WO2010098451A1 - 温暖化係数の低いハイドロフルオロプロペンを含む冷媒組成物 - Google Patents
温暖化係数の低いハイドロフルオロプロペンを含む冷媒組成物 Download PDFInfo
- Publication number
- WO2010098451A1 WO2010098451A1 PCT/JP2010/053108 JP2010053108W WO2010098451A1 WO 2010098451 A1 WO2010098451 A1 WO 2010098451A1 JP 2010053108 W JP2010053108 W JP 2010053108W WO 2010098451 A1 WO2010098451 A1 WO 2010098451A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- refrigerant composition
- stabilizer
- refrigerant
- hydrofluoropropene
- hfo
- Prior art date
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- 239000003507 refrigerant Substances 0.000 title claims abstract description 114
- 239000000203 mixture Substances 0.000 title claims abstract description 87
- 238000010792 warming Methods 0.000 title abstract description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 41
- 239000001301 oxygen Substances 0.000 claims abstract description 41
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 41
- 239000003381 stabilizer Substances 0.000 claims abstract description 40
- -1 alkyl catechols Chemical class 0.000 claims abstract description 24
- 150000004054 benzoquinones Chemical class 0.000 claims abstract description 10
- 150000002990 phenothiazines Chemical class 0.000 claims abstract description 10
- 239000002253 acid Substances 0.000 claims description 51
- 239000010721 machine oil Substances 0.000 claims description 37
- FXRLMCRCYDHQFW-UHFFFAOYSA-N 2,3,3,3-tetrafluoropropene Chemical group FC(=C)C(F)(F)F FXRLMCRCYDHQFW-UHFFFAOYSA-N 0.000 claims description 27
- 239000003921 oil Substances 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 18
- 238000005057 refrigeration Methods 0.000 claims description 18
- 238000011156 evaluation Methods 0.000 claims description 16
- 125000005498 phthalate group Chemical class 0.000 claims description 8
- CDOOAUSHHFGWSA-OWOJBTEDSA-N (e)-1,3,3,3-tetrafluoroprop-1-ene Chemical compound F\C=C\C(F)(F)F CDOOAUSHHFGWSA-OWOJBTEDSA-N 0.000 claims description 6
- 229920001289 polyvinyl ether Polymers 0.000 claims description 6
- 230000000087 stabilizing effect Effects 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 229920005862 polyol Polymers 0.000 claims description 4
- DMUPYMORYHFFCT-UPHRSURJSA-N (z)-1,2,3,3,3-pentafluoroprop-1-ene Chemical compound F\C=C(/F)C(F)(F)F DMUPYMORYHFFCT-UPHRSURJSA-N 0.000 claims description 3
- QAERDLQYXMEHEB-UHFFFAOYSA-N 1,1,3,3,3-pentafluoroprop-1-ene Chemical compound FC(F)=CC(F)(F)F QAERDLQYXMEHEB-UHFFFAOYSA-N 0.000 claims description 3
- FDMFUZHCIRHGRG-UHFFFAOYSA-N 3,3,3-trifluoroprop-1-ene Chemical compound FC(F)(F)C=C FDMFUZHCIRHGRG-UHFFFAOYSA-N 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 230000006835 compression Effects 0.000 claims description 3
- 238000007906 compression Methods 0.000 claims description 3
- 229920001515 polyalkylene glycol Polymers 0.000 claims description 2
- 239000002826 coolant Substances 0.000 claims 1
- 150000003021 phthalic acid derivatives Chemical class 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 37
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Inorganic materials [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 14
- 125000000217 alkyl group Chemical group 0.000 description 10
- 230000002401 inhibitory effect Effects 0.000 description 10
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 8
- 238000004458 analytical method Methods 0.000 description 7
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 7
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 7
- 238000007254 oxidation reaction Methods 0.000 description 7
- AZQWKYJCGOJGHM-UHFFFAOYSA-N para-benzoquinone Natural products O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethanethiol Chemical compound CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical group COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 6
- 230000001133 acceleration Effects 0.000 description 5
- 230000033228 biological regulation Effects 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 239000012760 heat stabilizer Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 150000007513 acids Chemical class 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 125000006165 cyclic alkyl group Chemical group 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 238000011049 filling Methods 0.000 description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 4
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 4
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical class OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 229940005561 1,4-benzoquinone Drugs 0.000 description 3
- XESZUVZBAMCAEJ-UHFFFAOYSA-N 4-tert-butylcatechol Chemical group CC(C)(C)C1=CC=C(O)C(O)=C1 XESZUVZBAMCAEJ-UHFFFAOYSA-N 0.000 description 3
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 238000006864 oxidative decomposition reaction Methods 0.000 description 3
- 229950000688 phenothiazine Drugs 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- LVGUZGTVOIAKKC-UHFFFAOYSA-N 1,1,1,2-tetrafluoroethane Chemical compound FCC(F)(F)F LVGUZGTVOIAKKC-UHFFFAOYSA-N 0.000 description 2
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 2
- OHMHBGPWCHTMQE-UHFFFAOYSA-N 2,2-dichloro-1,1,1-trifluoroethane Chemical compound FC(F)(F)C(Cl)Cl OHMHBGPWCHTMQE-UHFFFAOYSA-N 0.000 description 2
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical compound CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- PXBRQCKWGAHEHS-UHFFFAOYSA-N dichlorodifluoromethane Chemical compound FC(F)(Cl)Cl PXBRQCKWGAHEHS-UHFFFAOYSA-N 0.000 description 2
- 235000019404 dichlorodifluoromethane Nutrition 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- DXGLGDHPHMLXJC-UHFFFAOYSA-N oxybenzone Chemical compound OC1=CC(OC)=CC=C1C(=O)C1=CC=CC=C1 DXGLGDHPHMLXJC-UHFFFAOYSA-N 0.000 description 2
- MMSLOZQEMPDGPI-UHFFFAOYSA-N p-Mentha-1,3,5,8-tetraene Chemical compound CC(=C)C1=CC=C(C)C=C1 MMSLOZQEMPDGPI-UHFFFAOYSA-N 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 229920002620 polyvinyl fluoride Polymers 0.000 description 2
- IWZKICVEHNUQTL-UHFFFAOYSA-M potassium hydrogen phthalate Chemical compound [K+].OC(=O)C1=CC=CC=C1C([O-])=O IWZKICVEHNUQTL-UHFFFAOYSA-M 0.000 description 2
- 239000005297 pyrex Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 0 *N1c2ccccc2Sc2c1cccc2 Chemical compound *N1c2ccccc2Sc2c1cccc2 0.000 description 1
- PGJHURKAWUJHLJ-UHFFFAOYSA-N 1,1,2,3-tetrafluoroprop-1-ene Chemical compound FCC(F)=C(F)F PGJHURKAWUJHLJ-UHFFFAOYSA-N 0.000 description 1
- DMUPYMORYHFFCT-UHFFFAOYSA-N 1,2,3,3,3-pentafluoroprop-1-ene Chemical compound FC=C(F)C(F)(F)F DMUPYMORYHFFCT-UHFFFAOYSA-N 0.000 description 1
- RBACIKXCRWGCBB-UHFFFAOYSA-N 1,2-Epoxybutane Chemical compound CCC1CO1 RBACIKXCRWGCBB-UHFFFAOYSA-N 0.000 description 1
- JSZOAYXJRCEYSX-UHFFFAOYSA-N 1-nitropropane Chemical compound CCC[N+]([O-])=O JSZOAYXJRCEYSX-UHFFFAOYSA-N 0.000 description 1
- PIAOLBVUVDXHHL-UHFFFAOYSA-N 2-nitroethenylbenzene Chemical compound [O-][N+](=O)C=CC1=CC=CC=C1 PIAOLBVUVDXHHL-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 239000004338 Dichlorodifluoromethane Substances 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical class COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- XQVWYOYUZDUNRW-UHFFFAOYSA-N N-Phenyl-1-naphthylamine Chemical compound C=1C=CC2=CC=CC=C2C=1NC1=CC=CC=C1 XQVWYOYUZDUNRW-UHFFFAOYSA-N 0.000 description 1
- 229920001774 Perfluoroether Polymers 0.000 description 1
- RYYWUUFWQRZTIU-UHFFFAOYSA-N Thiophosphoric acid Chemical class OP(O)(S)=O RYYWUUFWQRZTIU-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000004378 air conditioning Methods 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- QPAXMPYBNSHKAK-UHFFFAOYSA-N chloro(difluoro)methane Chemical compound F[C](F)Cl QPAXMPYBNSHKAK-UHFFFAOYSA-N 0.000 description 1
- KYKAJFCTULSVSH-UHFFFAOYSA-N chloro(fluoro)methane Chemical compound F[C]Cl KYKAJFCTULSVSH-UHFFFAOYSA-N 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 238000009430 construction management Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 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 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 238000004255 ion exchange chromatography Methods 0.000 description 1
- 239000001282 iso-butane Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- MCSAJNNLRCFZED-UHFFFAOYSA-N nitroethane Chemical compound CC[N+]([O-])=O MCSAJNNLRCFZED-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 1
- YCIMNLLNPGFGHC-UHFFFAOYSA-N o-dihydroxy-benzene Natural products OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 1
- UJMWVICAENGCRF-UHFFFAOYSA-N oxygen difluoride Chemical class FOF UJMWVICAENGCRF-UHFFFAOYSA-N 0.000 description 1
- VDDWRTZCUJCDJM-PNHLSOANSA-N p-Naphtholbenzein Chemical compound C12=CC=CC=C2C(O)=CC=C1\C(=C\1C2=CC=CC=C2C(=O)C=C/1)C1=CC=CC=C1 VDDWRTZCUJCDJM-PNHLSOANSA-N 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920013636 polyphenyl ether polymer Polymers 0.000 description 1
- NEKYAYCEWWKFCB-UHFFFAOYSA-M potassium;phthalic acid;hydroxide Chemical compound [OH-].[K+].OC(=O)C1=CC=CC=C1C(O)=O NEKYAYCEWWKFCB-UHFFFAOYSA-M 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- IZUPJOYPPLEPGM-UHFFFAOYSA-M sodium;hydron;phthalate Chemical compound [Na+].OC(=O)C1=CC=CC=C1C([O-])=O IZUPJOYPPLEPGM-UHFFFAOYSA-M 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- 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
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- 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
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- 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
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
- G01N33/26—Oils; Viscous liquids; Paints; Inks
- G01N33/28—Oils, i.e. hydrocarbon liquids
- G01N33/2835—Specific substances contained in the oils or fuels
- G01N33/2876—Total acid number
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
- C09K2205/10—Components
- C09K2205/12—Hydrocarbons
- C09K2205/126—Unsaturated fluorinated hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/28—Esters
- C10M2207/283—Esters of polyhydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
- 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
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
- 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
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
- C10N2020/09—Characteristics associated with water
- C10N2020/097—Refrigerants
- C10N2020/101—Containing Hydrofluorocarbons
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/10—Inhibition of oxidation, e.g. anti-oxidants
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T436/00—Chemistry: analytical and immunological testing
- Y10T436/15—Inorganic acid or base [e.g., hcl, sulfuric acid, etc. ]
- Y10T436/153333—Halogen containing
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T436/00—Chemistry: analytical and immunological testing
- Y10T436/19—Halogen containing
- Y10T436/196666—Carbon containing compound [e.g., vinylchloride, etc.]
Definitions
- the present invention relates to a stabilized refrigerant composition containing hydrofluoropropene such as 2,3,3,3-tetrafluoropropene having a low global warming potential.
- chlorofluorofluorocarbon CFC
- hydrochlorofluorocarbon HCFC
- chlorofluorocarbons CFC
- chlorofluorocarbons released into the atmosphere destroy the ozone layer and have a serious adverse effect on the earth's ecosystem including humans. Therefore, the use and production of Freon, which already has a high risk of ozone depletion, has been regulated by international agreements.
- dichlorodifluoromethane (CFC-12) has been mainly used as a refrigerant for household refrigerators, car air conditioners, turbo chillers, container refrigeration equipment, etc., but it is a hydrofluorocarbon due to the aforementioned regulations.
- 1,1,2-tetrafluoroethane (HFC-134a).
- HFO-1225ye 1,2,3,3,3-pentafluoro-1-propene
- HFO-1234yf 2,3,3,3 Hydrofluoropropenes
- Patent Document 1 and the like report a stabilization technique.
- Patent Document 1 describes that stabilizers such as phenolic compounds, thiophosphates, benzoquinones, and arylalkyl ethers are added to the fluoroolefin.
- the present invention provides a refrigerant composition containing hydrofluoropropene having a low global warming potential (GWP), which can maintain a stable state for a long time even in the presence of air (oxygen).
- GWP global warming potential
- the present inventor has obtained at least one stabilizer (oxidation agent) selected from the group consisting of alkylcatechols, alkoxyphenols, benzoquinones, phenothiazines and phthalates. It has been found that a refrigerant composition containing an inhibitor) and at least one hydrofluoropropene can maintain a stable state for a long time even in the presence of air (oxygen). Such a refrigerant composition can maintain stability over a long period of time even when air (oxygen) is mixed during refrigerant filling construction of a stationary air conditioner such as a home air conditioner.
- oxidation agent selected from the group consisting of alkylcatechols, alkoxyphenols, benzoquinones, phenothiazines and phthalates.
- the conventional mechanism for decomposing HFC refrigerants without unsaturated bonds is the reduction of halogen atoms, and the durability of the refrigerant is determined by tests taking into account decomposition acceleration factors such as temperature, metal (catalyst), moisture, and air. Evaluating stability.
- a mixture of air and a metal catalyst (Fe, Cu, or Al) in refrigeration oil and refrigerant (HFO-1225ye) at 175 ° C. is 2 After heating for a week, the appearance of the mixture is evaluated. That is, the evaluation is performed by the same thermal stability acceleration test as that of the conventional (HFC refrigerant).
- this method merely evaluates the appearance of the liquid phase of the mixture (coloring grade; Rating), and does not allow the acid in the system to corrode or reduce the refrigeration capacity when hydrofluoropropene is used as a refrigerant. Sufficient evaluation has not been made on the occurrence.
- the decomposition mechanism of the refrigerant composition containing hydrofluoropropene is dominated by the oxidation reaction between the unsaturated bond and oxygen, and CF 3 COOH, HF which is the main cause of the above problem due to the oxidation reaction. It has been clarified that acids such as these are generated, and the evaluation method has been established. Specifically, after treating the refrigerant composition containing hydrofluoropropene for a predetermined time at a predetermined temperature, the acid content of the refrigerant composition after the treatment and the total acid value of the refrigerating machine oil that may be contained in the refrigerant composition are determined. The evaluation made it possible to evaluate the thermal stability of hydrofluoropropene more realistically.
- the present invention relates to a refrigerant composition containing the following hydrofluoropropene.
- a refrigerant composition comprising hydrofluoropropene and a stabilizer, wherein the stabilizer is at least one selected from the group consisting of alkylcatechols, alkoxyphenols, benzoquinones, phenothiazines and phthalates
- a refrigerant composition characterized by that. 2.
- the hydrofluoropropene is 2,3,3,3-tetrafluoropropene (HFO-1234yf), (Z or E-) 1,3,3,3-tetrafluoropropene (HFO-1234ze), (Z or E- ) 1,2,3,3,3-pentafluoropropene (HFO-1225ye), (Z or E-) 1,1,3,3,3-pentafluoropropene (HFO-1225zc), and (Z or E Item 2)
- the refrigerant composition according to item 1 which is at least one selected from the group consisting of 3,3,3-trifluoropropene (HFO-1243zf).
- the refrigerant composition according to Item 1 wherein the content of the stabilizer relative to 100 parts by weight of hydrofluoropropene is 0.1 to 5.0 parts by weight. 4).
- Item 2. The refrigerant composition according to Item 1, further comprising refrigerating machine oil. 5).
- the refrigerant composition is selected from the group consisting of a vapor compression heat pump such as a refrigerator, a refrigerator, a mobile air conditioner, a refrigerator (chiller), a container refrigeration apparatus, a home air conditioner, a commercial air conditioner, or a water heater.
- a vapor compression heat pump such as a refrigerator, a refrigerator, a mobile air conditioner, a refrigerator (chiller), a container refrigeration apparatus, a home air conditioner, a commercial air conditioner, or a water heater.
- Item 6 The refrigerant composition according to any one of Items 1 to 5, which is used in 7).
- a method for stabilizing a refrigerant composition comprising hydrofluoropropene wherein the refrigerant composition comprises at least one kind of stabilizer selected from the group consisting of alkylcatechols, alkoxyphenols, benzoquinones, phenothiazines and phthalates.
- a stabilizing method characterized by adding an agent. 8).
- a method for evaluating the stability of a refrigerant composition containing hydrofluoropropene and a stabilizer wherein the refrigerant composition is heated in a sealed container in the presence and / or absence of oxygen, and then treated.
- the evaluation method characterized by analyzing the acid content of a refrigerant composition after.
- a method for evaluating the stability of a refrigerant composition comprising hydrofluoropropene, refrigerating machine oil and a stabilizer, wherein the refrigerant composition is heat-treated in a sealed container in the presence and / or absence of oxygen.
- the refrigerant composition of the present invention does not contain chlorine and bromine, there is no danger of destroying the ozone layer even if released into the atmosphere.
- the global warming potential is low, the stability in the presence of air (oxygen) is at the same level as that of existing HFC refrigerants, and it has sufficient durability even when used as a refrigerant composition for stationary refrigerators.
- the refrigerant composition of the present invention contains hydrofluoropropene and a stabilizer, and the stabilizer is at least one selected from the group consisting of alkylcatechols, alkoxyphenols, benzoquinones, phenothiazines and phthalates. It is characterized by being.
- refrigerant hydrofluoropropene examples include 2,3,3,3-tetrafluoropropene (HFO-1234yf) and (Z or E-) 1,3,3,3-tetrafluoropropene (HFO-1234ze). , (Z or E-) 1,2,3,3,3-pentafluoropropene (HFO-1225ye), (Z or E-) 1,1,3,3,3-pentafluoropropene (HFO-1225zc) (Z or E-) 3,3,3-trifluoropropene (HFO-1243zf) and the like. These hydrofluoropropenes can be used alone or in admixture of two or more.
- the refrigerant composition of the present invention may be further mixed with an existing HFC refrigerant in addition to the hydrofluoropropene.
- the content ratio of the HFC refrigerant is 50% by weight or less, preferably 30% by weight or less, more preferably 20% by weight or less based on the total weight of the refrigerant.
- the refrigerant composition of the present invention may contain refrigerating machine oil in addition to hydrofluoropropene depending on applications.
- refrigerating machine oil A well-known thing can be used as refrigerating machine oil.
- at least one of poly (oxy) alkylene glycols, polyvinyl ethers, and polyol esters is particularly preferable.
- the kinematic viscosity of the refrigerating machine oil at 40 ° C. is preferably 5 to 400 cSt, more preferably 30 to 400 cSt.
- the kinematic viscosity in this specification is a value measured with a capillary viscometer among viscometers defined in JIS Z 8803 (liquid viscosity-measurement method).
- the amount of refrigerant containing hydrofluoropropene is usually 16 to 50 parts by weight with respect to 10 parts by weight of refrigerating machine oil, but it varies depending on the specifications of the oil tank of the refrigerating machine. It is not particularly limited to this range.
- the refrigerant composition of the present invention is at least one selected from the group consisting of alkylcatechols, alkoxyphenols, benzoquinones, phenothiazines, and phthalates in order to impart stability to oxygen of refrigerants containing hydrofluoropropene. Contains seeds as stabilizers (antioxidants).
- alkyl catechols examples include general formula (1):
- R 1 represents an alkyl group, and n represents an integer of 1 to 4.
- n represents an integer of 1 to 4.
- Examples of the alkyl group represented by R 1 include C 1 to C 10 linear, branched or cyclic alkyl groups. Specific examples include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and the like. Preferred is tert-butyl.
- n is preferably 1 or 2, more preferably 1.
- the groups R 1 may be the same or different.
- the bonding position of the group R 1 on the benzene ring is not particularly limited, but is preferably bonded to at least the 4-position or 5-position.
- a preferred specific example is 4-tert-butylpyrocatechol.
- alkoxyphenols include, for example, the general formula (2):
- Examples of the alkyl group represented by R 2 include C 1 to C 10 linear, branched or cyclic alkyl groups. Specific examples include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl and the like. Preferred are methyl, ethyl, isopropyl and tert-butyl. m is preferably 1 or 2, and more preferably 1. When n is an integer of 2 to 4, the groups R 2 O may be the same or different.
- the bonding position of the group R 2 O on the benzene ring is not particularly limited, but is preferably bonded to the p-position (4-position).
- a preferred specific example is 4-methoxyphenol.
- benzoquinones include general formula (3):
- Examples of the alkyl group represented by R 3 include C 1 to C 10 linear, branched or cyclic alkyl groups. Specific examples include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl and the like. Preferred are methyl, ethyl, isopropyl and tert-butyl.
- p is preferably 0, 1 or 2, more preferably 0.
- n is an integer of 2 to 4
- the groups R 3 may be the same or different.
- the bonding position of the group R 3 on the ring is not particularly limited.
- a preferred specific example is 1,4-benzoquinone.
- phenothiazines examples include, for example, the general formula (4):
- R 4 is a hydrogen atom or an alkyl group
- R 5 or R 6 is the same or different and a hydrogen atom, an alkyl group
- q and r are the same or different and each represents an integer of 1 to 4
- the phenothiazine compound represented by these is mentioned.
- Examples of the alkyl group represented by R 4 include C 1 to C 10 linear, branched or cyclic alkyl groups. Specific examples include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl and the like. Methyl, ethyl, isopropyl and tert-butyl are preferable.
- R 4 is preferably a hydrogen atom.
- the alkyl group represented by R 5 or R 6 can be appropriately selected from those represented by R 4 above.
- R 5 and R 6 are preferably hydrogen atoms.
- q and r are preferably 0, 1 or 2, and more preferably 0.
- the groups R 5 may be the same or different
- the groups R 6 may be the same or different.
- the bonding position on the benzene ring of the groups R 5 and R 6 on the ring is not particularly limited.
- Preferable specific examples include phenothiazines.
- phthalates examples include mono- or dialkali metal salts of phthalic acid.
- Preferred are monoalkali metal salts of phthalic acid, and specific examples include potassium hydrogen phthalate and sodium hydrogen phthalate. Preferably, it is potassium hydrogen phthalate.
- the blending amount of the stabilizer is usually 0.1 to 5.0 parts by weight, more preferably 0.3 to 3.0 parts by weight with respect to 100 parts by weight of hydrofluoropropene.
- a solvent may be optionally added within a range that does not adversely affect the stability of oxygen and hydrofluoropropene.
- a solvent include glyme compounds, preferably diglyme.
- the addition amount of the solvent is 30% by weight or less, preferably 15 to 25% by weight, more preferably 15 to 20% by weight, based on the total weight of the stabilizer.
- the stabilizer used in the present invention has a very high stabilizing (acid value prevention) effect compared to that exemplified in Patent Document 1 (see Examples and Comparative Examples).
- Patent Document 1 merely evaluates the appearance of the liquid phase of the mixture (coloring grade; Rating), and the corrosion in the system due to the oxidative decomposition of hydrofluoropropene and the reduction of the refrigerating capacity. This is because the generation of acid, which is the main cause of this, has not been evaluated.
- the heat treatment of the refrigerant composition in a sealed container in the presence and / or absence of oxygen, the acid content of the refrigerant composition after the treatment is performed. It is characterized by analyzing. Further, when the refrigerant composition contains refrigeration oil, the total acid value of the refrigeration oil contained in the refrigerant composition after the heat treatment is also analyzed.
- a shield tube for example, a shielded Pyrex (registered trademark) glass tube or the like
- the evaluation method of the present invention corresponds to a so-called acceleration test, for example, the heating temperature can be set in the range of 90 to 200 ° C.
- the heat treatment time can be set in the range of 72 to 720 hours.
- the analysis method of the acid content of the refrigerant composition after a process, and the total acid value analysis method in the case of containing refrigeration oil it can implement by the method as described in an Example.
- the evaluation method of the present invention it is possible to appropriately evaluate the generation of acids such as CF 3 COOH and HF due to the oxidation reaction, which is the main cause of problems such as corrosion in the system and a decrease in refrigeration capacity. Therefore, if the evaluation method of the present invention is used, it becomes possible to screen for a more realistic stabilizer.
- the refrigerant composition of the present invention is described in, for example, Japanese Patent Application Laid-Open No. 2000-178543, Japanese Patent Application Laid-Open No. 2008-308610, Japanese Patent No. 2863159 and the like when a high degree of thermal stability is required.
- An HFC refrigerant used in a conventional HFC refrigerant system or a heat stabilizer for refrigeration oil can be used in combination.
- heat stabilizer examples include (i) aliphatic nitro compounds such as nitromethane, nitroethane, and nitropropane, aromatic nitro compounds such as nitrobenzene and nitrostyrene, and aromatics such as p-isopropenyltoluene and disopropenylbenzene.
- Unsaturated fatty compounds (ii) phenols such as 2,6-di-t-butyl-p-cresol, epoxies such as 1,2-butylene oxide, and amines such as phenyl- ⁇ -naphthylamine It is done.
- one or more compounds selected from the above (i) and (ii) can be used, and in this case, two or more compounds from the above (i) or (ii) are used. May be.
- the amount of heat stabilizer used varies depending on the type of the stabilizer, but should be such that it does not interfere with the properties of the refrigerant performance.
- the amount of heat stabilizer used is usually preferably about 0.1 to 5% by weight, more preferably about 0.3 to 3% by weight in the refrigerant composition.
- the refrigerant composition of the present invention can be used for various applications such as a refrigerant, a heat transfer medium, a working fluid, and a foaming agent in the same manner as conventional chlorofluorocarbon.
- a refrigerant composition for various low-temperature equipment such as refrigerators, refrigerators, mobile air conditioners, chillers (chillers), container refrigeration equipment, home air conditioners, commercial air conditioners, steam compression heat pumps such as water heaters, etc. is there.
- Examples 1 to 13 and Comparative Examples 1 to 22 (Preparation of refrigerant composition) The following were prepared as refrigerants.
- X: HFO-1234yf (CF 3 CF CH 2 manufactured by Daikin Industries)
- Y comparative product
- HFC-32 manufactured by CF 2 H 2 Daikin Industries
- Z HFO-1225ye (CF 3 CH ⁇ CF 2 manufactured by Daikin Industries)
- a refrigerating machine oil having a kinematic viscosity at 40 ° C. of about 70 mm 2 / s mainly composed of a polyvinyl ether compound having a structural unit represented by the following general formula (i) was prepared.
- Each refrigerant composition was prepared so as to have the composition shown in Tables 1 and 2 below.
- Test example 1 Pyrex (registered trademark) glass tubes (ID8mm ⁇ ⁇ OD12mm ⁇ ⁇ L300mm) 37 types of refrigerant compositions (Examples 1-13, Comparative Examples 1-24) shown in Table 1 (refrigerant + stabilizer + refrigerator oil) ) was added, air was further adjusted to the oxygen concentration shown in Table 1, and the mixture was sealed. After that, an accelerated test was performed by heating at a temperature of 150 ° C. for one week (168 hours).
- Total acid value analysis of refrigerating machine oil The total acid value of the refrigerating machine oil after gas recovery was measured by a method based on the total acid value analysis method of JIS K-2211 (refrigerating machine oil). Refrigeration machine oil after acceleration test is weighed, dissolved in toluene / isopropanol / water mixed solvent, neutralized with 1 / 100N KOH / ethanol solution using ⁇ -naphtholbenzein as indicator, and frozen from titration. The machine oil total acid value (mg ⁇ KOH / g) was measured.
- Comparative Examples 1 to 3 each consisted of HFO-1234yf, HFC-32, and HFO-1225ye, all of which were evaluated for stability under anoxic conditions, and no signs of decomposition were observed.
- Comparative Examples 4 to 6 are obtained by coexisting oxygen with Comparative Examples 1 to 3, respectively.
- the production of acid content is greatly increased in HFO-1234yf and HFO-1225ye, which are hydrofluoropropenes. This indicates that the stability of hydrofluoropropene in the presence of oxygen is extremely low compared to that of the conventional HFC refrigerant (HFC-32).
- Comparative Example 7 a mixture of HFO-1234yf and HFC-32 and oxygen coexist, but the amount of acid produced is almost 80% of HFO-1234yf (Comparative Example 4), which is almost proportional to the composition ratio. .
- Comparative Examples 8 and 9 ethyl mercaptan described in Patent Document 1 (WO2008 / 027511) is added as the stabilizer A, but the comparative examples 4 and 6 without the stabilizer and the acid content are added. It can be seen that the amount produced is almost the same, and no inhibitory effect is observed. Further, in Comparative Examples 19 and 20 in which refrigeration oil was further added, stabilizer A (ethyl mercaptan) was also added, but the oil total acid value was also equivalent to Comparative Examples 16 and 18 in which no stabilizer was added. This shows that the addition of HFO-1234yf and HFO-1225ye has no effect of inhibiting oxidation.
- Comparative Examples 11 and 12 the total acid number of oil with and without oxygen was compared only with refrigerating machine oil, but it was low without oxygen (0.070 mg ⁇ KOH / g) and high with oxygen (0.334 mg ⁇ KOH / g). ).
- the value without oxygen (Comparative Example 11) approximates the total acid number of Comparative Examples 13 to 15, and is judged to be an increase in the total acid number due to thermal degradation of the ether oil without decomposition of the refrigerant.
- Comparative Example 12 The total acid value with oxygen (Comparative Example 12) approximates that of Comparative Example 17, and is determined to be the total acid value increase due to the reaction between ether oil and oxygen. Therefore, it can be seen that HFC-32 does not increase the total acid value even when coexisting with oxygen. Accordingly, Comparative Example 17 is used as an index for the inhibitory effect of the hydrofluoropropene (HFO-1234yf etc.) added by the stabilizer.
- Comparative Example 16 the total acid value of the refrigerating machine oil was increased, but the acid content was detected at a lower level than that of Comparative Example 4 in which the refrigerating machine oil was not allowed to coexist.
- the acids detected this time are HF (19.5 ° C) and CF 3 COOH (boiling point 72.4 ° C), so that many of them are dissolved in the refrigerating machine oil and the total acid value of the refrigerating machine oil is increased. .
- the acid value CF 3 COO ⁇ ; 1850 massppm, F ⁇ ; 310 massppm of Comparative Example 4 without oxygen in the presence of refrigerating machine oil in the presence of oxygen is 1.78 mg ⁇ KOH / g when converted to the total acid value of the refrigerating machine oil. It is about 9 times as large as 0.22 mg ⁇ KOH / g, which is the difference in oil total acid number between 16 and 18 and Comparative Example 17 as an index.
- Example 2 HFO-1225ye is used as the refrigerant, but the effect of the additive has been confirmed in the same manner as HFO-1234yf alone (Example 9), and the oil is also used for hydrofluoropropenes other than HFO-1234yf. The total acid value of was suppressed and an inhibitory effect was observed.
- Example 11 the composition of HFO-1234yf and HFC-32 is used as the refrigerant, but the total acid value of the oil is suppressed as in Example 9 where HFO-1234yf is used alone, and the composition with HFC is also used. The inhibitory effect was recognized.
- Example 12 a system that does not coexist with refrigerating machine oil, the inhibitory effect of the stabilizer due to the difference in hydrofluoropropene is compared.
- Example 13 HFO-1225ye
- Example 12 HFO-1234yf
- the acid content was suppressed, and an inhibitory effect was recognized regardless of the type of hydrofluoropropene.
- hydrofluoropropene such as 2,3,3,3-tetrafluoropropene and its refrigerant composition are stabilized by a stabilizer, which is equally stable to oxygen even in the presence of air (oxygen). I confirmed what I showed. Therefore, by adding the stabilizer of the present invention to the hydrofluoropropene having an unsaturated bond, the stability in the presence of oxygen could be improved to the same level as that of the HFC refrigerant. Therefore, it has been found that the refrigerant composition of the present invention is useful as a refrigerant composition for stationary air conditioners that does not affect the global environment as much as possible and exhibits the same stability as conventional HFC refrigerants.
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Abstract
Description
1. ハイドロフルオロプロペン及び安定化剤を含む冷媒組成物であって、該安定化剤が、アルキルカテコール類、アルコキシフェノール類、ベンゾキノン類、フェノチアジン類及びフタル酸塩類からなる群より選ばれる少なくとも1種であることを特徴とする冷媒組成物。
2. ハイドロフルオロプロペンが、2,3,3,3-テトラフルオロプロペン(HFO-1234yf)、(Z又はE-)1,3,3,3-テトラフルオロプロペン(HFO-1234ze)、(Z又はE-)1,2,3,3,3-ペンタフルオロプロペン(HFO-1225ye)、(Z又はE-)1,1,3,3,3-ペンタフルオロプロペン(HFO-1225zc)、及び(Z又はE-)3,3,3-トリフルオロプロペン(HFO-1243zf)からなる群より選ばれる少なくとも1種である、項1に記載の冷媒組成物。
3. ハイドロフルオロプロペン100重量部に対する安定化剤の含有量が0.1~5.0重量部である、項1に記載の冷媒組成物。
4. 更に冷凍機油を含有する、項1に記載の冷媒組成物。
5. 冷凍機油が、ポリアルキレングリコール、ポリオールエステル及びポリビニルエーテルからなる群より選ばれる少なくとも1種を含み、40℃における動粘度が5~400cStである、項4に記載の冷媒組成物。
6. 冷媒組成物が、冷凍機、冷蔵庫、モバイルエアコン、冷却機(チラー)、コンテナ用冷凍装置、家庭用エアコン、業務用エアコン、給湯器等の蒸気圧縮式ヒートポンプからなる群より選ばれる1種の用途に用いられる、項1~5のいずれかに記載の冷媒組成物。
7. ハイドロフルオロプロペンを含む冷媒組成物の安定化方法であって、該冷媒組成物に、アルキルカテコール類、アルコキシフェノール類、ベンゾキノン類、フェノチアジン類及びフタル酸塩類からなる群より選ばれる少なくとも1種の安定化剤を添加することを特徴とする安定化方法。
8. ハイドロフルオロプロペン及び安定化剤を含む冷媒組成物の安定性の評価方法であって、密閉容器中で、酸素の存在下及び/又は不存在下に、該冷媒組成物を加熱処理した後、処理後の冷媒組成物の酸分を分析することを特徴とする評価方法。
9. ハイドロフルオロプロペン、冷凍機油及び安定化剤を含む冷媒組成物の安定性の評価方法であって、密閉容器中で、酸素の存在下及び/又は不存在下に、該冷媒組成物を加熱処理した後、処理後の冷媒組成物の酸分を分析する及び/又は処理後の冷媒組成物に含まれる冷凍機油の全酸価を分析することを特徴とする評価方法。
で表されるピロカテコール化合物が挙げられる。
で表されるフェノール化合物が挙げられる。
で表されるキノン化合物が挙げられる。
で表されるフェノチアジン化合物が挙げられる。
(冷媒組成物の調製)
冷媒として次のものを用意した。
X:HFO-1234yf(CF3CF=CH2ダイキン工業製)
Y(比較品):HFC-32(CF2H2ダイキン工業製)
Z:HFO-1225ye(CF3CH=CF2ダイキン工業製)
安定化剤として次のものを用意した。
A(比較品):エチルメルカプタン
B(比較品):2-ヒドロキシ4-メトキシベンゾフェノン
C:1,4-ベンゾキノン
D:フェノチアジン
E:4-t-ブチルピロカテコール
F:4-メトキシフェノール
G:フタル酸水酸化カリウム
H(比較品、溶媒):ジグライム
I:(比較品)2-ヒドロキシ4-メトキシベンゾフェノン(2.5重量部)+ジグライム(0.5重量部)の混合物
J:1,4-ベンゾキノン(2.5重量部)+ジグライム(0.5重量部)の混合物
K:フェノチアジン(2.5重量部)+ジグライム(0.5重量部)の混合物
L:4-t-ブチルピロカテコール(2.5重量部)+ジグライム(0.5重量部)の混合物
M:4-メトキシフェノール(2.5重量部)+ジグライム(0.5重量部)の混合物
パイレックス(登録商標)ガラス製チューブ(ID8mmΦ×OD12mmΦ×L300mm)に表1に示される計37種類(実施例1~13、比較例1~24)の冷媒組成物(冷媒+安定化剤+冷凍機油)を入れ、更に表1に示される酸素濃度になるよう空気を入れて調整し封入後、温度150℃で1週間(168時間)加熱する加速試験を行った。
加速試験後のシールドチューブを液体窒素にてガスを完全に凝固させた。その後開封し、徐々に解凍し気化したガスをテドラーバッグに回収した。テドラーバッグに純水5gを注入し回収ガスとよく接触させ酸分を抽出し、抽出液をイオンクロマトグラフィーにてフッ化物イオン(F-)及びトリフルオロ酢酸イオン(CF3COO-)の含有量(重量ppm)を測定した。
JIS K-2211(冷凍機油)の全酸価分析方法に準拠した方法で、ガス回収後の冷凍機油全酸価値の測定を行った。加速試験後の冷凍機油を秤量し、トルエン/イソプロパノール/水混合溶媒に溶解させ、指示薬としてα-ナフトールベンゼインを用いて1/100N-KOH・エタノール溶液にて中和滴定し、滴定量から冷凍機油全酸価(mg・KOH/g)を測定した。
比較例1~7、11~18、24は、いずれも安定化剤を用いていない。
Claims (9)
- ハイドロフルオロプロペン及び安定化剤を含む冷媒組成物であって、該安定化剤が、アルキルカテコール類、アルコキシフェノール類、ベンゾキノン類、フェノチアジン類及びフタル酸塩類からなる群より選ばれる少なくとも1種であることを特徴とする冷媒組成物。
- ハイドロフルオロプロペンが、2,3,3,3-テトラフルオロプロペン(HFO-1234yf)、(Z又はE-)1,3,3,3-テトラフルオロプロペン(HFO-1234ze)、(Z又はE-)1,2,3,3,3-ペンタフルオロプロペン(HFO-1225ye)、(Z又はE-)1,1,3,3,3-ペンタフルオロプロペン(HFO-1225zc)、及び(Z又はE-)3,3,3-トリフルオロプロペン(HFO-1243zf)からなる群より選ばれる少なくとも1種である、請求項1に記載の冷媒組成物。
- ハイドロフルオロプロペン100重量部に対する安定化剤の含有量が0.1~5.0重量部である、請求項1に記載の冷媒組成物。
- 更に冷凍機油を含有する、請求項1に記載の冷媒組成物。
- 冷凍機油が、ポリアルキレングリコール、ポリオールエステル及びポリビニルエーテルからなる群より選ばれる少なくとも1種を含み、40℃における動粘度が5~400cStである、請求項4に記載の冷媒組成物。
- 冷媒組成物が、冷凍機、冷蔵庫、モバイルエアコン、冷却機(チラー)、コンテナ用冷凍装置、家庭用エアコン、業務用エアコン、給湯器等の蒸気圧縮式ヒートポンプからなる群より選ばれる1種の用途に用いられる、請求項1~5のいずれかに記載の冷媒組成物。
- ハイドロフルオロプロペンを含む冷媒組成物の安定化方法であって、該冷媒組成物に、アルキルカテコール類、アルコキシフェノール類、ベンゾキノン類、フェノチアジン類及びフタル酸塩類からなる群より選ばれる少なくとも1種の安定化剤を添加することを特徴とする安定化方法。
- ハイドロフルオロプロペン及び安定化剤を含む冷媒組成物の安定性の評価方法であって、密閉容器中で、酸素の存在下及び/又は不存在下に、該冷媒組成物を加熱処理した後、処理後の冷媒組成物の酸分を分析することを特徴とする評価方法。
- ハイドロフルオロプロペン、冷凍機油及び安定化剤を含む冷媒組成物の安定性の評価方法であって、密閉容器中で、酸素の存在下及び/又は不存在下に、該冷媒組成物を加熱処理した後、処理後の冷媒組成物の酸分を分析する及び/又は処理後の冷媒組成物に含まれる冷凍機油の全酸価を分析することを特徴とする評価方法。
Priority Applications (8)
Application Number | Priority Date | Filing Date | Title |
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EP10746330.9A EP2402412B1 (en) | 2009-02-26 | 2010-02-26 | Refrigerant composition containing hydrofluoropropene with low-global warming potential |
CN201080009287.4A CN102333839B (zh) | 2009-02-26 | 2010-02-26 | 包含变暖系数低的氢氟丙烯的致冷剂组合物 |
ES10746330.9T ES2621969T3 (es) | 2009-02-26 | 2010-02-26 | Composición refrigerante que contiene un hidrofluoropropeno con bajo potencial de calentamiento global |
US13/203,352 US20110312101A1 (en) | 2009-02-26 | 2010-02-26 | Refrigerant composition containing hydrofluoropropene with low-global warming potential |
JP2011501671A JP5590024B2 (ja) | 2009-02-26 | 2010-02-26 | 温暖化係数の低いハイドロフルオロプロペンを含む冷媒組成物 |
KR1020117021959A KR101446386B1 (ko) | 2009-02-26 | 2010-02-26 | 온난화 계수가 낮은 하이드로플루오로프로펜을 포함하는 냉매 조성물 |
KR1020147004179A KR101544333B1 (ko) | 2009-02-26 | 2010-02-26 | 온난화 계수가 낮은 하이드로플루오로프로펜을 포함하는 냉매 조성물 |
US14/277,385 US9303198B2 (en) | 2009-02-26 | 2014-05-14 | Hydrofluoropropene refrigerant composition comprising phthalates |
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US13/203,352 A-371-Of-International US20110312101A1 (en) | 2009-02-26 | 2010-02-26 | Refrigerant composition containing hydrofluoropropene with low-global warming potential |
US14/277,385 Division US9303198B2 (en) | 2009-02-26 | 2014-05-14 | Hydrofluoropropene refrigerant composition comprising phthalates |
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US (2) | US20110312101A1 (ja) |
EP (2) | EP2402412B1 (ja) |
JP (1) | JP5590024B2 (ja) |
KR (2) | KR101544333B1 (ja) |
CN (1) | CN102333839B (ja) |
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Publication number | Publication date |
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KR20140032010A (ko) | 2014-03-13 |
US20110312101A1 (en) | 2011-12-22 |
CN102333839B (zh) | 2015-02-18 |
KR101446386B1 (ko) | 2014-10-01 |
US9303198B2 (en) | 2016-04-05 |
EP2402412B1 (en) | 2017-03-29 |
ES2621969T3 (es) | 2017-07-05 |
EP2743325A3 (en) | 2014-09-10 |
EP2743325A2 (en) | 2014-06-18 |
JPWO2010098451A1 (ja) | 2012-09-06 |
KR20110116064A (ko) | 2011-10-24 |
CN102333839A (zh) | 2012-01-25 |
EP2402412A4 (en) | 2013-09-25 |
EP2402412A1 (en) | 2012-01-04 |
KR101544333B1 (ko) | 2015-08-12 |
JP5590024B2 (ja) | 2014-09-17 |
US20140248706A1 (en) | 2014-09-04 |
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