CN115491246B - Refrigerator oil, working fluid composition and application - Google Patents
Refrigerator oil, working fluid composition and application Download PDFInfo
- Publication number
- CN115491246B CN115491246B CN202211130038.1A CN202211130038A CN115491246B CN 115491246 B CN115491246 B CN 115491246B CN 202211130038 A CN202211130038 A CN 202211130038A CN 115491246 B CN115491246 B CN 115491246B
- Authority
- CN
- China
- Prior art keywords
- refrigerator oil
- oil
- acid
- refrigerator
- refrigerating machine
- 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.)
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- 239000000203 mixture Substances 0.000 title claims abstract description 24
- 239000012530 fluid Substances 0.000 title claims abstract description 10
- 239000003921 oil Substances 0.000 claims abstract description 84
- 239000002253 acid Substances 0.000 claims abstract description 51
- 239000010721 machine oil Substances 0.000 claims abstract description 32
- -1 phosphorothioate ester Chemical class 0.000 claims abstract description 23
- 239000002199 base oil Substances 0.000 claims abstract description 11
- 238000004378 air conditioning Methods 0.000 claims abstract description 7
- 239000003507 refrigerant Substances 0.000 claims description 27
- 239000003963 antioxidant agent Substances 0.000 claims description 25
- OSPSWZSRKYCQPF-UHFFFAOYSA-N dibutoxy(oxo)phosphanium Chemical compound CCCCO[P+](=O)OCCCC OSPSWZSRKYCQPF-UHFFFAOYSA-N 0.000 claims description 25
- 230000003078 antioxidant effect Effects 0.000 claims description 19
- IKXFIBBKEARMLL-UHFFFAOYSA-N triphenoxy(sulfanylidene)-$l^{5}-phosphane Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=S)OC1=CC=CC=C1 IKXFIBBKEARMLL-UHFFFAOYSA-N 0.000 claims description 14
- 150000002989 phenols Chemical class 0.000 claims description 11
- 239000002516 radical scavenger Substances 0.000 claims description 9
- 229920005862 polyol Polymers 0.000 claims description 8
- 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 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 7
- DKCPKDPYUFEZCP-UHFFFAOYSA-N 2,6-di-tert-butylphenol Chemical compound CC(C)(C)C1=CC=CC(C(C)(C)C)=C1O DKCPKDPYUFEZCP-UHFFFAOYSA-N 0.000 claims description 6
- 239000004593 Epoxy Substances 0.000 claims description 6
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 6
- 229930195729 fatty acid Natural products 0.000 claims description 6
- 239000000194 fatty acid Substances 0.000 claims description 6
- 150000004665 fatty acids Chemical class 0.000 claims description 6
- 239000006078 metal deactivator Substances 0.000 claims description 6
- IUHZYJKQGIPVFR-UHFFFAOYSA-N C=CC(C)(C)C1=CC(=CC(=C1O)C(C)(C)C)SC1=CC(=C(C(=C1)C(C)(C)C)O)C(C)(C)C Chemical compound C=CC(C)(C)C1=CC(=CC(=C1O)C(C)(C)C)SC1=CC(=C(C(=C1)C(C)(C)C)O)C(C)(C)C IUHZYJKQGIPVFR-UHFFFAOYSA-N 0.000 claims description 4
- 239000002518 antifoaming agent Substances 0.000 claims description 4
- 150000003077 polyols Chemical class 0.000 claims description 3
- 150000008301 phosphite esters Chemical class 0.000 abstract description 26
- RYYWUUFWQRZTIU-UHFFFAOYSA-K thiophosphate Chemical compound [O-]P([O-])([O-])=S RYYWUUFWQRZTIU-UHFFFAOYSA-K 0.000 abstract description 19
- 230000007774 longterm Effects 0.000 abstract description 12
- 230000002195 synergetic effect Effects 0.000 abstract description 11
- 238000005299 abrasion Methods 0.000 abstract description 7
- 238000005057 refrigeration Methods 0.000 abstract description 5
- 238000012360 testing method Methods 0.000 description 48
- 230000000052 comparative effect Effects 0.000 description 34
- 230000003647 oxidation Effects 0.000 description 16
- 238000007254 oxidation reaction Methods 0.000 description 16
- 239000000654 additive Substances 0.000 description 14
- 230000000694 effects Effects 0.000 description 11
- 239000000047 product Substances 0.000 description 11
- 230000000996 additive effect Effects 0.000 description 10
- 150000001412 amines Chemical class 0.000 description 6
- 230000002378 acidificating effect Effects 0.000 description 5
- 230000006698 induction Effects 0.000 description 5
- 230000001050 lubricating effect Effects 0.000 description 5
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 5
- 125000000217 alkyl group Chemical group 0.000 description 4
- 230000001965 increasing effect Effects 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 3
- 239000012964 benzotriazole Substances 0.000 description 3
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 description 3
- 230000003301 hydrolyzing effect Effects 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- VLLMWSRANPNYQX-UHFFFAOYSA-N thiadiazole Chemical compound C1=CSN=N1.C1=CSN=N1 VLLMWSRANPNYQX-UHFFFAOYSA-N 0.000 description 3
- NKBWMBRPILTCRD-UHFFFAOYSA-N 2-Methylheptanoic acid Chemical compound CCCCCC(C)C(O)=O NKBWMBRPILTCRD-UHFFFAOYSA-N 0.000 description 2
- YSEQNZOXHCKLOG-UHFFFAOYSA-N 2-methyl-octanoic acid Chemical compound CCCCCCC(C)C(O)=O YSEQNZOXHCKLOG-UHFFFAOYSA-N 0.000 description 2
- WLAMNBDJUVNPJU-UHFFFAOYSA-N 2-methylbutyric acid Chemical compound CCC(C)C(O)=O WLAMNBDJUVNPJU-UHFFFAOYSA-N 0.000 description 2
- CMGDVUCDZOBDNL-UHFFFAOYSA-N 4-methyl-2h-benzotriazole Chemical compound CC1=CC=CC2=NNN=C12 CMGDVUCDZOBDNL-UHFFFAOYSA-N 0.000 description 2
- OJTHHBCWUMTZEY-UHFFFAOYSA-N 5-methyl-heptanoic acid Chemical compound CCC(C)CCCC(O)=O OJTHHBCWUMTZEY-UHFFFAOYSA-N 0.000 description 2
- MHPUGCYGQWGLJL-UHFFFAOYSA-N 5-methyl-hexanoic acid Chemical compound CC(C)CCCC(O)=O MHPUGCYGQWGLJL-UHFFFAOYSA-N 0.000 description 2
- GPOPHQSTNHUENT-UHFFFAOYSA-N 6-Methyl caprylic acid Chemical compound CCC(C)CCCCC(O)=O GPOPHQSTNHUENT-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- QAPVYZRWKDXNDK-UHFFFAOYSA-N P,P-Dioctyldiphenylamine Chemical compound C1=CC(CCCCCCCC)=CC=C1NC1=CC=C(CCCCCCCC)C=C1 QAPVYZRWKDXNDK-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 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 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 150000001565 benzotriazoles Chemical class 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- GWYFCOCPABKNJV-UHFFFAOYSA-N isovaleric acid Chemical compound CC(C)CC(O)=O GWYFCOCPABKNJV-UHFFFAOYSA-N 0.000 description 2
- FBUKVWPVBMHYJY-UHFFFAOYSA-N nonanoic acid Chemical compound CCCCCCCCC(O)=O FBUKVWPVBMHYJY-UHFFFAOYSA-N 0.000 description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 2
- QQWAKSKPSOFJFF-UHFFFAOYSA-N oxiran-2-ylmethyl 2,2-dimethyloctanoate Chemical compound CCCCCCC(C)(C)C(=O)OCC1CO1 QQWAKSKPSOFJFF-UHFFFAOYSA-N 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- 239000002530 phenolic antioxidant Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 150000004867 thiadiazoles Chemical class 0.000 description 2
- UAXOELSVPTZZQG-UHFFFAOYSA-N tiglic acid Natural products CC(C)=C(C)C(O)=O UAXOELSVPTZZQG-UHFFFAOYSA-N 0.000 description 2
- YKELPEGGKIQKND-UHFFFAOYSA-N tri(nonoxy)-sulfanylidene-$l^{5}-phosphane Chemical compound CCCCCCCCCOP(=S)(OCCCCCCCCC)OCCCCCCCCC YKELPEGGKIQKND-UHFFFAOYSA-N 0.000 description 2
- AWESXHJYBKGOCI-UHFFFAOYSA-N tris[2-(2-methylpropyl)phenoxy]-sulfanylidene-$l^{5}-phosphane Chemical compound CC(C)CC1=CC=CC=C1OP(=S)(OC=1C(=CC=CC=1)CC(C)C)OC1=CC=CC=C1CC(C)C AWESXHJYBKGOCI-UHFFFAOYSA-N 0.000 description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- OBETXYAYXDNJHR-SSDOTTSWSA-M (2r)-2-ethylhexanoate Chemical compound CCCC[C@@H](CC)C([O-])=O OBETXYAYXDNJHR-SSDOTTSWSA-M 0.000 description 1
- 239000001706 (4R)-4-methyloctanoic acid Substances 0.000 description 1
- BIGYLAKFCGVRAN-UHFFFAOYSA-N 1,3,4-thiadiazolidine-2,5-dithione Chemical compound S=C1NNC(=S)S1 BIGYLAKFCGVRAN-UHFFFAOYSA-N 0.000 description 1
- RMSGQZDGSZOJMU-UHFFFAOYSA-N 1-butyl-2-phenylbenzene Chemical group CCCCC1=CC=CC=C1C1=CC=CC=C1 RMSGQZDGSZOJMU-UHFFFAOYSA-N 0.000 description 1
- 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 1
- KVHVVWNXJWZHGB-UHFFFAOYSA-N 2-ethyl-3-methylhexanoic acid Chemical compound CCCC(C)C(CC)C(O)=O KVHVVWNXJWZHGB-UHFFFAOYSA-N 0.000 description 1
- YNEGVNKIKLLHIO-UHFFFAOYSA-N 2-ethyl-4-methylhexanoic acid Chemical compound CCC(C)CC(CC)C(O)=O YNEGVNKIKLLHIO-UHFFFAOYSA-N 0.000 description 1
- MAQIPNRKAZZHBJ-UHFFFAOYSA-N 2-ethyl-5-methylhexanoic acid Chemical compound CCC(C(O)=O)CCC(C)C MAQIPNRKAZZHBJ-UHFFFAOYSA-N 0.000 description 1
- DZPKANIFTIMQQY-UHFFFAOYSA-N 3,4,5-trimethylhexanoic acid Chemical compound CC(C)C(C)C(C)CC(O)=O DZPKANIFTIMQQY-UHFFFAOYSA-N 0.000 description 1
- DVESMWJFKVAFSP-UHFFFAOYSA-N 3-Methyl-heptanoic acid Chemical compound CCCCC(C)CC(O)=O DVESMWJFKVAFSP-UHFFFAOYSA-N 0.000 description 1
- MCLMZMISZCYBBG-UHFFFAOYSA-N 3-ethylheptanoic acid Chemical compound CCCCC(CC)CC(O)=O MCLMZMISZCYBBG-UHFFFAOYSA-N 0.000 description 1
- UWWDUVVCVCAPNU-UHFFFAOYSA-N 3-ethylhexanoic acid Chemical compound CCCC(CC)CC(O)=O UWWDUVVCVCAPNU-UHFFFAOYSA-N 0.000 description 1
- YKSWLQPMYFCNBG-UHFFFAOYSA-N 3-methyl-octanoic acid Chemical compound CCCCCC(C)CC(O)=O YKSWLQPMYFCNBG-UHFFFAOYSA-N 0.000 description 1
- KJYXVWHRKCNYKU-UHFFFAOYSA-N 4-ethyl-hexanoic acid Chemical compound CCC(CC)CCC(O)=O KJYXVWHRKCNYKU-UHFFFAOYSA-N 0.000 description 1
- RCVXVULZIOSNEI-UHFFFAOYSA-N 4-ethylheptanoic acid Chemical compound CCCC(CC)CCC(O)=O RCVXVULZIOSNEI-UHFFFAOYSA-N 0.000 description 1
- LEGGANXCVQPIAI-UHFFFAOYSA-N 4-methyl-octanoic acid Chemical compound CCCCC(C)CCC(O)=O LEGGANXCVQPIAI-UHFFFAOYSA-N 0.000 description 1
- LXHFVSWWDNNDPW-UHFFFAOYSA-N 4-methylheptanoic acid Chemical compound CCCC(C)CCC(O)=O LXHFVSWWDNNDPW-UHFFFAOYSA-N 0.000 description 1
- GTKYBNNWJGLBNE-UHFFFAOYSA-N 5-methyl-octanoic acid Chemical compound CCCC(C)CCCC(O)=O GTKYBNNWJGLBNE-UHFFFAOYSA-N 0.000 description 1
- XZOYHFBNQHPJRQ-UHFFFAOYSA-N 7-methyloctanoic acid Chemical compound CC(C)CCCCCC(O)=O XZOYHFBNQHPJRQ-UHFFFAOYSA-N 0.000 description 1
- 229910001018 Cast iron Inorganic materials 0.000 description 1
- 241000208818 Helianthus Species 0.000 description 1
- 235000003222 Helianthus annuus Nutrition 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- XIHHEICNLHRJJU-UHFFFAOYSA-N [5-(2-ethylhexyl)-4-methylbenzotriazol-1-yl]methanamine Chemical compound CCCCC(CC)CC1=CC=C2N(CN)N=NC2=C1C XIHHEICNLHRJJU-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- YXIWHUQXZSMYRE-UHFFFAOYSA-N benzothiazolyl mercaptan Natural products C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- AMTWCFIAVKBGOD-UHFFFAOYSA-N dioxosilane;methoxy-dimethyl-trimethylsilyloxysilane Chemical compound O=[Si]=O.CO[Si](C)(C)O[Si](C)(C)C AMTWCFIAVKBGOD-UHFFFAOYSA-N 0.000 description 1
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical class C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000010696 ester oil Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 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
- 230000006872 improvement Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- VAKIVKMUBMZANL-UHFFFAOYSA-N iron phosphide Chemical compound P.[Fe].[Fe].[Fe] VAKIVKMUBMZANL-UHFFFAOYSA-N 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- XRQKARZTFMEBBY-UHFFFAOYSA-N oxiran-2-ylmethyl benzoate Chemical compound C=1C=CC=CC=1C(=O)OCC1CO1 XRQKARZTFMEBBY-UHFFFAOYSA-N 0.000 description 1
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 125000000864 peroxy group Chemical group O(O*)* 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 229940083037 simethicone Drugs 0.000 description 1
- VLDHWMAJBNWALQ-UHFFFAOYSA-M sodium;1,3-benzothiazol-3-ide-2-thione Chemical compound [Na+].C1=CC=C2SC([S-])=NC2=C1 VLDHWMAJBNWALQ-UHFFFAOYSA-M 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- DYWSVUBJGFTOQC-UHFFFAOYSA-N xi-2-Ethylheptanoic acid Chemical compound CCCCCC(CC)C(O)=O DYWSVUBJGFTOQC-UHFFFAOYSA-N 0.000 description 1
- 125000005023 xylyl group Chemical group 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
- 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
- C10M169/044—Mixtures of base-materials and additives the additives being a mixture of non-macromolecular and macromolecular 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
- C10M2207/02—Hydroxy compounds
- C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
- C10M2207/026—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings with tertiary alkyl groups
-
- 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
- C10M2207/04—Ethers; Acetals; Ortho-esters; Ortho-carbonates
- C10M2207/042—Epoxides
-
- 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
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
- C10M2215/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
- C10M2215/064—Di- and triaryl amines
-
- 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
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/22—Heterocyclic nitrogen compounds
- C10M2215/223—Five-membered rings containing nitrogen and carbon only
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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
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
- C10M2219/082—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
- C10M2219/087—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Derivatives thereof, e.g. sulfurised phenols
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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
- C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
- C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
- C10M2223/04—Phosphate esters
- C10M2223/047—Thioderivatives not containing metallic elements
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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
- C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
- C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
- C10M2223/049—Phosphite
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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
- C10M2229/00—Organic macromolecular compounds containing atoms of elements not provided for in groups C10M2205/00, C10M2209/00, C10M2213/00, C10M2217/00, C10M2221/00 or C10M2225/00 as ingredients in lubricant compositions
- C10M2229/04—Siloxanes with specific structure
- C10M2229/041—Siloxanes with specific structure containing aliphatic substituents
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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
- C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
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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
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/30—Refrigerators lubricants or compressors lubricants
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- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
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- Chemical & Material Sciences (AREA)
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- Organic Chemistry (AREA)
- Lubricants (AREA)
Abstract
The application relates to the technical field of refrigeration working media, in particular to refrigerating machine oil, a working fluid composition containing the refrigerating machine oil and application of the refrigerating machine oil. The refrigerator oil comprises base oil, acid phosphite ester and phosphorothioate, wherein the mass content of the acid phosphite ester in the refrigerator oil is 0.05-0.4 wt%, and the molar ratio of the acid phosphite ester to the phosphorothioate is 1:10-1:1. The refrigerator oil provided by the application realizes high-level stability and friction and abrasion resistance through the synergistic effect between the acid phosphite ester and the phosphorothioate ester, thereby ensuring long-term stable operation of an air conditioning system.
Description
Technical Field
The application relates to the technical field of refrigeration working media, in particular to refrigerating machine oil, a working fluid composition containing the refrigerating machine oil and application of the refrigerating machine oil.
Background
In order to cope with climate change, international society has established a series of policy regulations to advance the replacement work of refrigerants of various countries to cope with global warming by enhancing the management of products having high Global Warming Potential (GWP). According to the requirements of the montreal protocol, the kucali amendment, various countries will gradually cut down the use of refrigerants with high GWP values, including part of the HFC (hydrofluorocarbon) refrigerants currently in use, such as R404A, R a, etc. Accordingly, HFC refrigerants having a low GWP value, novel substitute refrigerants HFO (hydrofluoroolefins) and mixed refrigerants thereof are attracting attention at present.
The inventors of the present application found that at least the following problems exist in the HFC refrigerants having a low GWP value, the novel alternative refrigerants HFO and the mixed refrigerants thereof for the refrigerating machine oil which is currently used in common use:
1) HFC refrigerants such as R32 have higher pressure in the refrigerant than other refrigerants, which puts higher demands on the antiwear properties of the refrigerator oil composition used in the refrigerator.
2) The HFO refrigerant has a larger influence on the stability of the refrigerating machine oil, and has higher requirements on the chemical stability of the refrigerating machine oil.
3) The existing ester oil has lower dissolving viscosity in HFO refrigerant and has higher requirement on the antiwear performance of the refrigerating machine oil.
In addition, as the speed and efficiency of the refrigeration compressor are increased, the performance of the refrigerating machine oil is also increasingly demanded. Improving the antiwear properties and stability of a refrigerator oil by improving the additives of the refrigerator oil is a relatively cost effective option.
However, the related art, although improving the antiwear performance and stability of the additives, is still not fully satisfactory for the lubricity and stability of the current air conditioning systems.
Disclosure of Invention
In order to solve the technical problems, namely, how to realize the lubricity and the stability of the refrigerating machine oil at a high level, the application provides the refrigerating machine oil, the working fluid composition and the application of the refrigerating machine oil.
In order to achieve the above object, according to a first aspect of the present application, there is provided a refrigerator oil.
The refrigerator oil provided by the embodiment of the application comprises base oil, acid phosphite ester and phosphorothioate, wherein the mass content of the acid phosphite ester in the refrigerator oil is 0.05-0.4 wt%, and the molar ratio of the acid phosphite ester to the phosphorothioate is 1:10-1:1.
Further, the structure of the acid phosphite ester is shown as a formula (I),
wherein R is 1 、R 2 Respectively and independently replaceTable C 1 ～C 10 Is a hydrocarbon group of (a).
Further, the phosphorothioate is at least one selected from the group consisting of triphenyl phosphorothioate, tributylyl phosphorothioate, trinonyl phosphorothioate, tri (toluene) phosphorothioate, and tri (isobutylphenyl) phosphorothioate.
Further, the refrigerator oil further comprises an antioxidant, and the antioxidant is a phenolic compound.
Further, the phenol compound is at least one selected from the group consisting of 2, 6-di-t-butyl-p-cresol, 2, 6-di-t-butylphenol, 4 '-methylenebis (2, 6-di-t-butylphenol), and methylene4, 4' -thiobis- (2, 6-di-t-butylphenol).
Further, the mass content of the phenolic compound in the refrigerator oil is 0.1-1 wt%.
Further, the refrigerator oil further comprises an acid scavenger, and the acid scavenger is a glycidyl ester type epoxy compound.
Further, the mass content of the glycidyl ester type epoxy compound in the refrigerator oil is 0.5wt% to 1.5wt%.
Further, the base oil is a polyol ester formed from a polyol and a fatty acid.
Further, the refrigerator oil further includes at least one of a metal deactivator and an anti-foaming agent.
In order to achieve the above object, according to a second aspect of the present application, there is also provided a working fluid composition.
A working fluid composition according to an embodiment of the present application comprises a refrigerator oil and a refrigerant provided in accordance with the first aspect of the present application.
In order to achieve the above object, according to a third aspect of the present application, there is also provided an application of the refrigerating machine oil provided in the first aspect in an air conditioning system using HFC refrigerant or HFC/HFO mixed refrigerant.
The refrigerator oil provided by the application realizes high-level stability and friction and abrasion resistance through the synergistic effect between the acid phosphite ester and the phosphorothioate ester, thereby ensuring long-term stable operation of an air conditioning system.
Drawings
FIG. 1 is a photograph of pump body parts after a long-term durability test of a compressor 1000 h; wherein figure (a) is a photograph of pump body parts after the oil product of example 1 is subjected to a long-term durability test of the compressor for 1000 hours; fig. b is a photograph of the pump body parts after the oil product of comparative example 1 was subjected to a long-term durability test of the compressor 1000 h.
Detailed Description
Hereinafter, preferred embodiments of the present application will be described in detail.
The refrigerator oil provided by the embodiment of the application comprises base oil, acid phosphite ester and phosphorothioate, wherein the mass content of the acid phosphite ester in the refrigerator oil is 0.05-0.4 wt%, and the molar ratio of the acid phosphite ester to the phosphorothioate is 1:10-1:1.
The acidic phosphite ester has strong adsorption capacity on the metal surface and higher reactivity, and the extreme pressure property and the antiwear property of the acidic phosphite ester are far superior to those of common antiwear agents in refrigerating machine oil, such as tricresyl phosphate. The phosphorothioate has proper antiwear performance, good antiwear durability, and can ensure that the refrigerating machine oil keeps good antiwear performance for a long time by being matched with phosphite ester; in addition, the sulfur element in the phosphorothioate contributes to the strength and toughness of the resulting lubricating protective film. The refrigerator oil containing the acid phosphite ester and the phosphorothioate can generate a lubrication protective film on the metal friction surface, has excellent antiwear performance on the premise of not affecting the stability of oil products, and can maintain the antiwear performance for a long time, thereby ensuring the long-term stable and efficient operation of the refrigerating air conditioner.
Specifically, the structure of the acid phosphite ester in the refrigerator oil is shown as a formula (I),
wherein R is 1 、R 2 Respectively and independently represent C 1 ～C 10 Is a hydrocarbon group of (a). Alternatively, the hydrocarbyl group may be an alkyl, aryl or arylalkyl group. The alkyl groups include, but are not limited to, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, and sunflower groups. The aryl groups include, but are not limited to, phenyl. The alkylaryl groups include, but are not limited to, tolyl, xylyl, ethylphenyl, propylphenyl, butylphenyl. The alkyl group may be linear or branched. The substitution position of the above alkyl group on the aryl group is also arbitrary.
As an additive for refrigerator oil, the acid phosphite ester contains phosphorus element, and can generate an organic phosphate film or an inorganic iron phosphide film on the friction surface, thereby providing good friction and wear resistance. Compared with other phosphate additives, the acidic phosphite has strong adsorption capacity on the metal surface, higher reaction activity and more excellent extreme pressure property and antiwear property.
From the purpose of improving the lubricating property and stability of the refrigerating machine oil, the content of the acid phosphite ester in the refrigerating machine oil is 0.05-0.4 wt%, and the lubricating property and stability of the refrigerating machine oil can be further improved within the range. If the addition amount is less than 0.05wt%, the lubricating property of the refrigerator oil is not greatly improved; when the addition amount is more than 0.4wt%, the antiwear performance commensurate with the addition amount thereof cannot be obtained, and an excessively high content of the acid phosphite may become a cause of deterioration in the stability of the refrigerator oil.
In the refrigerator oil, the phosphorothioate may be at least one selected from triphenyl phosphorothioate, tributylyl phosphorothioate, trinonyl phosphorothioate, tris (toluene) phosphorothioate, tris (isobutylphenyl) phosphorothioate. As an additive of the refrigerator oil, the phosphorothioate contains sulfur and phosphorus elements, and has proper antiwear performance and good antiwear durability. The phosphorothioate and the acid phosphite ester are matched with each other to ensure that the refrigerating machine oil keeps good wear resistance for a long time. In addition, the sulfur element in the phosphorothioate contributes to the strength and toughness of the resulting lubricating protective film.
In order to exert the synergistic effect of the acid phosphate and the phosphorothioate, the friction and wear performance of the refrigerator oil is further improved, and the molar ratio of the acid phosphite to the phosphorothioate is 1/10-1:1. In the above range, the acid phosphite ester and the phosphorothioate ester can play a good synergistic effect, and the antiwear performance of the refrigerating machine oil is further improved. If the molar ratio is less than 1:10 or greater than 1:1, the acid phosphite and the phosphorothioate may not or may not be synergistic.
The refrigerator oil also comprises an antioxidant, and the antioxidant is selected as a phenolic compound. Examples of the phenolic antioxidant include: 2, 6-di-tert-butyl-p-cresol, 2, 6-di-tert-butylphenol, 4 '-methylenebis (2, 6-di-tert-butylphenol), methylene4, 4' -thiobis- (2, 6-di-tert-butylphenol), and the like.
As a phenol antioxidant, the oxidation induction period of the refrigerator oil can be effectively prolonged, and the phenol antioxidant has good synergistic effect with acid phosphite ester. Besides good extreme pressure antiwear performance, the acid phosphite ester has good synergistic effect with phenolic antioxidants, and the acid phosphite ester can decompose hydrogen peroxide, peroxy free radicals and alkoxy free radicals formed in the oxidation process of base oil, so that the acid phosphite ester has good synergistic effect with the antioxidants. The content of the phenolic compound in the refrigerator oil composition of the present application is 0.1wt% to 1wt% for the purpose of improving the antioxidant performance of the refrigerator oil. When the content is less than 0.1%, the effect of improving the antioxidant performance by the phenolic compound-based antioxidant may become insufficient; when it exceeds 1%, although the antioxidant performance is further improved, it is excessive in an air conditioning system without oxygen or micro-oxygen, which may be disadvantageous in terms of economy.
The refrigerator oil may further include an acid scavenger, and the acid scavenger is preferably a glycidyl ester type epoxy compound. The glycidyl ester type epoxy compound may be selected from glycidyl neodecanoate, glycidyl benzoate, glycidyl acrylate, and the like. As an acid scavenger for a refrigerator oil, free acid in the refrigerator oil can be scavenged, thereby preventing deterioration of the refrigerator oil and improving the stability of the refrigerator oil. In the refrigerator oil of the present application, the acid scavenger is particularly important in the refrigerator oil because the acid phosphite ester has high activity, and may adversely affect the stability of the refrigerator oil under high-temperature, moisture-containing environments. The content of the acid scavenger in the refrigerating machine oil of the present application is 0.5wt% to 1.5wt% from the viewpoint of improving the stability of the composition. When less than 0.5%, the acid capturing performance provided may become insufficient; when the content exceeds 1.5%, the acid trapping performance commensurate with the amount added cannot be obtained, and the stability of the refrigerator oil is not greatly improved.
In the refrigerator oil, the base oil is preferably a polyol ester formed from a polyol and a fatty acid. As the polyol ester, esters of pentaerythritol or dipentaerythritol with a linear or branched fatty acid having 5 to 9 carbon atoms are preferably used. The base oil may be a mixture of these esters.
Among them, the fatty acid is preferably composed of a C5, C8, C9 straight chain or branched chain mixed acid, and specifically includes, for example, n-valeric acid, 2-ethylpropionic acid, 2-methylbutyric acid, 3-methylbutyric acid, n-caprylic acid, 2-methylheptanoic acid, 3-methylheptanoic acid, 4-methylheptanoic acid, 5-methylheptanoic acid, 2-ethylhexanoic acid, 3-ethylhexanoic acid, 4-ethylhexanoic acid, 5-ethylhexanoic acid, n-nonanoic acid, 2-methyloctanoic acid, 3-methyloctanoic acid, 4-methyloctanoic acid, 5-methyloctanoic acid, 6-methyloctanoic acid, 7-methyloctanoic acid, 2-ethylheptanoic acid, 3-ethylheptanoic acid, 4-ethylheptanoic acid, 5-methylhexanoic acid, 3,4, 5-trimethylhexanoic acid, 2-ethyl-3-methylhexanoic acid, 2-ethyl-4-methylhexanoic acid, 2-ethyl-5-methylhexanoic acid, and the like.
The refrigerator oil may also include a metal deactivator. Metal deactivators are used to inhibit the catalytic action of metals on oxidation and corrosion. The metal deactivator is one of benzotriazole and benzotriazole derivatives, thiadiazole and thiadiazole derivatives. Specifically, the benzotriazole and the benzotriazole derivative may be methylbenzotriazole, N '-dialkylaminomethylene benzotriazole, N' -bis (2-ethylhexyl) -methyl-1H-benzotriazole-1-methylamine, or the like. Specifically, the thiadiazole and the thiadiazole derivative can be thiadiazole polysulfide, 2, 5-dimercapto-1, 3, 4-thiadiazole, 2-mercaptobenzothiazole, sodium 2-mercaptobenzothiazole and the like. The content of the metal deactivator in the refrigerating machine oil of the present application is preferably 0.01 to 0.05wt% based on the total amount of the composition.
The refrigerator oil provided by the embodiment of the application can be further added with an anti-foaming agent, so that foaming of the oil product in application is inhibited or eliminated. The content of the anti-foaming agent dimethyl silicone oil is preferably 0.0001-0.001 wt%.
The refrigerating machine oil provided by the embodiment of the application is used for forming a working fluid composition with a refrigerant, and is suitable for an air conditioning system. The refrigerant may be an HFC refrigerant and an HFC/HFO mixed refrigerant. I.e., refrigerator oil, may be used for refrigeration applications in refrigeration systems using HFC refrigerants or HFC/HFO mixed refrigerants. The refrigerator oil and working fluid composition according to the embodiment of the present application can be preferably used for an air conditioner having a reciprocating or rotary hermetic compressor, a refrigerator, an open or hermetic vehicle air conditioner, a dehumidifier, a refrigerator, a freezer, a refrigerator, a cooling device for a vending machine, a showcase, and the like, a refrigerator having a centrifugal compressor, and the like.
In order to better understand the solution of the present application, a technical solution of the embodiments of the present application will be clearly and completely described, and it is obvious that the described embodiments are only some embodiments of the present application, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the present application without making any inventive effort, shall fall within the scope of the present application.
Among them, in examples and comparative examples, polyol esters, specifically, esters synthesized from pentaerythritol and two fatty acids were used as base oils, and specific compositions and performance parameters thereof are shown in table 1. The composition ratios of the examples are shown in Table 2, and the composition ratios of the comparative examples are shown in Table 3. In each example and each comparative example, some substances are described as follows:
additive 1: di-n-butyl phosphite; additive 2: triphenyl thiophosphate;
additive 3: tricresyl phosphate; additive 4:2, 6-di-tert-butyl-p-toluene;
additive 5: glycidyl neodecanoate; additive 6: tolyltriazole;
additive 7: a simethicone mother liquor; additive 8: p, p-dioctyl diphenylamine.
Table 1 base oil parameter table
Table 2 composition ratio table of refrigerating machine oil of each example
Table 3 composition ratio table of refrigerator oil of each comparative example
The following tests were performed on the refrigerating machine oils of the respective examples and comparative examples of the present application.
(four-ball friction experiment)
Criteria for test basis: SHT 0189-four-ball method for determining antiwear properties of lubricating oils;
test temperature: 75 ℃;
test time: 1 hour;
load: 392N;
rotational speed: 1200rpm;
each of the examples and comparative examples was tested by the above test, and abrasion resistance was evaluated by the size of the spot diameter of the lower steel ball, and the smaller the spot diameter, the better the abrasion resistance. The results obtained are shown in Table 3.
(four-ball extreme pressure test)
Criteria for test basis: GB/T3142-four-ball method for determination of Lubricant carrying Capacity;
the extreme pressure performance was evaluated by the magnitude of the maximum seizure-free load, and the higher the maximum seizure-free load, the better the extreme pressure performance was, by testing each of the examples and comparative examples using the above test. The results obtained are shown in Table 3.
(Falex Loop test)
Criteria for test basis: ASTM D2714-method for calibration and operation Standard test of Fabricius ring block Friction testing machine and abrasion testing machine;
test materials: steel block and cast iron ring;
test initiation temperature: 25 ℃;
test time: 1 hour;
rotational speed: 1000rpm;
load: 100lbf;
the test results are shown in Table 3.
(hydrolytic stability test)
30g of a refrigerator oil composition having a water content of 1000ppm was charged into a 200mL autoclave, the air in the autoclave was completely removed by a vacuum pump, 17g of R32 refrigerant was sealed therein, and the acid value (mgKOH/g) after maintaining at 150℃for 1 week was measured. The evaluation was carried out with the acid value of comparative example 1 as a reference, A means that the acid value was significantly smaller than that of comparative example 1; b represents an acid value equivalent to that of comparative example 1; c means that the acid value is significantly greater than that of comparative example 1, and the test results are shown in Table 3.
(Oxidation stability test)
Oxidation stability was tested by pressure differential thermal scanning (PDSC).
The test is based on: SH 0719;
oxygen pressure: 3.5Mpa;
test temperature: 190 ℃.
The above test evaluates oxidation stability by testing the oxidation induction period of the sample, and the longer the oxidation induction period, the better the oxidation stability, the test results of the refrigerator oil of each example are shown in table 4, and the test results of the refrigerator oil of each comparative example are shown in table 5.
(compressor 1000h long-term durability test)
The refrigerating machine oils of example 1 and comparative example 1 were subjected to a long-term durability test for the compressor 1000 h. Injecting oil into a compressor, carrying out a long-term durability test of the compressor for 1000 hours, dissecting the compressor after the test is completed, observing the abrasion condition of the pump body part, carrying out analysis and test on the acid value, chromaticity and the like of the oil before and after the test, wherein the physicochemical properties of the oil before and after the test are shown in a table 6, and the photographs of the pump body part after the test are shown in fig. 1, wherein the photograph (a) is the photographs of the pump body part after the long-term durability test of the compressor for 1000 hours is carried out on the oil of the embodiment 1; fig. b is a photograph of the pump body parts after the oil product of comparative example 1 was subjected to a long-term durability test of the compressor 1000 h.
Table 4 test results of refrigerator oils of examples
Table 5 test results of refrigerator oils of comparative examples
TABLE 6 physicochemical Properties of oil before and after durability test
As can be seen from tables 4 and 5, in terms of frictional wear properties, the refrigerating machine oil of examples 1 to 5 of the present application had the respective plaque diameters of 458 μm, 502 μm, 574 μm, 447 μm, 459 μm in the four-ball friction test, and the maximum seizure-free loads of 637N, 588N, 525N, 642N, 639N in the extreme pressure test, which are far superior to 1121 μm and 412N of comparative example 1, respectively, and it can be demonstrated that the refrigerating machine oil composition obtained by the present application has better antiwear properties and extreme pressure properties.
The addition of di-n-butyl phosphite in examples 1-5 was between 0.05% and 0.4%, which showed superior antiwear and extreme pressure properties, and the plaque diameter of comparative example 2 with a small amount of di-n-butyl phosphite was slightly smaller than that of comparative example 1, and the maximum bite-free load was comparable to that of comparative example 1, and it was found that when the addition of di-n-butyl phosphite was less than 0.05%, the effect was not significant although it was a certain effect. Compared with examples 1-5, in comparative example 3, in which excessive di-n-butyl phosphite was added, the diameter of the mill plaque and the maximum bite-free load were not significantly improved, and it was found that when the addition amount of di-n-butyl phosphite was more than 0.4%, the improvement of the abrasion resistance effect was limited by further increasing the addition amount.
Compared with example 1, comparative example 4 without triphenyl phosphorothioate added has significantly reduced plaque diameter and slightly reduced maximum bite load, and has good synergistic effect of di-n-butyl phosphite and triphenyl phosphorothioate. The results of the Falex ring friction experiments further confirm the above conclusions. Specifically, the molar ratio of di-n-butyl phosphite to triphenyl thiophosphate in examples 1-5 is between 1:10 and 1:1, which shows superior antiwear performance and extreme pressure performance, and the effect of di-n-butyl phosphite and triphenyl thiophosphate is obvious. On the basis of example 3, the dosage of di-n-butyl phosphite is kept unchanged, and the dosage of triphenyl thiophosphate is adjusted to obtain comparative example 7, wherein the molar ratio of di-n-butyl phosphite to triphenyl thiophosphate is lower than 1:10, and the antiwear effect of the refrigerator oil is obviously inferior to that of example 3. On the basis of example 4, the dosage of di-n-butyl phosphite is kept unchanged, and the dosage of triphenyl thiophosphate is adjusted to obtain comparative example 8, wherein the molar ratio of di-n-butyl phosphite to triphenyl thiophosphate is higher than 1:1, and the antiwear effect of the refrigerator oil is obviously inferior to that of example 4. It can be seen that the ratio of di-n-butyl phosphite to triphenyl thiophosphate, in amounts ranging from 1:10 to 1:1, shows a significant synergistic effect.
In terms of oxidation stability, the oxidation induction periods of examples 1-4 are 30.94min, 25.42min, 23.71min and 31.22min respectively, and the oxidation stability of the product is improved greatly compared with that of comparative example 1, which is 15.78min, but the oxidation stability of the product without di-n-butyl phosphite is poorer, which means that di-n-butyl phosphite can cooperate with 2, 6-di-tert-butyl-p-cresol, so that the oxidation stability of the oil product is obviously improved, and in addition, technicians use 2, 6-di-tert-butylphenol, 4 '-methylenebis (2, 6-di-tert-butylphenol) and methylene 4,4' -thiobis- (2, 6-di-tert-butylphenol) to replace 2, 6-di-tert-butyl-p-cresol to perform the experiment, so that the equivalent effect is obtained, which means that di-n-butyl phosphite can cooperate with the antioxidant of the phenolic compound.
The technical staff adopts antioxidant p, p-dioctyl diphenylamine except the phenol type compound to replace 2, 6-di-tert-butyl p-toluene to prepare the refrigerator oil, so that the oxidation induction period of the example 5 and the comparative example 9 is 59.24min, which is equivalent to and slightly reduced compared with 60.54min of the comparative example 9, and the presence of di-n-butyl phosphite does not improve the oxidation stability of the refrigerator oil, so that the antioxidant of the di-n-butyl phosphite and the amine type compound does not have obvious synergistic effect. It should be noted that the antioxidant performance of amine antioxidants such as alkylated diphenylamine, especially the antioxidant performance at high temperature, is usually better than phenols, the addition amount of the amine antioxidants is not too high, and although the amine antioxidants have better antioxidant performance, the amine antioxidants have larger toxicity, are easy to discolor oil products, lose the antioxidant effect in the presence of acidic substances and have potential danger of generating precipitates, so that the amine antioxidants are not suitable to be added into refrigerator oil together with the acidic phosphite antioxidants in the application from the viewpoint.
The acid value after the test in example 1 was equivalent to that in comparative example 1, and the acid value after the test in example 2 was lower than that in comparative example 1, indicating that the refrigerator oil composition obtained in the present application was excellent in hydrolytic stability. While comparative example 3 containing an excessive amount of di-n-butyl phosphite, comparative example 5 containing no 2, 6-di-t-butyl p-cresol, and comparative example 6 containing no t-butylphenyl glycidyl ester are all higher in acid value, which means that di-n-butyl phosphite having higher reactivity has a negative effect on the stability of refrigerator oil when the addition amount is too high, the three additives of di-n-butyl phosphite, 2, 6-di-t-butyl p-cresol, t-butylphenyl glycidyl ester are compounded with each other at a proper concentration so that the hydrolytic stability of the refrigerator oil composition can be brought to a good level.
As can be seen from FIGS. 1 and 6, the roller and the sliding vane are not significantly worn after the test in example 1, the viscosity of the oil product is basically unchanged, the acid value is slightly increased, and the color is yellow and transparent; the roller is slightly worn after the test of the comparative example 1, the viscosity of the oil is basically unchanged, the acid value is greatly increased, and the color is brown yellow. It can be seen that example 1 performs better than comparative example 1 in the long-term durability test of the compressor 1000 h.
In this specification, some embodiments are described in a progressive manner, and each embodiment focuses on a difference from other embodiments, and identical and similar parts between the embodiments are enough to refer to each other.
The foregoing is only a specific embodiment of the application to enable those skilled in the art to understand or practice the application. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the application. Thus, the present application is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. The refrigerator oil is characterized by comprising base oil, di-n-butyl phosphite and triphenyl thiophosphate, wherein the mass content of the di-n-butyl phosphite in the refrigerator oil is 0.05-0.4 wt%, and the molar ratio of the di-n-butyl phosphite to the triphenyl thiophosphate is 1:10-1:1.
2. The refrigerator oil of claim 1, further comprising an antioxidant, the antioxidant being a phenolic compound.
3. The refrigerator oil according to claim 2, wherein the phenolic compound is at least one selected from the group consisting of 2, 6-di-t-butyl-p-cresol, 2, 6-di-t-butylphenol, 4 '-methylenebis (2, 6-di-t-butylphenol), and methylene4, 4' -thiobis- (2, 6-di-t-butylphenol).
4. The refrigerator oil according to claim 2, wherein the mass content of the phenolic compound in the refrigerator oil is 0.1wt% to 1wt%.
5. The refrigerator oil of claim 1, further comprising an acid scavenger, the acid scavenger being a glycidyl ester type epoxy compound.
6. The refrigerating machine oil according to claim 5, wherein the mass content of the glycidyl ester type epoxy compound in the refrigerating machine oil is 0.5wt% to 1.5wt%.
7. The refrigerator oil of claim 1, wherein the base oil is a polyol ester formed from a polyol and a fatty acid.
8. The refrigerator oil of claim 1, further comprising at least one of a metal deactivator and an anti-foaming agent.
9. A working fluid composition comprising:
the refrigerator oil of any one of claims 1-8; and
and (3) a refrigerant.
10. Use of a refrigerator oil according to any one of claims 1 to 8 in an air conditioning system using HFC refrigerants or HFC/HFO mixed refrigerants.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1930276A (en) * | 2004-03-04 | 2007-03-14 | 新日本石油株式会社 | Refrigerating machine oil composition |
| JP2016108406A (en) * | 2014-12-04 | 2016-06-20 | 東燃ゼネラル石油株式会社 | Lubricating oil composition |
| CN113166669A (en) * | 2019-02-22 | 2021-07-23 | 引能仕株式会社 | Refrigerator oil and working fluid composition for refrigerator |
| WO2022071486A1 (en) * | 2020-09-30 | 2022-04-07 | 出光興産株式会社 | Refrigeration machine oil composition, refrigerant lubricating oil mixed composition, and refrigerator |
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2022
- 2022-09-16 CN CN202211130038.1A patent/CN115491246B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1930276A (en) * | 2004-03-04 | 2007-03-14 | 新日本石油株式会社 | Refrigerating machine oil composition |
| JP2016108406A (en) * | 2014-12-04 | 2016-06-20 | 東燃ゼネラル石油株式会社 | Lubricating oil composition |
| CN113166669A (en) * | 2019-02-22 | 2021-07-23 | 引能仕株式会社 | Refrigerator oil and working fluid composition for refrigerator |
| WO2022071486A1 (en) * | 2020-09-30 | 2022-04-07 | 出光興産株式会社 | Refrigeration machine oil composition, refrigerant lubricating oil mixed composition, and refrigerator |
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