be used for determining alkene containing fluoro
The laboratory test of the Valid concentration of the composition of hydrocarbon is for example described in U.S. Patent number 5,759,430, should
Document is incorporated herein for reference.
Embodiment
Embodiment 1
The influence of steam leakage
If at -25 DEG C or having a regulation, 25 DEG C at a temperature of initial composition is fitted into container, and measure the composition
Initial vapour pressure.Allow the composition from container leakage, while keeping temperature-resistant, until the 50wt% of initial composition is removed
It goes, measures the vapour pressure of remaining composition in container at this time.As a result it is shown in table 9.
Table 9
For composition of the invention, original composition and after removing 50wt% between remaining composition
Vapour pressure difference is then less than about 10%.This shows that composition of the invention may be azeotropic or close to azeotropic.
Embodiment 2
Refrigeration performance data
Table 10 shows the performance of various refrigerant compositions of the invention compared with HFC-134a.In table 10, Evap
Pres is evaporator pressure, and Cond Pres is condenser pressure, and Comp Disch T is compressor outlet temperature, and COP is energy
Efficiency, CAP are capacity (capacity).Data are based on following condition.
It is noted that considering overheat in cooling capacity calculating.
Table 10
Several compositions have even energy efficiency (COP) more higher than HFC-134a, while lower discharge being maintained to press
Power and temperature.The capacity of the present composition is also similar to R134a, this shows that they may especially be transported in refrigeration and air-conditioning
Be used as R134a in dynamic air conditioning applications replaces refrigerant.Those of hydrocarbonaceous composition can also improve and conventional mineral oil and alkane
The oily dissolubility of base benzene lubricant.
Embodiment 3
Refrigeration performance data
Table 11 shows the performance of various refrigerant compositions of the invention compared with R404A and R422A.
In table 11, Evap Pres is evaporator pressure, and Cond Pres is condenser pressure, and Comp Disch T is pressure
Contracting device outlet temperature, EER are energy efficiencies, and CAP is capacity.Data are based on following condition.
It is noted that considering overheat in cooling capacity calculating.
Table 11
Several compositions have the energy efficiency (COP) similar with R404A and R422A.Exhaust temperature also below R404A and
R507A.The capacity of the present composition is also similar to R404A, R507A and R422A, this shows that they may be in refrigeration and air-conditioning
In be used as instead of refrigerant.Those of hydrocarbonaceous composition can also be improved to be dissolved with the oil of conventional mineral oil and alkyl benzene lubricants
Property.
Embodiment 4
Refrigeration performance data
Table 12 shows various refrigerant compositions of the invention compared with HCFC-22, R410A, R407C and R417A
Performance.In table 12, Evap Pres is evaporator pressure, and Cond Pres is condenser pressure, and Comp Disch T is compression
Device outlet temperature, EER are energy efficiencies, and CAP is capacity.Data are based on following condition.
It is noted that considering overheat in cooling capacity calculating.
Table 12
Composition has the energy efficiency (EER) similar with R22, R407C, R417A and R410A, while maintaining low row
Put temperature.The capacity of the present composition is also similar to R22, R407C and R417A, this shows that they may be in refrigeration and air-conditioning
In be used as instead of refrigerant.Those of hydrocarbonaceous composition can also be improved to be dissolved with the oil of conventional mineral oil and alkyl benzene lubricants
Property.
Embodiment 5
Refrigeration performance data
Table 13 shows the performance of various refrigerant compositions of the invention compared with HCFC-22 and R410A.In table 13
In, Evap Pres is evaporator pressure, and Cond Pres is condenser pressure, and Comp Disch T is compressor outlet temperature,
EER is energy efficiency, and CAP is capacity.Data are based on following condition.
It is noted that considering overheat in cooling capacity calculating.
Table 13
Composition has the energy efficiency (EER) similar with R22 and R410A, while maintaining reasonable exhaust temperature.This hair
The capacity of bright composition is also similar to R22, this shows that they may be used as in refrigeration and air-conditioning instead of refrigerant.
Embodiment 6
Flammability
Combustible cpd can be by ASTM (American Society of Testing andMaterials)
Under E681-01, test determination is carried out using electronic ignition source.In 101kPa (14.7psia), 100 DEG C (212 °F) and 50% phase
To under humidity, with aerial various concentration to the mixture of HFC-1234yf, HFC-1225ye and the disclosure of invention
Such burning test is carried out to determine flammability lower limit (LFL) and the flammability upper limit (UFL).As a result it is provided in table 14.
Table 14
The result shows that the addition of HFC-1225ye reduces flammability when HFC-1234yf is flammable.Therefore, comprising big
The composition of about 1wt%- about 49wt%HFC-1234yf and about 99wt%- about 51wt%HFC-1225ye are preferred
's.
Claims (30)
1. including the composition of HFC-1234ye and at least one compound selected from following substance: HFC-1243zf, HFC-32,
HFC-125、HFC-134、HFC-134a、HFC-143a、HFC-152a、HFC-161、HFC-227ea、HFC-236ea、HFC-
236fa, HFC-245fa, HFC-365mfc, propane, normal butane, iso-butane, 2- methybutane, pentane, pentamethylene, dimethyl
Ether, CF3SCF3、CO2And CF3I。
2. including the composition of HFC-1243zf and at least one compound selected from following substance: HFC-32, HFC-125,
HFC-134、HFC-134a、HFC-143a、HFC-152a、HFC-161、HFC-227ea、HFC-236ea、HFC-236fa、HFC-
245fa, HFC-365mfc, propane, normal butane, iso-butane, 2- methybutane, pentane, pentamethylene, dimethyl ether, CF3SCF3、
CO2And CF3I。
3. the composition of claim 2, is selected from:
HFC-1243zf, HFC-134 and HFC-227ea;
HFC-1243zf, HFC-134 and normal butane;
HFC-1243zf, HFC-134 and dimethyl ether;
HFC-1243zf, HFC-134 and CF3I;
HFC-1243zf, HFC-134a and HFC-152a;
HFC-1243zf, HFC-134a and normal butane;
HFC-1243zf, HFC-152a and propane;
HFC-1243zf, HFC-152a and normal butane;
HFC-1243zf, HFC-152a and iso-butane;
HFC-1243zf, HFC-152a and dimethyl ether;
HFC-1243zf, HFC-227ea and normal butane;
HFC-1243zf, HFC-227ea and iso-butane;
HFC-1243zf, HFC-227ea and dimethyl ether;
HFC-1243zf, normal butane and dimethyl ether;
HFC-1243zf, iso-butane and dimethyl ether;
HFC-1243zf, iso-butane and CF3I;With
HFC-1243zf, dimethyl ether and CF3SCF3。
4. the composition of claim 2, is selected from:
About 1wt%- about 98wt%HFC-1243zf, about 1wt%- about 98wt%HFC-134 and about 1wt%- is big
About 98wt%HFC-227ea;
About 1wt%- about 98wt%HFC-1243zf, about 1wt%- about 98wt%HFC-134 and about 1wt%- is big
About 40wt% normal butane;
About 1wt%- about 98wt%HFC-1243zf, about 1wt%- about 98wt%HFC-134 and about 1wt%- is big
About 98wt% dimethyl ether;
About 1wt%- about 98wt%HFC-1243zf, about 1wt%- about 98wt%HFC-134 and about 1wt%- is big
About 98wt%CF3I;
About 1wt%- about 98wt%HFC-1243zf, about 1wt%- about 98wt%HFC-134a and about 1wt%- is big
About 98wt%HFC-152a;
About 1wt%- about 98wt%HFC-1243zf, about 1wt%- about 98wt%HFC-134a and about 1wt%- is big
About 40wt% normal butane;
About 1wt%- about 70wt%HFC-1243zf, about 1wt%- about 70wt%HFC-152a and about 29wt%-
About 98wt% propane;
About 1wt%- about 98wt%HFC-1243zf, about 1wt%- about 98wt%HFC-152a and about 1wt%- is big
About 30wt% normal butane;
About 1wt%- about 98wt%HFC-1243zf, about 1wt%- about 98wt%HFC-152a and about 1wt%- is big
About 40wt% iso-butane;
About 1wt%- about 98wt%HFC-1243zf, about 1wt%- about 98wt%HFC-152a and about 1wt%- is big
About 98wt% dimethyl ether;
About 1wt%- about 98wt%HFC-1243zf, about 1wt%- about 98wt%HFC-227ea and about 1wt%-
About 40wt% normal butane;
About 1wt%- about 98wt%HFC-1243zf, about 1wt%- about 90wt%HFC-227ea and about 1wt%-
About 50wt% iso-butane;
About 1wt%- about 98wt%HFC-1243zf, about 1wt%- about 80wt%HFC-227ea and about 1wt%-
About 90wt% dimethyl ether;
About 1wt%- about 98wt%HFC-1243zf, about 1wt%- about 40wt% normal butane and about 1wt%- are about
98wt% dimethyl ether;
About 1wt%- about 98wt%HFC-1243zf, about 1wt%- about 60wt% iso-butane and about 1wt%- are about
98wt% dimethyl ether;
About 1wt%- about 98wt%HFC-1243zf, about 1wt%- about 40wt% iso-butane and about 1wt%- are about
98wt%CF3I;With
About 1wt%- about 98wt%HFC-1243zf, about 1wt%- about 40wt% dimethyl ether and about 1wt%- is big
About 90wt%CF3SCF3。
5. the composition of claim 2, is selected from:
About 10wt%- about 80wt%HFC-1243zf, about 10wt%- about 80wt%HFC-134 and about 10wt%-
About 80wt%HFC-227ea;
About 10wt%- about 80wt%HFC-1243zf, about 10wt%- about 80wt%HFC-134 and about 1wt%-
About 30wt% normal butane;
About 10wt%- about 80wt%HFC-1243zf, about 10wt%- about 80wt%HFC-134 and about 1wt%-
About 30wt% dimethyl ether;
About 10wt%- about 80wt%HFC-1243zf, about 10wt%- about 80wt%HFC-134 and about 10wt%-
About 80wt%CF3I;
About 10wt%- about 80wt%HFC-1243zf, about 10wt%- about 80wt%HFC-134a and about 1wt%-
About 50wt%HFC-152a;
About 10wt%- about 80wt%HFC-1243zf, about 10wt%- about 80wt%HFC-134a and about 1wt%-
About 30wt% normal butane;
About 10wt%- about 70wt%HFC-1243zf, about 1wt%- about 50wt%HFC-152a and about 29wt%-
About 40wt% propane;
About 10wt%- about 80wt%HFC-1243zf, about 1wt%- about 80wt%HFC-152a and about 1wt%-
About 20wt% normal butane;
About 10wt%- about 80wt%HFC-1243zf, about 1wt%- about 80wt%HFC-152a and about 1wt%-
About 30wt% iso-butane;
About 10wt%- about 80wt%HFC-1243zf, about 1wt%- about 80wt%HFC-152a and about 1wt%-
About 30wt% dimethyl ether;
About 10wt%- about 80wt%HFC-1243zf, about 1wt%- about 80wt%HFC-227ea and about 1wt%-
About 30wt% normal butane;
About 10wt%- about 80wt%HFC-1243zf, about 1wt%- about 80wt%HFC-227ea and about 1wt%-
About 30wt% iso-butane;
About 10wt%- about 80wt%HFC-1243zf, about 1wt%- about 80wt%HFC-227ea and about 1wt%-
About 30wt% dimethyl ether;
About 10wt%- about 90wt%HFC-1243zf, about 1wt%- about 30wt% normal butane and about 1wt%- is big
About 30wt% dimethyl ether;
About 10wt%- about 90wt%HFC-1243zf, about 1wt%- about 30wt% iso-butane and about 1wt%- is big
About 30wt% dimethyl ether;
About 10wt%- about 80wt%HFC-1243zf, about 1wt%- about 30wt% iso-butane and about 10wt%- is big
About 80wt%CF3I;With
About 10wt%- about 80wt%HFC-1243zf, about 1wt%- about 30wt% dimethyl ether and about 10wt%-
About 80wt%CF3SCF3。
6. the composition of claim 1, including azeotropic selected from the following or close to Azeotrope compositions:
About 38wt%- about 99wt%HFC-1234ye and about 62wt%- about 1wt%HFC-134;
About 1wt%- about 99wt%HFC-1234ye and about 99wt%- about 1wt%HFC-236ea;
About 1wt%- about 99wt%HFC-1234ye and about 99wt%- about 1wt%HFC-236fa;
About 1wt%- about 99wt%HFC-1234ye and about 99wt%- about 1wt%HFC-245fa;
About 1wt%- about 78wt%HFC-1234ye and about 99wt%- about 22wt% normal butane;
About 70wt%- about 99wt%HFC-1234ye and about 30wt%- about 1wt% pentamethylene;
About 1wt%- about 68wt%HFC-1234ye and about 99wt%- about 32wt% iso-butane;
About 47wt%- about 99wt%HFC-1234ye and about 53wt%- about 1wt%2- methybutane;With
About 57wt%- about 99wt%HFC-1234ye and about 43wt%- about 1wt% pentane.
7. the composition of claim 2, including azeotropic selected from the following or close to Azeotrope compositions:
About 1wt%- about 99wt%HFC-1243zf and about 99wt%- about 1wt%HFC-134;
About 1wt%- about 99wt%HFC-1243zf and about 99wt%- about 1wt%HFC-134a;
About 1wt%- about 99wt%HFC-1243zf and about 99wt%- about 1wt%HFC-152a;
About 1wt%- about 99wt%HFC-1243zf and about 99wt%- about 1wt%HFC-161;
About 1wt%- about 99wt%HFC-1243zf and about 99wt%- about 1wt%HFC-227ea;
About 53wt%- about 99wt%HFC-1243zf and about 47wt%- about 1wt%HFC-236ea;
About 49wt%- about 99wt%HFC-1243zf and about 51wt%- about 1wt%HFC-236fa;
About 66wt%- about 99wt%HFC-1243zf and about 34wt%- about 1wt%HFC-245fa;
About 1wt%- about 71wt%HFC-1243zf and about 99wt%- about 29wt% propane;
About 62wt%- about 99wt%HFC-1243zf and about 38wt%- about 1wt% normal butane;
About 45wt%- about 99wt%HFC-1243zf and about 55wt%- about 1wt% iso-butane;
About 1wt%- about 99wt%HFC-1243zf and about 99wt%- about 1wt% dimethyl ether;
About 1wt%- about 98wt%HFC-1243zf, about 1wt%- about 98wt%HFC-134 and about 1wt%- is big
About 98wt%HFC-227ea;
About 1wt%- about 98wt%HFC-1243zf, about 1wt%- about 98wt%HFC-134 and about 1wt%- is big
About 40wt% normal butane;
About 1wt%- about 98wt%HFC-1243zf, about 1wt%- about 98wt%HFC-134 and about 1wt%- is big
About 98wt% dimethyl ether;
About 1wt%- about 98wt%HFC-1243zf, about 1wt%- about 98wt%HFC-134 and about 1wt%- is big
About 98wt%CF3I;
About 1wt%- about 98wt%HFC-1243zf, about 1wt%- about 98wt%HFC-134a and about 1wt%- is big
About 98wt%HFC-152a;
About 1wt%- about 98wt%HFC-1243zf, about 1wt%- about 98wt%HFC-134a and about 1wt%- is big
About 40wt% normal butane;
About 1wt%- about 70wt%HFC-1243zf, about 1wt%- about 70wt%HFC-152a and about 29wt%-
About 98wt% propane;
About 1wt%- about 98wt%HFC-1243zf, about 1wt%- about 98wt%HFC-152a and about 1wt%- is big
About 30wt% normal butane;
About 1wt%- about 98wt%HFC-1243zf, about 1wt%- about 98wt%HFC-152a and about 1wt%- is big
About 40wt% iso-butane;
About 1wt%- about 98wt%HFC-1243zf, about 1wt%- about 98wt%HFC-152a and about 1wt%- is big
About 98wt% dimethyl ether;
About 1wt%- about 98wt%HFC-1243zf, about 1wt%- about 98wt%HFC-227ea and about 1wt%-
About 40wt% normal butane;
About 1wt%- about 98wt%HFC-1243zf, about 1wt%- about 90wt%HFC-227ea and about 1wt%-
About 50wt% iso-butane;
About 1wt%- about 98wt%HFC-1243zf, about 1wt%- about 80wt%HFC-227ea and about 1wt%-
About 90wt% dimethyl ether;
About 1wt%- about 98wt%HFC-1243zf, about 1wt%- about 40wt% normal butane and about 1wt%- are about
98wt% dimethyl ether;
About 1wt%- about 98wt%HFC-1243zf, about 1wt%- about 60wt% iso-butane and about 1wt%- are about
98wt% dimethyl ether;
About 1wt%- about 98wt%HFC-1243zf, about 1wt%- about 40wt% iso-butane and about 1wt%- are about
98wt%CF3I;With
About 1wt%- about 98wt%HFC-1243zf, about 1wt%- about 40wt% dimethyl ether and about 1wt%- is big
About 90wt%CF3SCF3。
8. the composition of claim 1, including Azeotrope compositions selected from the following:
In 24.0wt%HFC-1234ye that about -25 DEG C of at a temperature of vapour pressure is about 3.35psia (23.1kPa) and
76.0wt%HFC-236ea;
In 42.5wt%HFC-1234ye that about 25 DEG C of at a temperature of vapour pressure is about 22.8psia (157kPa) and
57.5wt%HFC-245fa;
In 41.2wt%HFC-1234ye that about 25 DEG C of at a temperature of vapour pressure is about 38.0psia (262kPa) and
58.8wt% normal butane;
In 16.4wt%HFC-1234ye that about 25 DEG C of at a temperature of vapour pressure is about 50.9psia (351kPa) and
83.6wt% iso-butane;
In 80.3wt%HFC-1234ye that about 25 DEG C of at a temperature of vapour pressure is about 23.1psia (159kPa) and
19.7wt%2- methybutane;
In 87.7wt%HFC-1234ye that about 25 DEG C of at a temperature of vapour pressure is about 21.8psia (150kPa) and
12.3wt% pentane.
9. the composition of claim 2, including Azeotrope compositions selected from the following:
In 63.0wt%HFC-1243zf that about -25 DEG C of at a temperature of vapour pressure is about 13.5psia (93kPa) and
37.0wt%HFC-134;
In 25.1wt%HFC-1243zf that about -25 DEG C of at a temperature of vapour pressure is about 15.9psia (110kPa) and
74.9wt%HFC-134a;
In 40.7wt%HFC-1243zf that about -25 DEG C of at a temperature of vapour pressure is about 15.2psia (104kPa) and
59.3wt%HFC-152a;
In 78.5wt%HFC-1243zf that about -25 DEG C of at a temperature of vapour pressure is about 13.1psia (90kPa) and
21.5wt%HFC-227ea;
In 32.8wt%HFC-1243zf that about -25 DEG C of at a temperature of vapour pressure is about 31.0psia (213kPa) and
67.2wt% propane;
In 90.3wt%HFC-1243zf that about -25 DEG C of at a temperature of vapour pressure is about 13.5psia (93kPa) and
9.7wt% normal butane;
In 80.7wt%HFC-1243zf that about -25 DEG C of at a temperature of vapour pressure is about 14.3psia (98kPa) and
19.3wt% iso-butane;With
In 72.7wt%HFC-1243zf that about -25 DEG C of at a temperature of vapour pressure is about 12.0psia (83kPa) and
27.3wt% dimethyl ether;
About -25 DEG C of at a temperature of vapour pressure be about 13.5psia (93.4kPa) 58.6wt%HFC-1243zf,
34.1wt%HFC-134 and 7.3wt%HFC-227ea;
About -25 DEG C of at a temperature of vapour pressure be about 14.7psia (101kPa) 27.5wt%HFC-1243zf,
58.7wt%HFC-134 and 13.9wt% normal butane;
About -25 DEG C of at a temperature of vapour pressure be about 10.1psia (69.7kPa) 18.7wt%HFC-1243zf,
63.5wt%HFC-134 and 17.8wt% dimethyl ether;
About -25 DEG C of at a temperature of vapour pressure be about 14.5psia (99.6kPa) 11.4wt%HFC-1243zf,
23.9wt%HFC-134 and 64.7wt%CF3I;
About -25 DEG C of at a temperature of vapour pressure be about 15.0psia (103kPa) 41.5wt%HFC-1243zf,
21.5wt%HFC-134a and 37.1wt%HFC-152a;
About -25 DEG C of at a temperature of vapour pressure be about 17.0psia (117kPa) 7.0wt%HFC-1243zf,
81.4wt%HFC-134a and 11.6wt% normal butane;
About -25 DEG C of at a temperature of vapour pressure be about 31.7psia (219kPa) 2.9wt%HFC-1243zf,
34.0wt%HFC-152a and 63.0wt% propane;
About -25 DEG C of at a temperature of vapour pressure be about 15.7psia (108kPa) 28.8wt%HFC-1243zf,
60.3wt%HFC-152a and 11.0wt% normal butane;
About -25 DEG C of at a temperature of vapour pressure be about 17.1psia (118kPa) 6.2wt%HFC-1243zf,
68.5wt%HFC-152a and 25.3wt% iso-butane;
About -25 DEG C of at a temperature of vapour pressure be about 11.4psia (78.7kPa) 33.1wt%HFC-1243zf,
36.8wt%HFC-152a and 30.1wt% dimethyl ether;
About -25 DEG C of at a temperature of vapour pressure be about 13.7psia (94.3kPa) 62.0wt%HFC-1243zf,
28.4wt%HFC-227ea and 9.6wt% normal butane;
About -25 DEG C of at a temperature of vapour pressure be about 15.0psia (103kPa) 27.9wt%HFC-1243zf,
51.0wt%HFC-227ea and 21.1wt% iso-butane;
About -25 DEG C of at a temperature of vapour pressure be about 12.8psia (88.1kPa) 48.1wt%HFC-1243zf,
44.8wt%HFC-227ea and 7.2wt% dimethyl ether;
About -25 DEG C of at a temperature of vapour pressure be about 12.3psia (84.7kPa) 60.3wt%HFC-1243zf,
10.1wt% normal butane and 29.6wt% dimethyl ether;
About -25 DEG C of at a temperature of vapour pressure be about 13.2psia (90.7kPa) 47.1wt%HFC-1243zf,
26.9wt% iso-butane and 25.9wt% dimethyl ether;
About -25 DEG C of at a temperature of vapour pressure be about 14.0psia (96.3kPa) 32.8wt%HFC-1243zf,
1.1wt% iso-butane and 66.1wt%CF3I;
About -25 DEG C of at a temperature of vapour pressure be about 13.6psia (93.8kPa) 41.1wt%HFC-1243zf,
2.3wt% dimethyl ether and 56.6wt%CF3SCF3。
10. the composition of any one of claim 1-9, also comprising being selected from polyol ester, polyalkylene glycol, polyvinyl
Ether, mineral oil, alkylbenzene, synthesis paraffin, the lubricant for synthesizing cycloalkane and poly- (α) alkene.
11. the composition of any one of claim 1-9 also includes tracer, is selected from hydrofluorocarbon, deuteroparaffin, hydrogen deuteride fluorine
Carbon, perfluoroparaffin, fluoro-ether, brominated compound, iodinated compounds, alcohol, aldehyde, ketone, nitrous oxide (N2) and their combination O.
12. the composition of claim 11, also comprising the tracer selected from following substance:
CD3CD3, CD3CD2CD3, CD2F2, CF3CD2CF3, CD2FCF3, CD3CF3, CDF2CF3, CF3CDFCF3, CF3CF2CDF2,
CDF2CDF2, CF3CF2CD3, CF3CD2CH3, CF2CH2CD3, CF3CF3, ring-CF2CF2CF2, CF3CF2CF3, ring-
CF2CF2CF2CF2, CF3CF2CF2CF3, CF3CF(CF3)2, ring-CF (CF3)CF2CF(CF3)CF2, trans- ring-CF2CF(CF3)
CF(CF3)CF2, cis- ring-CF2CF(CF3)CF(CF3)CF2, CF3OCHF2, CF3OCH2F, CF3OCH3, CF3OCHFCF3,
CF3OCH2CF3, CF3OCH2CHF2, CF3CH2OCHF2CH3OCF2CF3, CH3CF2OCF3CF3CF2CF2OCHFCF3, CF3CF2CF2OCF
(CF3)Cf2OCHFCF3, CHF3, CH2FCH3, CHF2CH3, CHF2CHF2, CF3CHFCF3, CF3CF2CHF2, CF3CF2CH2F,
CHF2CHFCF3, CF3CH2CF3, CF3CF2CH3, CF3CH2CHF2, CHF2CF2CH3, CF3CHFCH3, CF3CH2CH3, CH3CF2CH3,
CH3CHFCH3, CH2FCH2CH3,CHF2CF2CF2CF3, (CF3)2CHCF3, CF3CH2CF2CF3, CHF2CF2CF2CHF2,
CH3CF2CF2CF3, CF3CHFCHFCF2CF3,
Trifluoromethyl-cyclopentane, perfluoromethylcyclohexane (PFMCH), perfluorodimethylcyclohexane (o-, m- or p-), perfluoro-ethyl hexamethylene,
Perfluoroindan, perfluor trimethyl-cyclohexane and their isomers, perfluoroisopropyl hexamethylene, suitable perfluorodecalin, anti-perfluor naphthalene
Alkane, suitable or anti-perfluoromethyidecalin and their isomers, CH3Br、CH2FBr、CHF2Br、CHFBr2、CHBr3、CH2BrCH3、
CHBr=CH2、CH2BrCH2Br, CFBr=CHF, CF3I、CHF2I、CH2FI、CF2ICH2F、CF2ICHF2、CF2ICF2I、C6F5I、
Ethyl alcohol, normal propyl alcohol, isopropanol, acetone, positive propionic aldehyde, n-butanal, methyl ethyl ketone, nitrous oxide and their combination.
13. the composition of any one of claim 1-9, also comprising the expanding material selected from following substance:
A) by general formula R1[(OR2)xOR3] y indicate polyoxyalkylene glycol ether, in which: x is the integer of 1-3;Y is the whole of 1-4
Number;R1Aliphatic hydrocarbyl selected from hydrogen and containing 1-6 carbon atom and y bonded positions;R2It is sub- selected from the aliphatic series containing 2-4 carbon atom
Alkyl;R3Aliphatic series and alicyclic alkyl selected from hydrogen and containing 1-6 carbon atom;R1And R3In at least one be selected from the alkyl;And
And wherein the polyoxyalkylene glycol ether has the molecular weight of about 300 atomic mass unit of about 100-;
B) by general formula R1C(O)NR2R3With ring-[R4CON(R5The amide that) -] indicates, wherein R1、R2、R3And R5Independently selected from containing
The aliphatic series and alicyclic alkyl of 1-12 carbon atom, and an at most aromatic group containing 6-12 carbon atom;R4Selected from containing 3-12
The aliphatic hydrocarbylene of a carbon atom;And wherein the amide has the molecular weight of about 300 atomic mass unit of about 100-;
C) by general formula R1C(O)R2The ketone of expression, wherein R1And R2Independently selected from aliphatic, alicyclic containing 1-12 carbon atom and
Arylalkvl, and wherein the ketone has the molecular weight of about 300 atomic mass unit of about 70-;
D) by general formula R1The nitrile that CN is indicated, wherein R1Selected from aliphatic, the alicyclic or Arylalkvl containing 5-12 carbon atom, and
Wherein the nitrile has the molecular weight of about 200 atomic mass unit of about 90-;
E) chlorohydrocarbon indicated by general formula R Clx, in which: x is 1 or 2;R is selected from aliphatic series and clicyclic hydrocarbon containing 1-12 carbon atom
Base;And wherein the chlorocarbon has the molecular weight of about 200 atomic mass unit of about 100-;
F) by general formula R1OR2The aryl ether of expression, in which: R1Selected from the Arylalkvl containing 6-12 carbon atom;R2Selected from containing 1-4
The aliphatic hydrocarbyl of carbon atom;And wherein the aryl ether has the molecular weight of about 150 atomic mass unit of about 100-;
G) by general formula CF3R11,1, the 1- trifluoroalkanes indicated, wherein R1Selected from about 15 carbon atoms Han about 5- aliphatic series and
Alicyclic alkyl;
H) by general formula R1OCF2CF2The fluoro-ether that H is indicated, wherein R1Aliphatic series selected from about 15 carbon atoms Han about 5-, alicyclic ring
Race and aromatic hydrocarbyl;Or in which the fluoro-ether is derived from fluoroolefin and polyalcohol, wherein the fluoroolefin has CF2
=CXY pattern, wherein X is hydrogen, chlorine or fluorine, and Y is chlorine, fluorine, CF3Or ORf, wherein RfIt is CF3、C2F5Or C3F7;With the polyalcohol
It is linear or branching, wherein the polyalcohols have HOCH2(CHOH)x(CRR')yCH2OH pattern, wherein R and R' are
Hydrogen, CH3Or C2H5, x is the integer of 0-4, and y is the integer of 0-3, and z is that 0 or 1 and the Branched polyol have C (OH) t (R) u
(CH2OH)v[(CH2)mCH2OH] w pattern, wherein R can be hydrogen, CH3Or C2H5, m is the integer of 0-3, and t and u are 0 or 1, v and w
It is the integer of 0-4, furthermore wherein t+u+v+w=4;With
I) lactone indicated by structure [B], [C] and [D]:
Wherein, R1-R8Independently selected from hydrogen, linearly, branching is cyclic annular, two rings, saturation and undersaturated alkyl;And molecular weight is
About 100 to about 300 atomic mass units;With
J) by general formula R1CO2R2The ester of expression, wherein R1And R2Independently selected from linear and cyclic annular, saturation and unsaturated, alkyl
And aryl;And wherein the ester has the molecular weight of from about 80 to about 550 atomic mass units.
14. the composition of any one of claim 1-9 is also selected from naphthalimide comprising at least one, cumarin,
Anthracene, luxuriant and rich with fragrance, xanthene, thioxanthene, naphthoxanthene, fluorescein, the derivative of the dyestuff and the ultraviolet fluorescent of their combination
Dyestuff.
15. the composition of claim 14 is also selected from hydrocarbon, dimethyl ether, polyoxyalkylene glycol ether, acyl comprising at least one
Amine, ketone, nitrile, chlorohydrocarbon, ester, lactone, aryl ether, hydrogen fluoro-ether and 1, the solubilizer of 1,1- trifluoroalkanes.
16. the composition of any one of claim 1-9 also includes stabilizer, water scavenger or odor masking agent.
17. the composition of claim 16, wherein the stabilizer is selected from nitromethane, hindered phenol, azanol, mercaptan, phosphorous acid
Ester and lactone.
18. refrigerating method, which comprises by the composition of any one of claim 1-9 near body to be cooled
Evaporation, later condenses the composition.
19. the method for generating heat, which comprises by the group of any one of claim 1-9 near body to be heated
Object condensation is closed, later evaporates the composition.
20. the method for high GWP refrigerant in substitution refrigeration, air-conditioning or heat-pump apparatus, wherein the high GWP refrigerant is selected from
R134a、R22、R123、R11、R245fa、R114、R236fa、R124、R12、R410A、R407C、R417A、R422A、R507A、
R502 and R404A, which comprises the composition of any one of claim 1-9 is supplied to use, is used to or designs use
Carry out the refrigeration, air-conditioning or the heat-pump apparatus using the high GWP refrigerant.
21. use the composition of any one of claim 1-9 as the method for heat-transfer fluid composition, the method includes
The composition is transported to radiator from heat source.
22. a kind of refrigeration, air-conditioning or the heat-pump apparatus of the composition containing any one of claim 1-9.
23. a kind of refrigeration, air-conditioning or heat-pump apparatus including moving the claim 22 of air-conditioning equipment.
24. a kind of foaming agent of the composition comprising any one of claim 1-9.
25. a kind of method for forming foam, comprising:
(a) composition of any one of claim 1-9 is added in foamable composite;With
(b) foamable composite is reacted.
26. the Sprayable composition of the composition comprising any one of claim 1-9.
27. a kind of preparation method of aerosol product, comprising steps of addition right is wanted in active constituent into aerosol container
The composition of any one of 1-9 is sought, wherein the composition plays propellant.
28. a kind of suppressing method of flame, the fluid including making the flame Yu the composition comprising any one of claim 1-9
Contact.
29. the method that fire is put out or inhibited with total flooding application mode, comprising:
(a) reagent of the composition comprising any one of claim 1-9 is provided;
(b) reagent is arranged in pressurized discharge system;With
(c) reagent is discharged into the fire for putting out or inhibiting in region in the region.
30. the method for making islands inert to prevent fire or explosion, comprising:
(a) reagent of the composition comprising any one of claim 1-9 is provided;
(b) reagent is arranged in pressurized discharge system;With
(c) reagent is discharged into the region to prevent fire or explosion from occurring.
Applications Claiming Priority (9)
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US65854305P | 2005-03-04 | 2005-03-04 | |
US60/658543 | 2005-03-04 | ||
US71043905P | 2005-08-23 | 2005-08-23 | |
US60/710439 | 2005-08-23 | ||
US73276905P | 2005-11-01 | 2005-11-01 | |
US60/732769 | 2005-11-01 | ||
US11/369,227 US20060243944A1 (en) | 2005-03-04 | 2006-03-02 | Compositions comprising a fluoroolefin |
US11/369227 | 2006-03-02 | ||
CNA2006800154380A CN101297016A (en) | 2005-03-04 | 2006-03-03 | Compositions comprising a fluoroolefin |
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CN201910001475.5A Pending CN109971431A (en) | 2005-03-04 | 2006-03-03 | Composition comprising fluoroolefin |
CN201910000638.8A Pending CN109897604A (en) | 2005-03-04 | 2006-03-03 | Composition comprising fluoroolefin |
CN201910881175.0A Pending CN110564372A (en) | 2005-03-04 | 2006-03-03 | Compositions comprising fluoroolefins |
CN201910000605.3A Pending CN110003858A (en) | 2005-03-04 | 2006-03-03 | Composition comprising fluoroolefin |
CN201910001471.7A Pending CN110003859A (en) | 2005-03-04 | 2006-03-03 | Composition comprising fluoroolefin |
CN202111244244.0A Active CN113845884B (en) | 2005-03-04 | 2006-03-03 | Compositions comprising fluoroolefins |
CN201910001116.XA Active CN109897605B (en) | 2005-03-04 | 2006-03-03 | Compositions comprising fluoroolefins |
CN201910001095.1A Active CN109971428B (en) | 2005-03-04 | 2006-03-03 | Compositions comprising fluoroolefins |
CN202110841031.XA Active CN113549426B (en) | 2005-03-04 | 2006-03-03 | Compositions comprising fluoroolefins |
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CN201910000605.3A Pending CN110003858A (en) | 2005-03-04 | 2006-03-03 | Composition comprising fluoroolefin |
CN201910001471.7A Pending CN110003859A (en) | 2005-03-04 | 2006-03-03 | Composition comprising fluoroolefin |
CN202111244244.0A Active CN113845884B (en) | 2005-03-04 | 2006-03-03 | Compositions comprising fluoroolefins |
CN201910001116.XA Active CN109897605B (en) | 2005-03-04 | 2006-03-03 | Compositions comprising fluoroolefins |
CN201910001095.1A Active CN109971428B (en) | 2005-03-04 | 2006-03-03 | Compositions comprising fluoroolefins |
CN202110841031.XA Active CN113549426B (en) | 2005-03-04 | 2006-03-03 | Compositions comprising fluoroolefins |
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CN109971428A (en) | 2019-07-05 |
CN113549426A (en) | 2021-10-26 |
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CN110003859A (en) | 2019-07-12 |
CN109897604A (en) | 2019-06-18 |
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CN109897605B (en) | 2021-09-10 |
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