CN101024792A - 含有多元醇酯和烷基苯的混合物的润滑组合物 - Google Patents
含有多元醇酯和烷基苯的混合物的润滑组合物 Download PDFInfo
- Publication number
- CN101024792A CN101024792A CNA200710091365XA CN200710091365A CN101024792A CN 101024792 A CN101024792 A CN 101024792A CN A200710091365X A CNA200710091365X A CN A200710091365XA CN 200710091365 A CN200710091365 A CN 200710091365A CN 101024792 A CN101024792 A CN 101024792A
- Authority
- CN
- China
- Prior art keywords
- alkylbenzene
- polyol ester
- mixture
- lubricant
- weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 96
- -1 polyol ester Chemical class 0.000 title claims abstract description 68
- 150000004996 alkyl benzenes Chemical class 0.000 title claims abstract description 65
- 229920005862 polyol Polymers 0.000 title claims abstract description 61
- 230000001050 lubricating effect Effects 0.000 title abstract description 18
- 239000000314 lubricant Substances 0.000 claims abstract description 55
- 239000003507 refrigerant Substances 0.000 claims abstract description 21
- 230000006835 compression Effects 0.000 claims abstract description 13
- 238000007906 compression Methods 0.000 claims abstract description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- 229910052799 carbon Inorganic materials 0.000 claims description 14
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 14
- 125000000217 alkyl group Chemical group 0.000 claims description 12
- 125000004432 carbon atom Chemical group C* 0.000 claims description 11
- 239000012530 fluid Substances 0.000 claims description 9
- 229920001774 Perfluoroether Polymers 0.000 claims description 8
- 230000032050 esterification Effects 0.000 claims 1
- 238000005886 esterification reaction Methods 0.000 claims 1
- 238000005057 refrigeration Methods 0.000 abstract description 51
- 238000004378 air conditioning Methods 0.000 abstract description 6
- 239000007788 liquid Substances 0.000 abstract description 4
- OHMHBGPWCHTMQE-UHFFFAOYSA-N 2,2-dichloro-1,1,1-trifluoroethane Chemical compound FC(F)(F)C(Cl)Cl OHMHBGPWCHTMQE-UHFFFAOYSA-N 0.000 abstract description 2
- 239000003795 chemical substances by application Substances 0.000 description 37
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 34
- 229910052739 hydrogen Inorganic materials 0.000 description 32
- 239000001257 hydrogen Substances 0.000 description 31
- 239000000654 additive Substances 0.000 description 22
- 230000000996 additive effect Effects 0.000 description 21
- 238000005461 lubrication Methods 0.000 description 13
- 239000003963 antioxidant agent Substances 0.000 description 12
- 230000003078 antioxidant effect Effects 0.000 description 11
- 150000002148 esters Chemical class 0.000 description 11
- LVGUZGTVOIAKKC-UHFFFAOYSA-N 1,1,1,2-tetrafluoroethane Chemical compound FCC(F)(F)F LVGUZGTVOIAKKC-UHFFFAOYSA-N 0.000 description 10
- 239000002253 acid Substances 0.000 description 10
- 239000003921 oil Substances 0.000 description 9
- 239000002480 mineral oil Substances 0.000 description 8
- 235000010446 mineral oil Nutrition 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 150000001721 carbon Chemical group 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000010687 lubricating oil Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 5
- 229920001515 polyalkylene glycol Polymers 0.000 description 5
- HFDVRLIODXPAHB-UHFFFAOYSA-N 1-tetradecene Chemical compound CCCCCCCCCCCCC=C HFDVRLIODXPAHB-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
- 238000006073 displacement reaction Methods 0.000 description 4
- 230000008014 freezing Effects 0.000 description 4
- 238000007710 freezing Methods 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- 229940059574 pentaerithrityl Drugs 0.000 description 4
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- VOWYKPIPCKXPCR-UHFFFAOYSA-K F[C+3].[Cl-].[Cl-].[Cl-] Chemical compound F[C+3].[Cl-].[Cl-].[Cl-] VOWYKPIPCKXPCR-UHFFFAOYSA-K 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- OWYWGLHRNBIFJP-UHFFFAOYSA-N Ipazine Chemical compound CCN(CC)C1=NC(Cl)=NC(NC(C)C)=N1 OWYWGLHRNBIFJP-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000003342 alkenyl group Chemical group 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 3
- 229910052794 bromium Inorganic materials 0.000 description 3
- 238000007046 ethoxylation reaction Methods 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N pentanoic acid group Chemical group C(CCCC)(=O)O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 3
- 229920000570 polyether Polymers 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 230000035945 sensitivity Effects 0.000 description 3
- CFQZKFWQLAHGSL-FNTYJUCDSA-N (3e,5e,7e,9e,11e,13e,15e,17e)-18-[(3e,5e,7e,9e,11e,13e,15e,17e)-18-[(3e,5e,7e,9e,11e,13e,15e)-octadeca-3,5,7,9,11,13,15,17-octaenoyl]oxyoctadeca-3,5,7,9,11,13,15,17-octaenoyl]oxyoctadeca-3,5,7,9,11,13,15,17-octaenoic acid Chemical compound OC(=O)C\C=C\C=C\C=C\C=C\C=C\C=C\C=C\C=C\OC(=O)C\C=C\C=C\C=C\C=C\C=C\C=C\C=C\C=C\OC(=O)C\C=C\C=C\C=C\C=C\C=C\C=C\C=C\C=C CFQZKFWQLAHGSL-FNTYJUCDSA-N 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 2
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 2
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 2
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical class OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 2
- 239000005642 Oleic acid Substances 0.000 description 2
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- ZTHYODDOHIVTJV-UHFFFAOYSA-N Propyl gallate Chemical compound CCCOC(=O)C1=CC(O)=C(O)C(O)=C1 ZTHYODDOHIVTJV-UHFFFAOYSA-N 0.000 description 2
- 125000002252 acyl group Chemical group 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 150000004982 aromatic amines Chemical class 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000002199 base oil Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- GQEZCXVZFLOKMC-UHFFFAOYSA-N n-alpha-hexadecene Natural products CCCCCCCCCCCCCCC=C GQEZCXVZFLOKMC-UHFFFAOYSA-N 0.000 description 2
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid group Chemical group C(CCCCCCC\C=C/CCCCCCCC)(=O)O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 150000003077 polyols Chemical class 0.000 description 2
- 230000003449 preventive effect Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- GUEIZVNYDFNHJU-UHFFFAOYSA-N quinizarin Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C(O)=CC=C2O GUEIZVNYDFNHJU-UHFFFAOYSA-N 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- RINCXYDBBGOEEQ-UHFFFAOYSA-N succinic anhydride Chemical compound O=C1CCC(=O)O1 RINCXYDBBGOEEQ-UHFFFAOYSA-N 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 2
- 229940095068 tetradecene Drugs 0.000 description 2
- 150000003852 triazoles Chemical group 0.000 description 2
- BIIBYWQGRFWQKM-JVVROLKMSA-N (2S)-N-[4-(cyclopropylamino)-3,4-dioxo-1-[(3S)-2-oxopyrrolidin-3-yl]butan-2-yl]-2-[[(E)-3-(2,4-dichlorophenyl)prop-2-enoyl]amino]-4,4-dimethylpentanamide Chemical compound CC(C)(C)C[C@@H](C(NC(C[C@H](CCN1)C1=O)C(C(NC1CC1)=O)=O)=O)NC(/C=C/C(C=CC(Cl)=C1)=C1Cl)=O BIIBYWQGRFWQKM-JVVROLKMSA-N 0.000 description 1
- RAADJDWNEAXLBL-UHFFFAOYSA-N 1,2-di(nonyl)naphthalene Chemical compound C1=CC=CC2=C(CCCCCCCCC)C(CCCCCCCCC)=CC=C21 RAADJDWNEAXLBL-UHFFFAOYSA-N 0.000 description 1
- BZJTUOGZUKFLQT-UHFFFAOYSA-N 1,3,5,7-tetramethylcyclooctane Chemical group CC1CC(C)CC(C)CC(C)C1 BZJTUOGZUKFLQT-UHFFFAOYSA-N 0.000 description 1
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 1
- FEXBEKLLSUWSIM-UHFFFAOYSA-N 2-Butyl-4-methylphenol Chemical group CCCCC1=CC(C)=CC=C1O FEXBEKLLSUWSIM-UHFFFAOYSA-N 0.000 description 1
- DHTAIMJOUCYGOL-UHFFFAOYSA-N 2-ethyl-n-(2-ethylhexyl)-n-[(4-methylbenzotriazol-1-yl)methyl]hexan-1-amine Chemical compound C1=CC=C2N(CN(CC(CC)CCCC)CC(CC)CCCC)N=NC2=C1C DHTAIMJOUCYGOL-UHFFFAOYSA-N 0.000 description 1
- IKEHOXWJQXIQAG-UHFFFAOYSA-N 2-tert-butyl-4-methylphenol Chemical compound CC1=CC=C(O)C(C(C)(C)C)=C1 IKEHOXWJQXIQAG-UHFFFAOYSA-N 0.000 description 1
- BKZXZGWHTRCFPX-UHFFFAOYSA-N 2-tert-butyl-6-methylphenol Chemical compound CC1=CC=CC(C(C)(C)C)=C1O BKZXZGWHTRCFPX-UHFFFAOYSA-N 0.000 description 1
- YAXXOCZAXKLLCV-UHFFFAOYSA-N 3-dodecyloxolane-2,5-dione Chemical class CCCCCCCCCCCCC1CC(=O)OC1=O YAXXOCZAXKLLCV-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- CKLJMWTZIZZHCS-UHFFFAOYSA-N D-OH-Asp Natural products OC(=O)C(N)CC(O)=O CKLJMWTZIZZHCS-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- CKLJMWTZIZZHCS-REOHCLBHSA-N L-aspartic acid Chemical compound OC(=O)[C@@H](N)CC(O)=O CKLJMWTZIZZHCS-REOHCLBHSA-N 0.000 description 1
- OYHQOLUKZRVURQ-HZJYTTRNSA-N Linoleic acid Chemical compound CCCCC\C=C/C\C=C/CCCCCCCC(O)=O OYHQOLUKZRVURQ-HZJYTTRNSA-N 0.000 description 1
- 241000158728 Meliaceae Species 0.000 description 1
- KEQFTVQCIQJIQW-UHFFFAOYSA-N N-Phenyl-2-naphthylamine Chemical compound C=1C=C2C=CC=CC2=CC=1NC1=CC=CC=C1 KEQFTVQCIQJIQW-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000002730 additional effect Effects 0.000 description 1
- 230000002152 alkylating effect Effects 0.000 description 1
- JXLHNMVSKXFWAO-UHFFFAOYSA-N azane;7-fluoro-2,1,3-benzoxadiazole-4-sulfonic acid Chemical compound N.OS(=O)(=O)C1=CC=C(F)C2=NON=C12 JXLHNMVSKXFWAO-UHFFFAOYSA-N 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- KYKAJFCTULSVSH-UHFFFAOYSA-N chloro(fluoro)methane Chemical compound F[C]Cl KYKAJFCTULSVSH-UHFFFAOYSA-N 0.000 description 1
- 239000000306 component Substances 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 1
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- RIZMRRKBZQXFOY-UHFFFAOYSA-N ethion Chemical compound CCOP(=S)(OCC)SCSP(=S)(OCC)OCC RIZMRRKBZQXFOY-UHFFFAOYSA-N 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 229960004232 linoleic acid Drugs 0.000 description 1
- 239000003879 lubricant additive Substances 0.000 description 1
- 239000010721 machine oil Substances 0.000 description 1
- 239000006078 metal deactivator Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 150000002763 monocarboxylic acids Chemical class 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 150000002989 phenols Chemical class 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
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 229920000223 polyglycerol Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000000473 propyl gallate Substances 0.000 description 1
- 229940075579 propyl gallate Drugs 0.000 description 1
- 235000010388 propyl gallate Nutrition 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229940014800 succinic anhydride Drugs 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 239000003784 tall oil Substances 0.000 description 1
- 230000006209 tert-butylation Effects 0.000 description 1
- RJDVGKCBHFINOK-UHFFFAOYSA-N tris(2-methylphenoxy)-sulfanylidene-$l^{5}-phosphane Chemical compound CC1=CC=CC=C1OP(=S)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C RJDVGKCBHFINOK-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- C10M111/00—Lubrication compositions characterised by the base-material being a mixture of two or more compounds covered by more than one of the main groups C10M101/00 - C10M109/00, each of these compounds being essential
- C10M111/02—Lubrication compositions characterised by the base-material being a mixture of two or more compounds covered by more than one of the main groups C10M101/00 - C10M109/00, each of these compounds being essential at least one of them being a non-macromolecular organic compound
-
- 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
- C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
- C10M169/04—Mixtures of base-materials and additives
-
- 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
-
- 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
- C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
- C10M2203/06—Well-defined aromatic 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
- C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
- C10M2203/06—Well-defined aromatic compounds
- C10M2203/065—Well-defined aromatic compounds used as base material
-
- 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
- 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
- C10M2207/2835—Esters of polyhydroxy compounds used as base material
-
- 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
- C10N2020/01—Physico-chemical properties
- C10N2020/04—Molecular weight; Molecular weight distribution
-
- 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
- C10N2020/099—Containing Chlorofluorocarbons
-
- 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
-
- 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
- C10N2030/40—Low content or no content compositions
- C10N2030/41—Chlorine free or low chlorine content compositions
-
- 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
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/30—Refrigerators lubricants or compressors lubricants
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Lubricants (AREA)
Abstract
本发明涉及一种用于氢氟烃和任选地氢氯氟烃制冷剂的混合物的润滑基本原料，其包含：(A)至少一种烷基苯和(B)至少一种多元醇酯的混合物。尽管在制冷或空调系统所需要的操作温度和压力下烷基苯不能与制冷剂混合物混溶，但是发现加入低浓度的多元醇酯可显著提高烷基苯和多元醇酯混合物的混溶性。本发明的重要标准是在压缩制冷系统的整个操作温度下多元醇酯和烷基苯的润滑混合物既可与作为液态制冷剂又可与作为气态制冷剂的氢氟烃制冷剂混合物充分混溶。
Description
发明领域
本发明涉及一种压缩制冷用的润滑组合物，其含有多元醇酯和特定烷基苯的混合物。在优选的实施方案中，所述烷基苯是一组窄范围的具有特定粘度范围的支化或线型烷基取代的苯，其混合了与氢氟烃制冷剂具有良好混溶性的多元醇酯。可以在有或者没有添加剂(包括具有润滑粘度的其它油类)的情况下使用含有多元醇酯和烷基苯的混合物来形成润滑组合物。所述组合物可以用于正位移压缩机，例如往复旋转叶片式、涡管式或者旋转螺杆式空气压缩机。
发明背景
过去一直使用润滑油来润滑正位移压缩机的轴承、密封转子以及冷却压缩气体。工业中常用的润滑油包含作为基油的矿物油或合成油以及用于特定用途的多种添加剂。热稳定性和氧化稳定性以及光泽和沉积控制是润滑剂中希望的用以最大限度地延长润滑剂的寿命并且由此最大限度地延长设备寿命的一些重要性质，特别是在运行正位移压缩机(例如往复旋转叶片式、涡管式或旋转螺杆式压缩机)时产生的高温和高压条件下。
工业中还希望提供这样的润滑组合物：不会因为暴露于湿气或高温条件下或者长期使用而损害其性能。烃油具有非常好的抵抗与水分反应的性能。多元醇酯具有良好的耐高温性能，但是与水反应的稳定性较差。
专利US 4,046,533教导了支链烷基苯可被用作制冷剂的润滑剂，所述制冷剂包含具有1-3个碳原子的卤素取代烃类和至少40重量％的氟。在该文献的第二栏30行至第3栏50行中，详细描述了如何识别烷基基团中支化量高的烷基苯以及如何识别卤素取代烃类。所述卤素取代烃类的实例均含有氯原子。
专利US 4,302,343介绍了具有3-8个羟基和5-10个碳原子的受阻多元醇与具有4-18个碳原子的一种或多种链烷酸的酯。该专利的润滑剂是这些酯与聚醚型多元醇的混合物。该润滑剂被用于旋转螺杆式压缩机。
专利US 4,755,316介绍了与新型制冷剂R-134(四氟乙烷)一起使用的聚亚烷基二醇润滑剂，开发这种新型制冷剂是为了使由卤素-碳氟化合物导致的臭氧损耗问题最小化。该专利讨论了矿物油这种用于R-12的常规润滑剂不能与R134a混溶，并因此对满足所有压缩制冷要求以及与R134a混溶性的润滑油进行了研究。
Lubrizol Corporation的EP0 422 185B公开了多元醇酯与氢氟烃润滑剂例如R134a的用途。该申请中优选的多元醇酯是那些在压缩制冷系统中工作流体的整个操作范围内可与氢氟烃润滑剂混溶的多元醇酯。该申请概述了如何选择不同的多元醇酯以获得与R134a的混溶性和其它性能。
专利US 5,342,533介绍了压缩机的冷冻机油组合物，其包含US4,302,343和EP0 4 222 185B所述的多元醇的羧酸酯和氢氟烃。US5,342,533还在所述润滑剂中包含了磷酸酯或亚磷酸酯，并任选地包含少量的矿物油和/或烷基苯。
专利US 6,207,071和6,252,300涉及压缩制冷系统中与R134a和/或R125一起使用的分子量为200-350的烷基苯。该申请表明如果60％烷基苯的分子量没有落入该范围，那么在长期使用后主要由烷基苯组成的润滑组合物会导致压缩机部件的胶住。该润滑剂中任选地包含含磷化合物。
发明概述
本发明涉及一种包含多元醇酯和烷基苯的混合物的润滑流体，其中烷基苯具有高支化的烷基和低粘度。所述润滑流体不同于大多数烷基苯油或烷基苯与其它油的混合物，因为其可在空调装置、冷藏装置、冷冻装置等用的压缩制冷系统的操作温度范围内与氢氟烃润滑剂混溶。在实施方案A中，该润滑剂可与基本上没有含氯或含溴制冷剂的制冷剂混溶。在实施方案B中，该制冷剂可含有含氯的碳氟制冷剂。多元醇酯可为该混合物提供良好的温度稳定性、润滑性和与氢氟烃的混溶性。烷基苯可提供良好的温度稳定性、润滑性，并且可降低该混合物的吸水作用和水敏性。可以向所述润滑混合物中加入添加剂例如抗氧化剂、缓蚀剂、金属钝化剂和其它润滑油。在实施方案A中，烷基苯是每个苯环上主要具有9-15碳原子的单一的高支化烷基的ISO 5烷基苯。在更优选的实施方案中，烷基苯与具有2-6个OH基团的受阻多元醇的多元醇酯混合。该混合物还可以在其中结合或者不结合添加剂的情况下使用。
根据本发明，所述润滑组合物显示出高能效操作所必需的低粘度、降低的吸水作用和水敏性以及润滑剂的出色的长期稳定性。
优选实施方案的详细说明
本公开将首先描述本发明的实施方案A，其中制冷剂基本上没有含氯或含溴制冷剂。实施方案A受益于低粘度的烷基苯和大量的的多元醇酯，以能够获得润滑混合物和氢氟烃制冷剂之间混溶性。之后描述的实施方案B中制冷剂是氢氟烃制冷剂和氟氯碳制冷剂的混合物。在实施方案B中，所需多元醇酯的百分比较低，并希望烷基苯的粘度稍高。
实施方案A和润滑混合物的一般讨论
本发明的润滑混合物的组分选自类型较广的多元醇酯和烷基苯。多元醇酯类物质包括由具有2个或更多个OH基团的醇与一元和/或多元羧酸缩合以在反应产物中形成酯键而得到的酯。这些类型物质的粘度和热稳定性的变化范围宽。烷基苯类物质的变化范围同样广泛，其包括粘度很低到粘度相对高的单和多烷基官能化的苯。烷基苯包括分子量较低的物质例如甲苯，这些物质通常不被视为润滑油，并且会在压缩制冷系统中的某些条件下呈气体而不是液体。
本发明实施方案A的重要标准是：在压缩制冷系统的整个操作温度下多元醇酯和烷基苯的润滑混合物可与所选择的氢氟烃制冷剂或制冷剂混合物混溶。对于实施例A和B来说润滑剂与制冷剂在整个操作温度范围内的混溶性确保了从压缩机出来进入制冷系统的润滑油可经过蒸发孔和传热装置送回压缩机，在那里它起到润滑剂的作用，并且确保在该系统中不混溶的润滑剂部分不会作为限制制冷剂穿过该系统的阻塞物出现。这种混溶性同样确保了传热装置上存在的润滑油膜最少，而这种润滑油膜会通过充当绝热膜而干扰传热效率。尽管润滑混合物和制冷剂所需的混溶程度可以依照实施方案A中的应用而改变，但是理想的范围是在约-20℃～80℃、更优选约-10℃～70℃下制冷剂(其可以是其它氢氟烃或氢氟烃混合物)中润滑剂的浓度为5、10和/或20重量％。
润滑混合物的特别有利之处在于：可以配制低粘度的润滑剂从而易于通过最大限度地减小能量损失而提高制冷系统的效率。尽管可以使多元醇酯与烷基苯的混合物配制达到许多种粘度，但是实施方案A的纯净润滑混合物(即没有添加剂、制冷剂和其它稀释剂的润滑剂)的优选粘度为约ISO5～70，较理想地5～68，更加理想地5～32，并且优选地5～15。ISO粘度本质上是40℃下以厘沲(cSt)为单位的物质的粘度数值。
尽管烷基苯与氢氟烃不混溶，但是当烷基苯与本公开的特定多元醇酯混合时其变得可与氢氟烃混溶。多元醇酯的高温稳定性好且使用寿命长，但是对水分敏感并且会水解形成原料醇和羧酸。单独的烷基苯在与氢氟烃的混溶性方面存在问题，但是其可以降低混合物的水敏性。
在实施方案A的混合物中烷基苯的用量理想地为烷基苯与多元醇酯的混合物的约5～45重量％，较理想地约10～40重量％，更加理想地约15～35重量％，并且优选地约25～35重量％。多元醇酯的用量互补地例如为烷基苯与多元醇酯的混合物的约55～95重量％，理想地约60～90重量％，更理想地约65～85重量％，并且优选约65～75重量％。理想的是混合物的油类的至少80、85或90重量％为下文所述的多元醇酯和烷基苯。可将其它油、组分和添加剂加入润滑混合物中以提供特定应用所需的附加性能。烷基苯和多元醇酯润滑剂的添加剂是本领域公知的。
用于实施方案A的烷基苯的分子量理想地为约100～500，更理想地约200～350，并且优选约200～300。用于实施方案A的烷基苯的粘度理想地为40℃下约1～15厘沲，并且更理想地约3～10厘沲，并且优选约3～7厘沲。在实施方案A中理想的是烷基苯中至少50mol％、更理想地至少75mol％、并且优选至少85mol％被单烷基取代。在实施方案A中，理想的是所述烷基苯的烷基中至少50mol％、更理想地至少75mol％、并且优选至少85mol％具有两个或更多个从烷基主链伸出的甲基和/或乙基支链。在两个实施方案中，由于烷基苯是烷基化反应的反应产物，因此理想的是烷基苯中至少50或60％、更理想地至少75％、并且优选至少85％具有总共约5～40、更理想地约7～30、并且优选约8～16个碳原子与苯环连接。
用于实施方案A或B的多元醇酯可选自EP0 422 185B教导的那些。多元醇酯的数均分子量理想地为约300～1000g/mol，并且更理想地约300～600。实施方案A的多元醇酯的纯粘度(在没有添加剂或制冷剂的情况下)理想地为40℃下约5～70厘沲，理想地约5～68厘沲，更理想地约5～32厘沲，并且优选地约5～22厘沲。
一般地，所述酯的多元醇组分和羧酸组分中的烷基支化可以促进与R134a型氢氟烃制冷剂更好的混溶性，但是也会增加粘度。较低分子量的多元醇和羧酸易于促进较低的粘度。具有4个或更少碳原子的羧酸就引入多元醇酯中来说趋于不利。为了维持低温下与氢氟烃的混溶性，只能允许少量(例如以多元醇酯中羧酸总量计小于10mol％)的碳原子数多于10的羧酸。
通过多元醇与羧酸的反应来制备多元醇酯。理想的是每个多元醇分子中具有2～10个羟基和3～30个碳原子，任选地多元醇中具有一个或多个醚键(例如二季戊四醇)。更理想的是多元醇平均具有4～10个碳原子。尽管多元醇酯中可以存在除C、H和O外的其它杂原子，但是它们通常是不利的。出于稳定性和混溶性的原因，优选的多元醇是受阻多元醇和由受阻多元醇制得的缩合产物(聚醚)。受阻多元醇的优选的碳原子数为5～7。理想的是，多元醇酯的至少50mol％、并且更理想地至少80mol％源自于具有5～7个碳原子和2～4个OH基团的受阻多元醇的反应。受阻多元醇酯是润滑领域公知的。它们包括但不限于新戊二醇、三羟甲基丙烷、季戊四醇、二季戊四醇和季戊四醇的较高级的聚醚齐聚物。它们的特征在于：没有直接与β碳连接的氢原子(α碳与多元醇或多元醇酯的氧连接(这取决于你关注的是否是多元醇或多元醇酯))。不是让氢原子与β碳连接，而是让其它烷基或羟甲基与β碳连接。在制备多元醇酯时使用这些受阻多元醇导致改进了多元醇酯的稳定性。属于多元醇的较广泛的定义范围的其它多元醇包括乙二醇、二甘醇、丙三醇、聚丙三醇等。
制备多元醇酯所用的羧酸理想地主要是具有5～10个碳原子的羧酸，从而使至少50mol％、并且更理想地至少80mol％多元醇酯具有5～10个碳原子的一元羧酸的残基(进入多元醇酯的羧酸反应物部分)。理想的是二官能度或更高官能度的多元羧酸的量小于多元醇酯中羧酸残基总量的10mol％。少量(例如，小于用于制备多元醇酯所用的羧酸的10mol％)羧酸可以具有多于10个碳原子，并且这些酸残基可以以超过其相对量为润滑剂提供的特殊性质。
本发明的润滑混合物还可与添加剂或同时与油类和添加剂混合。
制冷剂
本公开的实施方案A所用的制冷剂理想地主要是(例如至少80、90或95重量％)氢氟烃或可为特定应用提供所需性质的不同氢氟烃的混合物。氢氟烃被定义为每分子具有1～5个碳原子、至少一个氢原子和至少一个氟原子的化合物。对于实施方案A而言，理想的是制冷剂中没有含氯的碳氟化合物。氢氟烃中通常不包含氯、溴或其它原子，除非其作为来自制备工艺或处理过程的杂质。氢氟烃包括但不限于R-134a、R-125、R-32、R-143a及其混合物。对本公开有利的氢氟烃是那些具有适于压缩制冷的蒸汽压以及处理特性的氢氟烃。对于本公开而言，压缩制冷可以包括尤其是冷藏、空调、冷却、热泵等。
添加剂
如前所述，本发明的润滑混合物或润滑组合物也可以包含有效量的添加剂例如抗氧化剂、防锈剂和缓蚀剂、金属钝化剂、润滑性添加剂、抗磨添加剂或者根据需要的添加剂。市售可得的抗磨添加剂的实例是例如可从Akzo-Noble以Syn-O-Add，8484得到的磷酸三甲苯酯(TCP)、或可从CibaGeigy得到的硫代磷酸三苯基酯(TPPT)。一般地，成品润滑组合物会含有较少量的添加剂组分，所述用量足以改进具有润滑粘度的油或者基本原料混合物的性能特征和性质，或者改进基油和基本原料混合物两者的性能特征和性质。一般地，用于其已知用途的添加剂可占润滑组合物总重量的约10～0.01重量％，并且优选占润滑组合物总重量的约5～0.001重量％。
有用的抗氧化剂的实例包括苯基萘基胺(α和/或β)、包括烷基化的二苯胺在内的二苯胺。市售可得的这些抗氧化剂的实例是可从Ciba Geigy得到的Irganox L-57和可从Vanderbilt Chemical得到的Valube 81。合适的抗氧化剂的实例还有酚类抗氧化剂、芳族胺类抗氧化剂、硫化的酚类抗氧化剂和有机亚磷酸酯等。酚类抗氧化剂的实例包括2，6-二-叔丁基苯酚、叔丁基化苯酚的液体混合物、2，6-二-叔丁基-4-甲基苯酚、4，4’-亚甲基双(2，6-二叔丁基苯酚)、2，2’-亚甲基双(4-甲基-6-叔丁基苯酚)、混合的亚甲基-桥接的多烷基酚和4，4’-硫代双(2-甲基-6-叔丁基苯酚)。N，N’-二仲丁基-对亚苯基二胺、4-异丙基氨基二苯胺、苯基-α-萘胺、苯基-β-萘胺和环烷基化的二苯胺是芳族胺抗氧化剂的实例。可用于本发明的市售抗氧化剂还包括可从Ethyl Corporation得到的Ethanox702、可从Ciba Geigy得到的IrganoxL-135和IrganoxL-118、IrganoxL-06以及可从RheinChemie得到的RC-7130。
合适的防锈剂和缓蚀剂的实例是中性的金属磺酸盐例如磺酸钙、磺酸镁、磺酸钠、二壬基萘磺酸钡和石油磺酸钙。可使用的其它类型的防锈剂和缓蚀剂包括一元羧酸和多元羧酸。合适的一元羧酸的实例是油酸和十二烷酸。合适的多元羧酸包括二聚酸和三聚酸，例如由松浆油脂肪酸、油酸和亚油酸制得的二聚酸和三聚酸。还可使用基于羧酸的不含金属的物质例如羧酸羟烷基酯。另一类用于实施本发明的防锈剂包括链烯基琥珀酸和链烯基琥珀酸酐缓蚀剂，例如四丙烯基琥珀酸、四丙烯基琥珀酸酐、十四烯基琥珀酸、十四烯基琥珀酸酐、十六烯基琥珀酸和十六烯基琥珀酸酐等。还可使用链烯基中具有约8～24个碳原子的链烯基琥珀酸和醇(例如聚乙二醇)的半酯。其它合适的防锈剂或缓蚀剂包括醚胺；酸式磷酸盐；胺类；聚乙氧基化的化合物例如乙氧基化的胺类、乙氧基化的酚类和乙氧基化的醇类；咪唑啉；以及氨基琥珀酸及其衍生物。可以使用这些防锈剂或缓蚀剂的混合物。这里引用专利US 5,773,393的全文，目的在于有关防锈剂和缓蚀剂的公开部分。市售可得的缓蚀剂的实例是可从Lubrizol Corporation得到的L-859。
合适的金属钝化剂的实例是含氮、氧和硫的有机化合物。对于铜而言，有用的化合物是例如取代的苯并三唑、烷基或酰基取代的5，5’-亚甲基-二苯并三唑、烷基或酰基取代的2，5-二巯基噻唑、水杨基氨基胍盐和醌茜。棓酸丙酯是用于镁的金属钝化剂的实例，癸二酸是用于铅的钝化剂的实例。市售可得的三唑金属钝化剂的实例是可从Ciba Geigy得到的Irgamet 39。
对于抗氧化剂而言，上述添加剂的有效量通常为润滑组合物总重量的约0.005～5重量％；对于缓蚀剂而言，上述添加剂的有效量通常为润滑组合物的总重量的约0.005～0.5重量％；对于金属钝化剂而言，上述添加剂的有效量通常为润滑组合物的总重量的约0.001～0.5重量％。应理解的是依据润滑组合物的使用环境，可以使用更多或者更少量的添加剂。
本发明还涉及一种润滑设备(例如正位移压缩机例如往复旋转叶片式、涡管式或旋转螺杆式空气压缩机)的方法，由此最大限度地延长润滑剂和设备的寿命，因为所述润滑剂具有出色的氧化稳定性和热稳定性。
空调系统和制冷系统对制冷润滑剂具有多种操作温度要求。一般地，空调设施需要能够在约0℃～70或80℃下与制冷剂混溶的润滑剂，而制冷系统需要低于0℃(例如-10℃或-20℃，以使冷冻室内保持冷冻温度)的下的混溶性。在HFC(氢氟烃，通常不含氯和溴)体系中，这些混溶性要求可以通过使用基于PAG(聚亚烷基乙二醇)和基于POE(多元醇酯)的润滑剂来达到。然而，由表1的数据所示，采用AB(烷基苯)不能达到混溶性要求。可以认为粘度低于ISO 7的AB与HFCs的混溶性是有限的。然而，它们(具有ISO7粘度的AB润滑剂)由于润滑膜的强度不够而不能用于冷冻或空调压缩机。
表1.AB与R-134a的混溶性
| AB | AB-7 | AB-10 | AB-22 | AB-32 |
| 酯 | 无 | 无 | 无 | 无 |
| 粘度(40℃)，cSt | 7 | 10 | 22 | 32 |
| R-134a，5％* | X | X | X | X |
| R-134a，10％ | X | X | X | X |
*R-134a/润滑剂溶液中有5％润滑剂。
X：在-60℃～60℃的任何温度下不混溶。
AB-7：来自Shrieve Chemical的ISO 7 AB。
AB-10：来自Shrieve Chemical的ISO 10 AB。
AB-22：来自Shrieve Chemical的ISO 22 AB。
AB-32：来自Shrieve Chemical的ISO 32 AB。
表2显示了POE/AB混合物的混溶性。这些混合物中POE/AB比率的设计应使得混合物的粘度处于ISO 10～ISO 32的变化范围内。选择的POE是与HCFs混溶性高的那些，因为这对于改进混合物的混溶性至关重要。
B1-B4实施例是制备的满足ISO 10要求的混合物。在制冷剂/润滑剂溶液中的润滑剂粘度为5％和10％下，B3和B4实施例表现出明显优于B1和B2实施例的混溶性，并且满足制冷润滑剂的要求。较好的混溶性归因于所述混合物选择的低粘度AB和高混溶性POE。预计润滑剂与HFCs的混溶性会在较高粘度时下降。这使得难以配制出与HFCs具有足够混溶性的粘度较高的POE/AB混合物。表2中B5-B8实施例的粘度变化范围是22～32，数据表明B8是唯一可适用于空调或制冷系统的具有足够粘度的混合物。与ISO 10的情形类似，B8的良好的混溶性归因于AB的低粘度和POE 4与HFC制冷剂的高混溶性。
表2.POE/AB混合物与R-134a的混溶性
(℃温度下的较低混溶性)
| B1 | B2 | B3 | B4 | B5 | B6 | B7 | B8 | |
| AB | 70％AB-7 | 30％AB-22 | 30％AB-5 | 30％AB-5 | 50％AB-10 | 30％AB-7 | 70％AB-22 | 25％AB-5 |
| 酯 | 30％POE1 | 70％POE2 | 50％POE320％POE2 | 30％POE140％POE2 | 50％POE1 | 75％POE4 | 30％POE4 | 75％POE4 |
| 粘度(40℃)，cSt | 10 | 10 | 10 | 10 | 22 | 32 | 32 | 32 |
| R-134a，5％ | 5 | 40 | -30 | -25 | -20 | -10 | X | -25 |
| R-134a，10％ | 25 | 55 | -25 | -20 | 20 | 15 | X | -5 |
POE1：nC5、nC7、iC9、PE(季戊四醇)
POE2：2EH、NPG(新戊二醇)
POE3：nC5、PE
POE4：nC5、iC8、iC9、PE
实施方案B
与实施方案A相似，实施方案B的的重要标准是：在压缩制冷系统的整个操作温度下，多元醇酯和烷基苯的润滑混合物可与实施方案B的制冷剂充分混溶，其中所述制冷剂是既可作为液体制冷剂又可作为气体制冷剂的氢氯氟烃和氢氟烃制冷剂的混合物。在实施方案B中，对于制冷剂混合物(其可以是R-22和R-152a的混合物或氢氯氟烃和氢氟烃的其它混合物)中润滑剂浓度为5、10和/或20重量％而言，操作温度为约-30℃～80℃，更优选约-30℃～60℃。
实施方案B中润滑混合物的特别有利之处在于：可以配制出低至中等粘度的润滑剂，从而通过最大限度地减小能量损失来提高制冷系统的效率。在实施方案B中尽管可以使多元醇酯与烷基苯的混合物配制达到许多种粘度，但是纯净润滑混合物(即没有添加剂、制冷剂和其它稀释剂的润滑剂)的优选粘度为约ISO 5～70，较理想地ISO 5～68，更加理想地ISO5～46，并且优选地ISO 5～35。该粘度范围的上限稍高于实施方案A的。
尽管烷基苯通常不与氢氟烃混溶，但是当烷基苯与本公开的特殊的多元醇酯混合时其变得可与氢氯氟烃/氢氟烃混合物混溶。
在实施方案B中，烷基苯在混合物中的用量理想地为烷基苯与多元醇酯的混合物的约1～99重量％，较理想地约50～99％，更加理想地约60～99％。在实施方案B中多元醇酯的用量互补地为烷基苯与多元醇酯的混合物的约99～1重量％，较理想地约50～1重量％，更加理想地约40～1重量％。
实施方案B中烷基苯的数均分子量理想地为约100～500，较理想地约200～350，优选地约200～300。理想的是烷基苯在40℃下的粘度为约1～100cSt，较理想地约3～68cSt，优选地约5～68cSt。该粘度范围的上限通常稍高于实施方案A的。理想地烷基苯的至少50mol％、较理想地至少75mol％、优选地至少85mol％是单烷基或二烷基取代的。所述烷基可以是线型的或支化的。理想的是实施方案B中多元醇酯在40℃下的纯粘度(即没有添加剂或制冷剂)为约5～120cSt，理想地约5～68cSt。
用于实施方案B的制冷剂
理想的是实施方案B所用的制冷剂主要(例如至少80、90或95重量％)是氢氯氟烃和氢氟烃的混合物，或者是可为特定应用提供所需性质的氢氯氟烃和氢氟烃的混合物。氢氯氟烃被定义为每分子具有1～4个碳原子、至少一个氢原子、至少一个氟原子和至少一个氯原子的化合物。氢氯氟烃包括但不限于R-22、R-123、R-124、R-133a；R-31、R-141b、R-142b及其混合物。理想的是制冷剂的氢氟烃部分不存在含氯的碳氟化合物。氢氟烃中通常不包含氯、溴或其它原子，除非其作为来自制备工艺或处理过程的杂质。氢氟烃包括但不限于R-134a、R-125、R-32、R-143a、R-152a及其混合物。理想的是氢氯氟烃和氢氟烃的重量比为5∶95～95∶5，较理想地10∶90～90∶10，更加理想地15∶85～85∶15。进一步优选的范围是约10∶90～35∶65，并且更优选地15∶85～30∶70。本公开中有利的氢氯氟烃和氢氟烃的混合物是那些具有适于压缩制冷的蒸汽压以及处理特性的氢氟烃。希望使用氢氯氟烃和氢氟烃制冷剂的混合物的理由有许多，其包括在允许使用氢氯氟烃的国家里混合物的氢氯氟烃部分具有价格优势。
实施方案B的空调系统和制冷系统对制冷润滑剂的操作温度有多种要求。一般地，空调设施要求润滑剂可在约-10℃～70℃或80℃下与制冷剂混溶，而制冷系统要求在低于0℃(例如低至-10℃或-40℃，以使冷冻室内保持冷冻温度)下的混溶性。在HCFC(氢氯氟烃)体系中，可以通过使用AB(烷基苯)和矿物油来达到这些混溶性要求，因此制冷剂中通常不需要较为昂贵的基于PAG(聚亚烷基乙二醇)和基于POE(多元醇酯)润滑剂。然而，当使用氢氯氟烃和氢氟烃的混合物作为制冷剂时，由表3的数据所示，通过采用矿物油或AB(烷基苯)无法达到混溶性要求。
表3.AB和矿物油与R-22a/R-152a(25/75)混合物的混溶性
| AB | AB-1 | AB-2 | MO-1 | MO-2 |
| 粘度(40℃)，cSt | 32 | 46 | 32 | 46 |
| 10％× | X | X | X | X |
| 20％× | X | X | X | X |
*R-22a/R-152a润滑剂溶液中有10％或20％的润滑剂。
X：在-40℃～15℃的任何温度下都不混溶
AB-1：来自Shrieve Chemical的ISO 32烷基苯
AB-2：来自Shrieve Chemical的ISO 46烷基苯
MO-1：来自Galumet的ISO 32 Group I矿物油
MO-2：来自Galumet的ISO 46 Group I矿物油
表4显示了POE/AB混合物的混溶性。这些数据表明通过将低浓度的POE混入AB中可以实现氢氯氟烃和氢氟烃混合制冷剂与润滑剂之间的充分混溶性。预计通过增加AB中的POE浓度可进一步改进这种混溶性。
表4.POE/AB混合物与R-22a/R-152a(25/75)混合物的混溶性
| B9 | B10 | B11 | B12 | |
| 烷基苯 | 95％AB-1 | 85％AB-1 | 95％AB-1 | 85％AB-1 |
| 酯 | 5％POE1 | 15％POE1 | 5％POE5 | 15％POE5 |
| 粘度(40℃)，cSt | 31 | 31 | 30 | 28 |
| 10％* | 低至-40℃可混溶 | 低至-40℃可混溶 | 低至-40℃可混溶 | 低至-40℃可混溶 |
*R-22a/R-152a润滑剂溶液中有10％的润滑剂。
AB-1：来自Shrieve Chemical的ISO 32 AB
POE 5：2-乙基己酸(EH)和NPG(新戊二醇)的酯与2EH和PE
(季戊四醇)的酯的混合物
尽管通过参照某些优选实施方案说明并描述了本发明，但是显然本领域技术人员通过阅读和理解本说明书而意识到等同的变化方案和改进方案。本发明包括所有这些等同的变化方案和改进方案，并且仅由权利要求书来限定本发明的范围。
Claims (6)
1.一种压缩制冷系统用的工作流体，其含有：a)氢氯氟烃和氢氟烃制冷剂的混合物，b)包含约1～99重量％的数均分子量约100～500的烷基苯和约99～1重量％的数均分子量约300～1000的多元醇酯的润滑剂。
2.根据权利要求1的工作流体，其中所述烷基苯的数均分子量为约200～350并且其中至少80mol％被单烷基化或被二烷基化。
3.根据权利要求2的工作流体，其中所述烷基苯的烷基基团是支化或线型的C8～C16烷基。
4.根据权利要求3的工作流体，其中至少80重量％所述多元醇酯源自受阻多元醇与具有5-10个碳原子的羧酸的酯化。
5.根据权利要求1的工作流体，其中所述烷基苯占所述润滑剂的约60～99重量％，并且所述多元醇酯占所述润滑剂的约40～1重量％。
6.根据权利要求4的工作流体，其中所述烷基苯占所述润滑剂的约90～99重量％，并且所述多元醇酯占所述润滑剂的约10～1重量％。
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US33271001P | 2001-11-19 | 2001-11-19 | |
| US60/332,710 | 2001-11-19 | ||
| US38859502P | 2002-06-13 | 2002-06-13 | |
| US60/388,595 | 2002-06-13 |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB028255542A Division CN100455645C (zh) | 2001-11-19 | 2002-11-13 | 含有多元醇酯和烷基苯的混合物的润滑组合物 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101024792A true CN101024792A (zh) | 2007-08-29 |
| CN100588703C CN100588703C (zh) | 2010-02-10 |
Family
ID=26988353
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB028255542A Expired - Lifetime CN100455645C (zh) | 2001-11-19 | 2002-11-13 | 含有多元醇酯和烷基苯的混合物的润滑组合物 |
| CN200710091365A Expired - Lifetime CN100588703C (zh) | 2001-11-19 | 2002-11-13 | 含有多元醇酯和烷基苯的混合物的润滑组合物 |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB028255542A Expired - Lifetime CN100455645C (zh) | 2001-11-19 | 2002-11-13 | 含有多元醇酯和烷基苯的混合物的润滑组合物 |
Country Status (7)
| Country | Link |
|---|---|
| US (2) | US7208098B2 (zh) |
| EP (2) | EP2077314A1 (zh) |
| KR (2) | KR100983741B1 (zh) |
| CN (2) | CN100455645C (zh) |
| AU (1) | AU2002346463B2 (zh) |
| BR (1) | BR0214272A (zh) |
| WO (1) | WO2003044137A2 (zh) |
Families Citing this family (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7910017B2 (en) * | 2003-11-14 | 2011-03-22 | Paratherm Corporation | Low temperature heat transfer fluid composition comprising alkylbenzene and dibutyl ether |
| BRPI0502759B1 (pt) * | 2005-06-30 | 2014-02-25 | óleo lubrificante e composição lubrificante para uma máquina de refrigeração | |
| CN101248164A (zh) * | 2005-07-27 | 2008-08-20 | 卢布里佐尔公司 | 高粘合成酯润滑剂基础油料掺合物 |
| US8535556B2 (en) * | 2006-03-30 | 2013-09-17 | E I Du Pont De Nemours And Company | Compositions comprising iodotrifluoromethane and stabilizers |
| WO2008013844A2 (en) * | 2006-07-25 | 2008-01-31 | General Vortex Energy, Inc. | System, apparatus and method for combustion of metal and other fuels |
| WO2008027515A2 (en) * | 2006-09-01 | 2008-03-06 | E. I. Du Pont De Nemours And Company | Phosphorus-containing stabilizers for fluoroolefins |
| CN101528887B (zh) | 2006-09-01 | 2014-07-16 | 纳幕尔杜邦公司 | 氟烯烃用的环氧化物和氟化环氧化物稳定剂 |
| WO2008027514A1 (en) * | 2006-09-01 | 2008-03-06 | E. I. Du Pont De Nemours And Company | Terpene, terpenoid, and fullerene stabilizers for fluoroolefins |
| US10246621B2 (en) | 2007-11-16 | 2019-04-02 | Honeywell International Inc. | Heat transfer methods, systems and compositions |
| US9938442B2 (en) * | 2007-11-16 | 2018-04-10 | Honeywell International Inc. | Hydrofluorocarbon/trifluoroiodomethane/ hydrocarbons refrigerant compositions |
| US9481852B2 (en) * | 2008-01-24 | 2016-11-01 | The Lubrizol Corporation | High viscosity synthetic ester lubricant base stock blends |
| US8402778B2 (en) * | 2008-03-31 | 2013-03-26 | National Refrigerants, Inc. | Method for enhancing mineral oil miscibility and oil return |
| JP2016535103A (ja) * | 2013-04-11 | 2016-11-10 | シュリーブ ケミカル プロダクツ，インク． | 潤滑油及びその使用 |
| CN105209582A (zh) * | 2013-04-11 | 2015-12-30 | 瑞弗化工有限公司 | 润滑油及其用途 |
| BR102013032982A2 (pt) * | 2013-12-20 | 2015-09-08 | Whirlpool Sa | óleo, composição lubrificante com lubricidade melhorada e coeficiente de desempenho aumentado, usos e máquina de refrigeração |
| CN114543379A (zh) | 2015-03-30 | 2022-05-27 | 开利公司 | 低油制冷剂和蒸汽压缩系统 |
| CN105505540A (zh) * | 2016-01-04 | 2016-04-20 | 武汉杰生润滑科技有限公司 | 一种冷冻机油组合物及其应用 |
| JP2017133808A (ja) * | 2016-01-29 | 2017-08-03 | ダイキン工業株式会社 | 冷凍装置 |
| CN115651740A (zh) * | 2016-05-10 | 2023-01-31 | 特灵国际有限公司 | 减少制冷剂溶解度的润滑剂共混物 |
| US10301521B2 (en) | 2016-07-29 | 2019-05-28 | Honeywell International Inc. | Heat transfer methods, systems and compositions |
Family Cites Families (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4046533A (en) | 1972-12-21 | 1977-09-06 | Chevron Research Company | Refrigeration working fluid containing branched chain alkylbenzene lubricant |
| US4302343A (en) | 1979-04-02 | 1981-11-24 | The Dow Chemical Company | Rotary screw compressor lubricants |
| JPS6162596A (ja) | 1984-09-03 | 1986-03-31 | Nippon Oil & Fats Co Ltd | 冷凍機油 |
| US4755316A (en) | 1987-10-23 | 1988-07-05 | Allied-Signal Inc. | Refrigeration lubricants |
| AU638710B2 (en) | 1989-04-25 | 1993-07-08 | Lubrizol Corporation, The | Liquid compositions containing carboxylic esters |
| JP3142321B2 (ja) | 1991-09-03 | 2001-03-07 | 日石三菱株式会社 | 冷凍機油組成物 |
| CA2095921A1 (en) | 1991-09-16 | 1993-03-17 | The Lubrizol Corporation | Oil compositions |
| JPH05125374A (ja) * | 1991-11-07 | 1993-05-21 | Sanyo Electric Co Ltd | 冷凍機油組成物 |
| AU661756B2 (en) * | 1992-02-18 | 1995-08-03 | Idemitsu Kosan Co. Ltd | Lubricant for refrigerating machine employing refrigerant comprising tetrafluoroethane |
| ES2214487T5 (es) | 1994-07-19 | 2009-06-15 | Nippon Mitsubishi Oil Corporation | Composicion de un aceite refrigerante y composicion liquida para refrigerador. |
| CA2155166C (en) * | 1994-08-03 | 2005-04-26 | Katsuya Takigawa | Refrigerator oil composition and fluid composition for refrigerator |
| US6251300B1 (en) * | 1994-08-03 | 2001-06-26 | Nippon Mitsubishi Oil Corporation | Refrigerator oil compositions and fluid compositions for refrigerator |
| JPH09143486A (ja) * | 1995-11-24 | 1997-06-03 | Matsushita Electric Ind Co Ltd | 冷凍機油組成物および冷凍サイクル |
| EP0905219A1 (en) * | 1997-02-13 | 1999-03-31 | Japan Energy Corporation | Lubricating oil for compression refrigerators, working fluid for refrigerators, and method for lubricating refrigeration system |
| JP4885339B2 (ja) * | 1998-05-13 | 2012-02-29 | 出光興産株式会社 | 冷凍機油組成物 |
| GB0105065D0 (en) * | 2001-03-01 | 2001-04-18 | Ici Plc | Lubricant compositions |
-
2002
- 2002-11-13 KR KR1020097011323A patent/KR100983741B1/ko active IP Right Grant
- 2002-11-13 KR KR1020047007565A patent/KR100927754B1/ko active IP Right Grant
- 2002-11-13 WO PCT/US2002/037315 patent/WO2003044137A2/en active Application Filing
- 2002-11-13 EP EP09153988A patent/EP2077314A1/en not_active Withdrawn
- 2002-11-13 EP EP02784527A patent/EP1451273A2/en not_active Withdrawn
- 2002-11-13 CN CNB028255542A patent/CN100455645C/zh not_active Expired - Lifetime
- 2002-11-13 CN CN200710091365A patent/CN100588703C/zh not_active Expired - Lifetime
- 2002-11-13 AU AU2002346463A patent/AU2002346463B2/en not_active Ceased
- 2002-11-13 BR BR0214272-4A patent/BR0214272A/pt not_active Application Discontinuation
- 2002-11-13 US US10/495,887 patent/US7208098B2/en not_active Expired - Lifetime
-
2007
- 2007-04-23 US US11/738,560 patent/US20070187640A1/en not_active Abandoned
Also Published As
| Publication number | Publication date |
|---|---|
| EP2077314A1 (en) | 2009-07-08 |
| BR0214272A (pt) | 2004-12-14 |
| EP1451273A2 (en) | 2004-09-01 |
| CN1708575A (zh) | 2005-12-14 |
| US7208098B2 (en) | 2007-04-24 |
| KR100983741B1 (ko) | 2010-09-24 |
| AU2002346463A1 (en) | 2003-06-10 |
| US20070187640A1 (en) | 2007-08-16 |
| KR100927754B1 (ko) | 2009-11-20 |
| US20050029488A1 (en) | 2005-02-10 |
| AU2002346463B2 (en) | 2007-08-23 |
| KR20090064485A (ko) | 2009-06-18 |
| WO2003044137A3 (en) | 2003-08-07 |
| CN100588703C (zh) | 2010-02-10 |
| CN100455645C (zh) | 2009-01-28 |
| KR20050044519A (ko) | 2005-05-12 |
| WO2003044137A2 (en) | 2003-05-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100588703C (zh) | 含有多元醇酯和烷基苯的混合物的润滑组合物 | |
| TWI601811B (zh) | Refrigerant oil and freezer are used as dynamic fluid composition | |
| JP5214151B2 (ja) | 炭化水素冷媒用冷凍機油及びそれを用いた冷凍機システム | |
| DK2267309T3 (en) | CHILLING UNIT | |
| JP6232371B2 (ja) | 冷凍機用作動流体組成物、冷凍機油及びその製造方法 | |
| TWI599652B (zh) | Freezer oil and freezer are used as dynamic fluid composition | |
| CN102712862B (zh) | 用于制冷系统的润滑剂 | |
| JP3909743B2 (ja) | 冷凍機用潤滑油組成物 | |
| CN109576037A (zh) | 一种冷冻机油、冷冻机油组合物及其应用 | |
| JP2006342357A (ja) | 冷凍機用潤滑油組成物 | |
| KR100349096B1 (ko) | 고온에서작동하는압축기를냉각시키기위한,광유와혼화성이있는폴리올에스테르윤활제 | |
| CN111560285A (zh) | 一种适用于多种冷媒的抗磨冷冻机油及其制备方法 | |
| CN105255567A (zh) | 一种冷冻机油组合物及其应用 | |
| JPH0532985A (ja) | 冷凍機油組成物 | |
| JP2002105471A (ja) | 冷凍機用潤滑油組成物及びそれを用いた冷凍機用作動流体組成物 | |
| AU2007203564B2 (en) | A lubricating composition containing a blend of a polyol ester and an alkylbenzene | |
| JPH05194968A (ja) | 合成潤滑油 | |
| JPH0688086A (ja) | 潤滑油組成物 | |
| WO2002087821A1 (fr) | Procede de decoupe et de broyage de pieces d'un appareil refrigerant |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| EE01 | Entry into force of recordation of patent licensing contract |
Application publication date: 20070829 Assignee: Lubrizol additive (Zhuhai) Co.,Ltd. Assignor: The Lubrizol Corp. Contract record no.: 2014990000201 Denomination of invention: Lubricating composition containing a blend of a polyol ester and an alkylbenzene Granted publication date: 20100210 License type: Common License Record date: 20140411 |
|
| LICC | Enforcement, change and cancellation of record of contracts on the licence for exploitation of a patent or utility model | ||
| C56 | Change in the name or address of the patentee | ||
| CP01 | Change in the name or title of a patent holder |
Address after: Ohio, USA Patentee after: THE LUBRIZOL Corp. Address before: Ohio, USA Patentee before: The Lubrizol Corp. |
|
| EC01 | Cancellation of recordation of patent licensing contract | ||
| EC01 | Cancellation of recordation of patent licensing contract |
Assignee: Lubrizol additive (Zhuhai) Co.,Ltd. Assignor: The Lubrizol Corp. Contract record no.: 2014990000201 Date of cancellation: 20180313 |
|
| EE01 | Entry into force of recordation of patent licensing contract |
Application publication date: 20070829 Assignee: Lubrizol additive (Zhuhai) Co.,Ltd. Assignor: THE LUBRIZOL Corp. Contract record no.: 2018990000081 Denomination of invention: Lubricating composition containing a blend of a polyol ester and an alkylbenzene Granted publication date: 20100210 License type: Common License Record date: 20180410 |
|
| EE01 | Entry into force of recordation of patent licensing contract | ||
| EC01 | Cancellation of recordation of patent licensing contract |
Assignee: Lubrizol additive (Zhuhai) Co.,Ltd. Assignor: THE LUBRIZOL Corp. Contract record no.: 2018990000081 Date of cancellation: 20190322 |
|
| EC01 | Cancellation of recordation of patent licensing contract | ||
| EE01 | Entry into force of recordation of patent licensing contract |
Application publication date: 20070829 Assignee: Lubrizol additive (Zhuhai) Co.,Ltd. Assignor: THE LUBRIZOL Corp. Contract record no.: 2019990000109 Denomination of invention: Lubricating composition containing a blend of a polyol ester and an alkylbenzene Granted publication date: 20100210 License type: Common License Record date: 20190403 |
|
| EE01 | Entry into force of recordation of patent licensing contract | ||
| EC01 | Cancellation of recordation of patent licensing contract | ||
| EC01 | Cancellation of recordation of patent licensing contract |
Assignee: Lubrizol additive (Zhuhai) Co.,Ltd. Assignor: THE LUBRIZOL Corp. Contract record no.: 2019990000109 Date of cancellation: 20200309 |
|
| EE01 | Entry into force of recordation of patent licensing contract |
Application publication date: 20070829 Assignee: Lubrizol additive (Zhuhai) Co.,Ltd. Assignor: THE LUBRIZOL Corp. Contract record no.: X2020990000241 Denomination of invention: Lubricating composition containing a blend of a polyol ester and an alkylbenzene Granted publication date: 20100210 License type: Common License Record date: 20200512 |
|
| EE01 | Entry into force of recordation of patent licensing contract | ||
| EC01 | Cancellation of recordation of patent licensing contract | ||
| EC01 | Cancellation of recordation of patent licensing contract |
Assignee: Lubrizol additive (Zhuhai) Co.,Ltd. Assignor: THE LUBRIZOL Corp. Contract record no.: X2020990000241 Date of cancellation: 20210311 |
|
| EE01 | Entry into force of recordation of patent licensing contract | ||
| EE01 | Entry into force of recordation of patent licensing contract |
Application publication date: 20070829 Assignee: Lubrizol additive (Zhuhai) Co.,Ltd. Assignor: THE LUBRIZOL Corp. Contract record no.: X2021990000246 Denomination of invention: Lubricating composition containing mixture of polyol ester and alkyl benzene Granted publication date: 20100210 License type: Common License Record date: 20210427 |
|
| CX01 | Expiry of patent term | ||
| CX01 | Expiry of patent term |
Granted publication date: 20100210 |
|
| EC01 | Cancellation of recordation of patent licensing contract |
Assignee: Lubrizol additive (Zhuhai) Co.,Ltd. Assignor: THE LUBRIZOL Corp. Contract record no.: X2021990000246 Date of cancellation: 20230808 |
|
| EC01 | Cancellation of recordation of patent licensing contract |