JP5537999B2 - Refrigerating machine oil for refrigerant R32 - Google Patents
Refrigerating machine oil for refrigerant R32 Download PDFInfo
- Publication number
- JP5537999B2 JP5537999B2 JP2010050207A JP2010050207A JP5537999B2 JP 5537999 B2 JP5537999 B2 JP 5537999B2 JP 2010050207 A JP2010050207 A JP 2010050207A JP 2010050207 A JP2010050207 A JP 2010050207A JP 5537999 B2 JP5537999 B2 JP 5537999B2
- Authority
- JP
- Japan
- Prior art keywords
- acid
- refrigerant
- machine oil
- refrigerating machine
- ester
- 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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- 239000003507 refrigerant Substances 0.000 title claims description 54
- 239000010721 machine oil Substances 0.000 title claims description 42
- 150000002148 esters Chemical class 0.000 claims description 44
- 239000002253 acid Substances 0.000 claims description 34
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 25
- 229930195729 fatty acid Natural products 0.000 claims description 25
- 239000000194 fatty acid Substances 0.000 claims description 25
- 150000004665 fatty acids Chemical class 0.000 claims description 25
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 22
- -1 phenol compound Chemical class 0.000 claims description 20
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 18
- 239000002199 base oil Substances 0.000 claims description 16
- 238000005057 refrigeration Methods 0.000 claims description 15
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 claims description 14
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 14
- 125000004432 carbon atom Chemical group C* 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 10
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 10
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 claims description 10
- 239000001361 adipic acid Substances 0.000 claims description 9
- 235000011037 adipic acid Nutrition 0.000 claims description 9
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 claims description 8
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 claims description 8
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 claims description 8
- 239000004593 Epoxy Substances 0.000 claims description 7
- 150000001718 carbodiimides Chemical class 0.000 claims description 6
- OBETXYAYXDNJHR-SSDOTTSWSA-M (2r)-2-ethylhexanoate Chemical compound CCCC[C@@H](CC)C([O-])=O OBETXYAYXDNJHR-SSDOTTSWSA-M 0.000 claims description 5
- OILUAKBAMVLXGF-UHFFFAOYSA-N 3,5,5-trimethyl-hexanoic acid Chemical compound OC(=O)CC(C)CC(C)(C)C OILUAKBAMVLXGF-UHFFFAOYSA-N 0.000 claims description 5
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 claims description 5
- BODRLKRKPXBDBN-UHFFFAOYSA-N 3,5,5-Trimethyl-1-hexanol Chemical compound OCCC(C)CC(C)(C)C BODRLKRKPXBDBN-UHFFFAOYSA-N 0.000 claims description 4
- 239000002826 coolant Substances 0.000 claims description 4
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- 239000010452 phosphate Substances 0.000 claims description 3
- 239000003921 oil Substances 0.000 description 20
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 239000000654 additive Substances 0.000 description 8
- 238000004821 distillation Methods 0.000 description 8
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 6
- 238000005886 esterification reaction Methods 0.000 description 6
- 229920001515 polyalkylene glycol Polymers 0.000 description 6
- 230000000996 additive effect Effects 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 229920005862 polyol Polymers 0.000 description 5
- 238000010792 warming Methods 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 150000001298 alcohols Chemical class 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- RWRIWBAIICGTTQ-UHFFFAOYSA-N difluoromethane Chemical compound FCF RWRIWBAIICGTTQ-UHFFFAOYSA-N 0.000 description 4
- 238000010292 electrical insulation Methods 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- 150000002989 phenols Chemical class 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 3
- 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 3
- 239000004927 clay Substances 0.000 description 3
- 239000010687 lubricating oil Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 3
- 229920013639 polyalphaolefin Polymers 0.000 description 3
- 229920001289 polyvinyl ether Polymers 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- LVGUZGTVOIAKKC-UHFFFAOYSA-N 1,1,1,2-tetrafluoroethane Chemical compound FCC(F)(F)F LVGUZGTVOIAKKC-UHFFFAOYSA-N 0.000 description 2
- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-heptanol Chemical compound CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 description 2
- RUFPHBVGCFYCNW-UHFFFAOYSA-N 1-naphthylamine Chemical compound C1=CC=C2C(N)=CC=CC2=C1 RUFPHBVGCFYCNW-UHFFFAOYSA-N 0.000 description 2
- OHMHBGPWCHTMQE-UHFFFAOYSA-N 2,2-dichloro-1,1,1-trifluoroethane Chemical compound FC(F)(F)C(Cl)Cl OHMHBGPWCHTMQE-UHFFFAOYSA-N 0.000 description 2
- QWQNFXDYOCUEER-UHFFFAOYSA-N 2,3-ditert-butyl-4-methylphenol Chemical compound CC1=CC=C(O)C(C(C)(C)C)=C1C(C)(C)C QWQNFXDYOCUEER-UHFFFAOYSA-N 0.000 description 2
- BBBUAWSVILPJLL-UHFFFAOYSA-N 2-(2-ethylhexoxymethyl)oxirane Chemical compound CCCCC(CC)COCC1CO1 BBBUAWSVILPJLL-UHFFFAOYSA-N 0.000 description 2
- WXUAQHNMJWJLTG-UHFFFAOYSA-N 2-methylbutanedioic acid Chemical compound OC(=O)C(C)CC(O)=O WXUAQHNMJWJLTG-UHFFFAOYSA-N 0.000 description 2
- XJMMNTGIMDZPMU-UHFFFAOYSA-N 3-methylglutaric acid Chemical compound OC(=O)CC(C)CC(O)=O XJMMNTGIMDZPMU-UHFFFAOYSA-N 0.000 description 2
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- VOPWNXZWBYDODV-UHFFFAOYSA-N Chlorodifluoromethane Chemical compound FC(F)Cl VOPWNXZWBYDODV-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N Propionic acid Chemical compound CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 150000004996 alkyl benzenes Chemical class 0.000 description 2
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 2
- KBPLFHHGFOOTCA-UHFFFAOYSA-N caprylic alcohol Natural products CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- PXBRQCKWGAHEHS-UHFFFAOYSA-N dichlorodifluoromethane Chemical compound FC(F)(Cl)Cl PXBRQCKWGAHEHS-UHFFFAOYSA-N 0.000 description 2
- 235000019404 dichlorodifluoromethane Nutrition 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- MNWFXJYAOYHMED-UHFFFAOYSA-N heptanoic acid Chemical compound CCCCCCC(O)=O MNWFXJYAOYHMED-UHFFFAOYSA-N 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000002480 mineral oil Substances 0.000 description 2
- CMESPBFFDMPSIY-UHFFFAOYSA-N n,n'-diphenylmethanediimine Chemical compound C1=CC=CC=C1N=C=NC1=CC=CC=C1 CMESPBFFDMPSIY-UHFFFAOYSA-N 0.000 description 2
- ZWRUINPWMLAQRD-UHFFFAOYSA-N nonan-1-ol Chemical compound CCCCCCCCCO ZWRUINPWMLAQRD-UHFFFAOYSA-N 0.000 description 2
- FBUKVWPVBMHYJY-UHFFFAOYSA-N nonanoic acid Chemical compound CCCCCCCCC(O)=O FBUKVWPVBMHYJY-UHFFFAOYSA-N 0.000 description 2
- 150000003014 phosphoric acid esters Chemical class 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 125000005480 straight-chain fatty acid group Chemical group 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- CYRMSUTZVYGINF-UHFFFAOYSA-N trichlorofluoromethane Chemical compound FC(Cl)(Cl)Cl CYRMSUTZVYGINF-UHFFFAOYSA-N 0.000 description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- WVUYYXUATWMVIT-UHFFFAOYSA-N 1-bromo-4-ethoxybenzene Chemical compound CCOC1=CC=C(Br)C=C1 WVUYYXUATWMVIT-UHFFFAOYSA-N 0.000 description 1
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- GOHPTLYPQCTZSE-UHFFFAOYSA-N 2,2-dimethylsuccinic acid Chemical compound OC(=O)C(C)(C)CC(O)=O GOHPTLYPQCTZSE-UHFFFAOYSA-N 0.000 description 1
- KLZYRCVPDWTZLH-UHFFFAOYSA-N 2,3-dimethylsuccinic acid Chemical compound OC(=O)C(C)C(C)C(O)=O KLZYRCVPDWTZLH-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- FDYJJKHDNNVUDR-UHFFFAOYSA-N 2-ethyl-2-methylbutanedioic acid Chemical compound CCC(C)(C(O)=O)CC(O)=O FDYJJKHDNNVUDR-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- DUHQIGLHYXLKAE-UHFFFAOYSA-N 3,3-dimethylglutaric acid Chemical compound OC(=O)CC(C)(C)CC(O)=O DUHQIGLHYXLKAE-UHFFFAOYSA-N 0.000 description 1
- GAYWCADKXYCKCG-UHFFFAOYSA-N 5-pyridin-3-yl-1,2-dihydro-1,2,4-triazole-3-thione Chemical compound N1NC(=S)N=C1C1=CC=CN=C1 GAYWCADKXYCKCG-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- UUNBFTCKFYBASS-UHFFFAOYSA-N C(CCCCCCC)C=1C(=C(C=CC1)NC1=CC=CC=C1)CCCCCCCC Chemical compound C(CCCCCCC)C=1C(=C(C=CC1)NC1=CC=CC=C1)CCCCCCCC UUNBFTCKFYBASS-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000004338 Dichlorodifluoromethane Substances 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
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical group CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 125000003354 benzotriazolyl group Chemical class N1N=NC2=C1C=CC=C2* 0.000 description 1
- SYEOWUNSTUDKGM-UHFFFAOYSA-N beta-methyladipic acid Natural products OC(=O)CC(C)CCC(O)=O SYEOWUNSTUDKGM-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 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
- 239000003054 catalyst Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- KYKAJFCTULSVSH-UHFFFAOYSA-N chloro(fluoro)methane Chemical compound F[C]Cl KYKAJFCTULSVSH-UHFFFAOYSA-N 0.000 description 1
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 1
- 229940018557 citraconic acid Drugs 0.000 description 1
- 238000004320 controlled atmosphere Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical group C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- OREAFAJWWJHCOT-UHFFFAOYSA-N dimethylmalonic acid Chemical compound OC(=O)C(C)(C)C(O)=O OREAFAJWWJHCOT-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000010696 ester oil Substances 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- UKFXDFUAPNAMPJ-UHFFFAOYSA-N ethylmalonic acid Chemical compound CCC(C(O)=O)C(O)=O UKFXDFUAPNAMPJ-UHFFFAOYSA-N 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- HNEGQIOMVPPMNR-NSCUHMNNSA-N mesaconic acid Chemical compound OC(=O)C(/C)=C/C(O)=O HNEGQIOMVPPMNR-NSCUHMNNSA-N 0.000 description 1
- 239000006078 metal deactivator Substances 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- HNEGQIOMVPPMNR-UHFFFAOYSA-N methylfumaric acid Natural products OC(=O)C(C)=CC(O)=O HNEGQIOMVPPMNR-UHFFFAOYSA-N 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- AFFLGGQVNFXPEV-UHFFFAOYSA-N n-decene Natural products CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 1
- 235000014593 oils and fats Nutrition 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 150000002898 organic sulfur compounds Chemical class 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000010726 refrigerant oil Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 150000004671 saturated fatty acids Chemical class 0.000 description 1
- 235000003441 saturated fatty acids Nutrition 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 229940029284 trichlorofluoromethane Drugs 0.000 description 1
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 1
Description
本発明は、地球温暖化係数の低いＲ３２（ジフルオロメタン、ＣＨ2Ｆ2）を冷媒として使用する冷凍機油に関するものである。 The present invention relates to a refrigerating machine oil that uses R32 (difluoromethane, CH 2 F 2 ) having a low global warming potential as a refrigerant.
従来、冷凍機、空調機、冷蔵庫等には、冷媒としてフッ素と塩素を構成元素とするフロン、例えばクロロフルオロカーボン（ＣＦＣ）であるＲ‐１１（トリクロロモノフルオロメタン）、Ｒ‐１２（ジクロロジフルオロメタン）、ハイドロクロロフルオロカーボン（ＨＣＦＣ）であるＲ‐２２（モノクロロジフルオロメタン）等のフロンが使用されてきたが、最近のオゾン層破壊問題に関連し、国際的にその生産及び使用が規制され、現在では、塩素を含有しない、例えば、テトラフルオロエタン（Ｒ‐１３４またはＲ‐１３４ａ）や混合冷媒であるＲ４１０Ａ、Ｒ４０７Ｃなどの新しい水素含有フロン冷媒に転換されてきている。しかし、これらのＨＦＣは、オゾン層を破壊しないものの温室効果が大きく、近年問題となっている地球温暖化の観点からは必ずしも優れた冷媒ではない。 Conventionally, in refrigerators, air conditioners, refrigerators, etc., chlorofluorocarbons (CFCs) such as R-11 (trichloromonofluoromethane) and R-12 (dichlorodifluoromethane) containing fluorine and chlorine as refrigerants are used as refrigerants. ), CFCs such as hydrochlorofluorocarbon (HCFC) R-22 (monochlorodifluoromethane) have been used, but related to the recent depletion of the ozone layer, its production and use are regulated internationally. However, it has been converted to new hydrogen-containing chlorofluorocarbon refrigerants that do not contain chlorine, such as tetrafluoroethane (R-134 or R-134a) and mixed refrigerants R410A and R407C. However, although these HFCs do not destroy the ozone layer, they have a large greenhouse effect and are not necessarily excellent refrigerants from the viewpoint of global warming, which has become a problem in recent years.
そこで、Ｒ３２がオゾン層を破壊することなく、地球温暖化への影響も前記の塩素系あるいは非塩素系フッ化炭化水素に比べて非常に低いことから、最近、注目されている。この化合物は冷媒として、上記フロン系冷媒で培われた圧縮機、凝縮器、絞り装置、蒸発器等からなるルームエアコン、産業用冷凍機等の冷却効率の高い冷凍システムに採用することが検討されており、現在、ルームエアコン用冷媒として幅広く使用されているハイドロフルオロカーボン（ＨＦＣ）の混合冷媒であるＲ４１０Ａと比較すると地球温暖化係数は１／３程度であり、効率も良く、エアコンの大掛かりな設計変更も必要なしで経済的に温暖化への影響を大幅に削減できる可能性があります。しかし、わずかな燃焼性があるため、安全に使用するための技術開発と、潤滑剤としてこの冷媒と相溶性のある冷凍機油の選定が課題となっている。 Thus, R32 has recently been attracting attention because it does not destroy the ozone layer and has a much lower impact on global warming than the above-mentioned chlorinated or non-chlorinated fluorinated hydrocarbons. It is considered to use this compound as a refrigerant in refrigeration systems with high cooling efficiency such as room air conditioners and industrial refrigerators composed of compressors, condensers, throttle devices, evaporators, etc., cultivated with the above-mentioned fluorocarbon refrigerants. Compared with R410A, which is a mixed refrigerant of hydrofluorocarbon (HFC), which is currently widely used as a refrigerant for room air conditioners, the global warming potential is about 1/3, high efficiency, and large-scale design of air conditioners There is a possibility that the impact on global warming can be greatly reduced without any changes. However, since there is slight combustibility, technical development for safe use and selection of refrigerating machine oil compatible with this refrigerant as a lubricant are problems.
特許文献１および２には、Ｒ３２（ジフルオロメタン、ＣＨ2Ｆ2）を冷媒として用る冷凍装置、あるいは冷凍サイクル、空気調和機が提示され、冷凍機油として、ポリビニルエーテル、ポリオールエステル、炭酸エステル、アルキルベンゼン、鉱油、または４０℃における動粘度が３２cSt以上のエステル油、エーテル油又はＰＡＧ油等が挙げられている。
しかしながら、冷凍機油に必須の性能である相溶性、溶解性、冷媒混合状態での潤滑性等は、冷媒の種類により異なるので、炭素が一個であり高圧で使用される冷媒Ｒ３２にも、どのような冷凍機油でもそのまま良好に用いることができるとは一概にはいえない。特に、冷媒との相溶性は重要であり、冷凍システム内での油戻りの観点から、相溶しない冷凍機油は使用できない。冷凍サイクルの場合、コンプレッサーから持ち出された油が冷媒と相溶せずに、サイクル内に滞留してコンプレッサーに戻らないと、しゅう動部に供給される潤滑油（冷凍機油）が少なくなり、摩耗さらには焼付きに至り、システムが壊れる原因となる。すなわち、冷媒Ｒ３２に好適な潤滑剤は、冷媒との相溶性を有するとともに、上述したような性能を評価することにより分かるものであるが、未だそれはなされておらず、適切な冷凍機油は提案されていない。
In Patent Documents 1 and 2, a refrigeration apparatus using R32 (difluoromethane, CH 2 F 2 ) as a refrigerant, a refrigeration cycle, or an air conditioner is presented. As refrigeration oil, polyvinyl ether, polyol ester, carbonate ester, Examples include alkylbenzene, mineral oil, ester oil, ether oil or PAG oil having a kinematic viscosity at 40 ° C. of 32 cSt or more.
However, the compatibility, solubility, lubricity in the refrigerant mixed state, etc., which are essential performances for refrigeration oil, vary depending on the type of refrigerant. It cannot be generally said that even a freezer oil can be used satisfactorily as it is. In particular, compatibility with the refrigerant is important, and incompatible refrigerating machine oil cannot be used from the viewpoint of oil return in the refrigeration system. In the case of the refrigeration cycle, if the oil taken out from the compressor is not compatible with the refrigerant and stays in the cycle and does not return to the compressor, the lubricating oil (refrigerant oil) supplied to the sliding part decreases and wear occurs. In addition, seizure occurs, causing the system to break. That is, the lubricant suitable for the refrigerant R32 has compatibility with the refrigerant and can be understood by evaluating the performance as described above, but it has not been done yet, and an appropriate refrigerating machine oil has been proposed. Not.
本発明は、上記問題を解決したもので、冷媒Ｒ３２に対して適度の相溶性、溶解性を有し、潤滑性を損なわない粘度を保持でき、冷媒の充填量を少なくすることができるとともに、優れた安定性や潤滑性等を有する冷凍機油を提供することを課題とするものである。 The present invention solves the above problems, has moderate compatibility and solubility with respect to the refrigerant R32, can maintain a viscosity that does not impair the lubricity, and can reduce the amount of refrigerant charged, An object of the present invention is to provide a refrigerating machine oil having excellent stability and lubricity.
本発明者は、上記課題を解決するために鋭意研究を進めた結果、特定のエステルが、冷媒Ｒ３２に対し程良い相溶性、溶解性を有するとともに、高い安定性、低い吸湿性、良好な潤滑性を有しており、冷媒Ｒ３２用の冷凍機油として優れていることを見出し、本発明に想到した。 As a result of intensive studies to solve the above problems, the present inventor has a specific ester having moderate compatibility and solubility with respect to the refrigerant R32, high stability, low hygroscopicity, and good lubrication. Therefore, the present invention has been found out that it is excellent as a refrigerating machine oil for the refrigerant R32.
上記課題を解決するための手段としての本発明は次のとおりである。
（１）トリメチロールプロパン及び／又はネオペンチルグリコールと炭素数２〜１２の二塩基酸とを反応させたエステル中間体を、さらに炭素数１〜１２の一価アルコール又は炭素数２〜１２の一価脂肪酸でエステル化した酸価が０.１mgKOH/g以下であるエステルを基油とする１００℃における動粘度が２〜３０mm2/sである冷媒Ｒ３２用冷凍機油。
The present invention as means for solving the above problems is as follows.
(1) An ester intermediate obtained by reacting trimethylolpropane and / or neopentyl glycol with a dibasic acid having 2 to 12 carbon atoms is further converted to a monohydric alcohol having 1 to 12 carbon atoms or one having 2 to 12 carbon atoms. A refrigerating machine oil for refrigerant R32 having a kinematic viscosity at 100 ° C. of 2 to 30 mm 2 / s based on an ester esterified with a hydric fatty acid and having an acid value of 0.1 mg KOH / g or less.
（２）二塩基酸がアジピン酸、ピメリン酸、スベリン酸、アゼライン酸又はセバシン酸から選ばれるいずれか１種以上であり、一価アルコールが分岐アルコール、一価脂肪酸が分岐脂肪酸である上記（１）に記載の冷媒Ｒ３２用冷凍機油。
（３）一価アルコールが２‐エチルヘキサノール及び／又は３,５,５‐トリメチルヘキサノール、一価脂肪酸が２‐エチルヘキサン酸及び／又は３,５,５‐トリメチルヘキサン酸である上記（１）又は（２）に記載の冷媒Ｒ３２用冷凍機油。
(2) The dibasic acid is any one or more selected from adipic acid, pimelic acid, suberic acid, azelaic acid or sebacic acid, the monohydric alcohol is a branched alcohol, and the monovalent fatty acid is a branched fatty acid. ) Refrigerating machine oil for refrigerant R32.
(3) The above (1), wherein the monohydric alcohol is 2-ethylhexanol and / or 3,5,5-trimethylhexanol, and the monohydric fatty acid is 2-ethylhexanoic acid and / or 3,5,5-trimethylhexanoic acid Or the refrigerating machine oil for refrigerant | coolant R32 as described in (2).
（４）トリメチロールプロパンの１モルに対して、二塩基酸を１.５モル超、３モル未満で反応させたエステル中間体を、さらに２‐エチルヘキサノール及び／又は３,５,５‐トリメチルヘキサノールでエステル化したエステルを基油とする上記（１）〜（３）のいずれかに記載のＲ３２用冷凍機油。
（５）ヒンダードフェノール化合物、芳香族アミン化合物、エポキシ化合物、カルボジイミド又はリン酸エステルのいずれか１種以上を合わせて、冷凍機油全量基準で０.０５〜５.０重量％添加したことからなる上記（１）〜（４）のいずれかに記載の冷媒Ｒ３２用冷凍機油。
（６）体積抵抗率が１０11Ω・cm以上である上記（１）〜（５）のいずれかに記載の冷媒Ｒ３２用冷凍機油。
(4) An ester intermediate obtained by reacting a dibasic acid with more than 1.5 mol and less than 3 mol with respect to 1 mol of trimethylolpropane is further converted into 2-ethylhexanol and / or 3,5,5-trimethyl. The refrigerating machine oil for R32 according to any one of the above (1) to (3), wherein an ester esterified with hexanol is used as a base oil.
(5) Containing one or more of hindered phenol compounds, aromatic amine compounds, epoxy compounds, carbodiimides or phosphate esters, and adding 0.05 to 5.0% by weight based on the total amount of refrigerating machine oil Refrigerating machine oil for refrigerant | coolant R32 in any one of said (1)-(4).
(6) The refrigerating machine oil for refrigerant R32 according to any one of (1) to (5), wherein the volume resistivity is 10 11 Ω · cm or more.
本発明の冷凍機油は、冷媒Ｒ３２に対し程良い相溶性、溶解性を有するとともに、高い電気絶縁性、低い吸湿性、良好な潤滑性、高い熱酸化安定性を有しているため、冷媒の充填量を少なくすることができ、冷媒Ｒ３２用冷凍機油として総合性能に優れている。 The refrigerating machine oil of the present invention has moderate compatibility and solubility with respect to the refrigerant R32, and also has high electrical insulation, low moisture absorption, good lubricity, and high thermal oxidation stability. The filling amount can be reduced, and the refrigerating machine oil for the refrigerant R32 is excellent in overall performance.
本発明では、ネオペンチルポリオールであるトリメチロールプロパン及び／又はネオペンチルグリコールと炭素数２〜１２の二塩基酸とを反応させたエステル中間体を合成し、さらにこれと一価アルコール又は一価脂肪酸でエステル化したエステルを基油として用いる。
冷媒Ｒ３２は極性が大きいため、従来のＨＦＣ冷媒用として使用されてきたネオペンチルグリコールと一価脂肪酸で合成されたポリオールエステルでは低分子量、つまり低粘度のものでないと相溶しないため、冷凍コンプレッサーに必要な適正粘度では、冷媒Ｒ３２と相溶する冷凍機油を選定することができない。
In the present invention, an ester intermediate obtained by reacting trimethylolpropane and / or neopentyl glycol, which is a neopentyl polyol, and a dibasic acid having 2 to 12 carbon atoms is synthesized, and this is further synthesized with a monohydric alcohol or monovalent fatty acid. The ester esterified with is used as the base oil.
Since the refrigerant R32 has a large polarity, the polyol ester synthesized with neopentyl glycol and monohydric fatty acid, which has been used for conventional HFC refrigerants, is compatible with a low molecular weight, that is, having a low viscosity. A refrigerating machine oil that is compatible with the refrigerant R32 cannot be selected with the necessary appropriate viscosity.
本発明では、二段階のエステル化により、より極性が大きくてＲ３２と相溶しやすくするとともに、冷凍コンプレッサーに必要な粘度を有するエステルとする。すなわち、第一段階のトリメチロールプロパン及び／又はネオペンチルグリコールと二塩基酸とエステル化反応させ、それらの使用モル比を調整して中間体としてカルボキシル基あるいは水酸基が残るものを任意に得、カルボキシル基が残る場合は一価アルコールで、水酸基が残る場合は一価脂肪酸でさらにエステル化して、所望の性能を有するエステルを得る。この場合、ネオペンチルポリオールのうち炭素数が７を超えるものは、炭化水素部分が大きくなりすぎて、これから合成されたエステルは冷媒Ｒ３２との相溶性、溶解性が低い。冷媒Ｒ３２との相溶性を有し、かつ高粘度のエステルを合成できるため、トリメチロールプロパンが特に好ましい。 In the present invention, the esterification with two steps of esterification has a higher polarity and is easily compatible with R32, and has a viscosity necessary for a refrigeration compressor. That is, the first stage trimethylolpropane and / or neopentyl glycol and dibasic acid are esterified, and the molar ratio of these is adjusted to arbitrarily obtain a carboxyl group or hydroxyl group as an intermediate. When the group remains, it is esterified with a monohydric alcohol, and when the hydroxyl group remains, it is further esterified with a monovalent fatty acid to obtain an ester having a desired performance. In this case, the neopentyl polyol having more than 7 carbon atoms has a too large hydrocarbon portion, and the ester synthesized therefrom has low compatibility and solubility with the refrigerant R32. Trimethylolpropane is particularly preferable because it has compatibility with the refrigerant R32 and can synthesize a highly viscous ester.
要するに、トリメチロールプロパンを用いる場合は、先ず、トリメチロールプロパン１モルに対し、二塩基酸を、等モルである１.５モルより過剰又は過少、好ましくは、０.１モル以上、１.５モル未満、或いは１.５モル超、５モル以下を用いてエステル化反応を行う。次いで、二塩基酸が１.５モル未満の場合、残存する水酸基を一価脂肪酸を用いてエステル化させ、残存する一価脂肪酸を常圧あるいは減圧下の蒸留により除去する。また、二塩基酸が１.５モル超の場合は、残存するカルボキシル基を一価アルコールを用いてエステル化させ、残存する一価アルコールを常圧あるいは減圧下の蒸留により除去する。
なお、第一段でトリメチロールプロパンの１モルに対して、二塩基酸を１.５モル超、３モル未満用い、第二段で残存するカルボキシル基を２‐エチルヘキサノール及び／又は３,５,５‐トリメチルヘキサノールでエステル化させると、冷媒Ｒ３２に対する相溶性及び潤滑性に極めて優れたエステルが得られるため、より好ましい。
In short, when trimethylolpropane is used, first, the dibasic acid is more or less than 1.5 mol which is an equimolar amount, preferably 0.1 mol or more, 1.5 mol per mol of trimethylolpropane. The esterification reaction is carried out using less than 1 mol or more than 1.5 mol and 5 mol or less. Next, when the dibasic acid is less than 1.5 mol, the remaining hydroxyl group is esterified using a monovalent fatty acid, and the remaining monovalent fatty acid is removed by distillation under normal pressure or reduced pressure. When the dibasic acid exceeds 1.5 mol, the remaining carboxyl group is esterified with a monohydric alcohol, and the remaining monohydric alcohol is removed by distillation under normal pressure or reduced pressure.
The first stage uses more than 1.5 moles of dibasic acid and less than 3 moles per mole of trimethylolpropane, and the remaining carboxyl group in the second stage is 2-ethylhexanol and / or 3,5. , 5-trimethylhexanol is more preferable because an ester having excellent compatibility with the refrigerant R32 and lubricity can be obtained.
一方、ネオペンチルグリコールを用いる場合は、ネオペンチルグリコール１モルに対し、二塩基酸を、等モルである１モルより、過剰又は過少、好ましくは、０.１モル以上、１モル未満、或いは１モル超、５モル以下を用いてエステル化反応を行う。次いで、二塩基酸が１モル未満の場合、残存する水酸基を一価脂肪酸を用いてエステル化させ、残存する一価脂肪酸を蒸留により除去する。二塩基酸が１モル超の場合は、残存するカルボキシル基を一価アルコールを用いてエステル化させ、残存する一価アルコールを蒸留により除去する。
なお、得られたエステルは、白土吸着などの方法により酸価が０.１mgKOH/g以下となるようにする。
On the other hand, when neopentyl glycol is used, the dibasic acid is used in excess or less than 1 mol which is equimolar to 1 mol of neopentyl glycol, preferably 0.1 mol or more, less than 1 mol, or 1 The esterification reaction is carried out using more than 5 moles and less than 5 moles. Next, when the dibasic acid is less than 1 mol, the remaining hydroxyl group is esterified using a monovalent fatty acid, and the remaining monovalent fatty acid is removed by distillation . When the dibasic acid exceeds 1 mol, the remaining carboxyl group is esterified with a monohydric alcohol, and the remaining monohydric alcohol is removed by distillation.
The obtained ester has an acid value of 0.1 mg KOH / g or less by a method such as adsorption of clay.
炭素数２〜１２の二塩基酸としては、具体的には、シュウ酸、マロン酸、コハク酸、グルタル酸、アジピン酸、ピメリン酸、スバリン酸、アゼライン酸、セバシン酸、ドデカ二酸、メチルマロン酸、エチルマロン酸、ジメチルマロン酸、メチルコハク酸、２,２‐ジメチルコハク酸、２,３‐ジメチルコハク酸、２‐エチル‐２‐メチルコハク酸、２‐メチルグルタル酸、３‐メチルグルタル酸、３,３‐ジメチルグルタル酸、３‐メチルアジピン酸等の飽和脂肪族ジカルボン酸、マレイン酸、フマル酸、イタコン酸、シトラコン酸、メサコン酸等の不飽和脂肪族ジカルボン酸、フタル酸、イソフタル酸、テレフタル酸等の芳香族ジカルボン酸等を用いることができる。
特には、次の構造を有する、
ＨＯＯＣ（ＣＨ2）ｎＣＯＯＨ （ｎは１〜１０の正数）
炭素数３〜１２の直鎖飽和脂肪族ジカルボン酸が好適であり、ｎが４〜８のアジピン酸、ピメリン酸、スベリン酸、アゼライン酸、セバシン酸が極性が比較的大きく、Ｒ３２と相溶性に優れるエステルを合成できるので、特に好ましい。
Specific examples of the dibasic acid having 2 to 12 carbon atoms include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, subvalic acid, azelaic acid, sebacic acid, dodecadic acid, and methylmalon. Acid, ethylmalonic acid, dimethylmalonic acid, methylsuccinic acid, 2,2-dimethylsuccinic acid, 2,3-dimethylsuccinic acid, 2-ethyl-2-methylsuccinic acid, 2-methylglutaric acid, 3-methylglutaric acid, Saturated aliphatic dicarboxylic acids such as 3,3-dimethylglutaric acid and 3-methyladipic acid, unsaturated aliphatic dicarboxylic acids such as maleic acid, fumaric acid, itaconic acid, citraconic acid and mesaconic acid, phthalic acid, isophthalic acid, Aromatic dicarboxylic acids such as terephthalic acid can be used.
In particular, it has the following structure:
HOOC (CH 2) nCOOH (n is a positive number of 1 to 10)
C3-C12 straight-chain saturated aliphatic dicarboxylic acids are preferred, and n is 4-8 adipic acid, pimelic acid, suberic acid, azelaic acid, and sebacic acid are relatively large in polarity and compatible with R32 It is particularly preferable because an excellent ester can be synthesized.
炭素数１〜１２の一価アルコールとしては、直鎖及び分岐鎖の飽和アルコールが好適で、メタノール、エタノール、ｎ‐プロパノール、ｎ‐ブタノール、ｎ‐ペンタノール、ｎ‐ヘプタノール、ｎ‐オクタノール、ｎ‐ノナノール等の直鎖アルコール或いは前記直鎖アルコールの構造異性体である分岐アルコールのいずれも用いることができる。
Ｒ３２とより相溶性に優れるエステルを合成するためには分岐アルコールが好ましく、なかでも２‐エチルヘキサノール、３,５,５‐トリメチルヘキサノールがより好ましい。
As the monohydric alcohol having 1 to 12 carbon atoms, linear and branched saturated alcohols are preferable, and methanol, ethanol, n-propanol, n-butanol, n-pentanol, n-heptanol, n-octanol, n -Linear alcohols such as nonanol or branched alcohols that are structural isomers of the linear alcohols can be used.
In order to synthesize an ester having higher compatibility with R32, a branched alcohol is preferable, and 2-ethylhexanol and 3,5,5-trimethylhexanol are more preferable.
炭素数２〜１２の直鎖の一価脂肪酸としては、直鎖及び分岐鎖の飽和脂肪酸が好適で、酢酸、ｎ‐プロパン酸、ｎ‐ブタン酸、ｎ‐ペンタン酸、ｎ‐ヘプタン酸、ｎ‐オクタン酸、ｎ‐ノナン酸等の直鎖脂肪酸又は前記直鎖脂肪酸の構造異性体である分岐鎖１価脂肪酸のいずれも用いることができる。相溶性、溶解性及び最適の潤滑性を得るためには分岐脂肪酸が好ましく、なかでも２‐エチルヘキサン酸、３,５,５‐トリメチルヘキサン酸またはそれらの混合物を用いることがより好ましい。 As the linear monovalent fatty acid having 2 to 12 carbon atoms, linear and branched saturated fatty acids are preferable, and acetic acid, n-propanoic acid, n-butanoic acid, n-pentanoic acid, n-heptanoic acid, n Either a straight chain fatty acid such as -octanoic acid or n-nonanoic acid or a branched monovalent fatty acid which is a structural isomer of the straight chain fatty acid can be used. In order to obtain compatibility, solubility and optimum lubricity, branched fatty acids are preferred, and among them, 2-ethylhexanoic acid, 3,5,5-trimethylhexanoic acid or a mixture thereof is more preferred.
本発明エステルは、上記特定のネオペンチルポリオールと二塩基酸、さらには特定の一価アルコールあるいは一価脂肪酸との脱水反応によるエステル化反応、あるいは脂肪酸の誘導体である酸無水物、酸クロライド等を経由しての一般的なエステル化反応や各誘導体のエステル交換反応によって得ることができる。 The ester of the present invention comprises the above-mentioned specific neopentyl polyol and dibasic acid, further esterification reaction by dehydration reaction with a specific monohydric alcohol or monohydric fatty acid, or an acid anhydride or acid chloride which is a derivative of fatty acid. It can be obtained by a general esterification reaction via or a transesterification reaction of each derivative.
また、上記方法で得られるエステルは、未反応で残存する酸および水酸基を特に制限するものではないが、カルボキシル基は残存しないことが好ましい。カルボキシル基の残存量が多いと、冷凍機内部に使用されている金属との反応により金属石けんなどを生成し、沈殿するなどの好ましくない現象も起こるため、酸価が０.１mgKOH/g以下のエステルを基油として用い、冷凍機油としての酸価も０.１mgKOH/g以下とする。また、水酸基の残存量が多すぎると、冷凍機油が低温において白濁し、冷凍サイクルのキャピラリー装置を閉塞させる等、好ましくない現象が起こるため、エステル及び冷凍機油の水酸基価をともに１００mgKOH/g以下とすることが好ましく、３０mgKOH/g以下がより好ましい。 Further, the ester obtained by the above method does not particularly limit the unreacted remaining acid and hydroxyl group, but preferably no carboxyl group remains. If the residual amount of carboxyl groups is large, an undesired phenomenon such as the formation and precipitation of metal soap due to the reaction with the metal used in the refrigerator occurs, so the acid value is less than 0.1 mgKOH / g Esters are used as the base oil, and the acid value of the refrigerating machine oil is 0.1 mgKOH / g or less. In addition, if the residual amount of hydroxyl groups is too large, the refrigeration machine oil becomes cloudy at low temperatures, and undesired phenomena such as clogging the capillary device of the refrigeration cycle occur. Therefore, both the hydroxyl values of the ester and the refrigeration machine oil are 100 mgKOH / g or less. Preferably, it is more preferably 30 mgKOH / g or less.
さらに、本発明の冷凍機油は、冷凍機を適正に作動させ、かつ高い効率を確保するため、１００℃における動粘度が２〜３０mm2/sになるようする。この動粘度は、好ましくは、５〜１５mm2/sであり、コンプレッサーの耐摩耗の信頼性を高める適正な粘度としては８〜１２mm2/sがより好ましい。 Furthermore, the refrigerating machine oil of the present invention has a kinematic viscosity at 100 ° C. of 2 to 30 mm 2 / s in order to properly operate the refrigerating machine and ensure high efficiency. This kinematic viscosity is preferably 5 to 15 mm 2 / s, and 8 to 12 mm 2 / s is more preferable as an appropriate viscosity for improving the reliability of the wear resistance of the compressor.
上記エステルを主成分とする本発明の冷凍機油は、冷媒Ｒ３２用の冷凍機油として、低温から高温までの広い領域で、相互に適切な相溶性、溶解性を示してその潤滑性及び熱安定性を大幅に向上させることができる。さらに、代替フロン用冷凍機油として用いられているポリアルキレングリコール（ＰＡＧ）等に較べると、はるかに電気絶縁性が高く、かつ吸湿性も小さい。 The refrigerating machine oil of the present invention having the above ester as a main component is a refrigerating machine oil for refrigerant R32, and exhibits appropriate compatibility and solubility in a wide range from low temperature to high temperature, and its lubricity and thermal stability. Can be greatly improved. Furthermore, compared with polyalkylene glycol (PAG) etc. which are used as refrigerating machine oil for alternative CFCs, the electrical insulation is much higher and the hygroscopicity is also smaller.
なお、本発明に係る冷凍機油には、冷凍機油としての機能を満足する範囲において、他のタイプのエステル、ＰＡＧやポリビニルエーテル（ＰＶＥ）などのエーテルあるいは炭化水素系であるアルキルベンゼンや鉱油等の潤滑油を適宜混合できる。
本発明の冷凍機油には、さらに冷媒と冷凍機油の混合物流体の安定性を高めるため、安定性向上添加剤を添加するとよい。この安定性向上添加剤として、ヒンダードフェノール化合物、芳香族アミン化合物、エポキシ化合物、またはカルボジイミドのうち１種以上を添加するとよく、さらにはエポキシ化合物とカルボジイミドを合わせて添加することがより好ましい。また、耐摩耗剤としてのリン酸エステルの添加も有効であり、これらの添加剤は、冷凍機油全量基準で合計量として０.０５〜５.０重量％添加すれば十分である。
In the refrigerating machine oil according to the present invention, other types of esters, ethers such as PAG and polyvinyl ether (PVE), or hydrocarbon-based alkylbenzenes and mineral oils, etc., can be used as long as the functions of the refrigerating machine oil are satisfied. Oil can be mixed as appropriate.
In order to further improve the stability of the mixture fluid of the refrigerant and the refrigerating machine oil, a stability improving additive may be added to the refrigerating machine oil of the present invention. As the stability improving additive, one or more of hindered phenol compounds, aromatic amine compounds, epoxy compounds, and carbodiimides may be added, and it is more preferable to add the epoxy compound and carbodiimide together. It is also effective to add phosphate esters as antiwear agents, and it is sufficient to add these additives in a total amount of 0.05 to 5.0% by weight based on the total amount of the refrigerating machine oil.
ヒンダードフェノール化合物としては、２,６‐ジ‐ターシャリーブチルフェノール、２,６‐ジ‐ターシャリ‐ブチル‐Ｐ‐クレゾール、４,４‐メチレン‐ビス‐（２,６‐ジ‐ターシャリ‐ブチル‐Ｐ‐クレゾール）などが、芳香族アミン化合物としてはα‐ナフチルアミン、ｐ,ｐ'‐ジ‐オクチル‐ジフェニルアミンなどが、エポキシ化合物としては、グリシジルエーテル基含有化合物、エポキシ化脂肪酸モノエステル類、エポキシ化油脂、エポキシシクロアルキル基含有化合物などが好適である。また、リン酸エステルとしてはトリフェニルフォスフェート、トリクレジルフォスフェートなどが好適である。 Examples of hindered phenol compounds include 2,6-di-tert-butylphenol, 2,6-di-tert-butyl-P-cresol, 4,4-methylene-bis- (2,6-di-tert-butyl- P-cresol), α-naphthylamine, p, p'-di-octyl-diphenylamine, etc. as aromatic amine compounds, glycidyl ether group-containing compounds, epoxidized fatty acid monoesters, epoxidized as epoxy compounds Oils and fats, epoxycycloalkyl group-containing compounds and the like are suitable. Further, as the phosphate ester, triphenyl phosphate, tricresyl phosphate and the like are suitable.
また従来、冷凍機油に使用されている有機硫黄化合物などの摩耗防止剤、アルコール、高級脂肪酸類などの油性剤、ベンゾトリアゾール誘導体などの金属不活性化剤、シリコーンオイルなどの消泡剤等の添加剤を適宜添加することができる。 Addition of anti-wear agents such as organic sulfur compounds used in refrigeration oils, oil-based agents such as alcohol and higher fatty acids, metal deactivators such as benzotriazole derivatives, and antifoaming agents such as silicone oil An agent can be added as appropriate.
冷媒Ｒ３２はルームエアコンなどに用いられることから、モーター内蔵型（密閉タイプ）のコンプレッサーに適した冷凍機油の特性、つまり高い電気絶縁性を有することも必要である。そこで、本発明の冷凍機油は添加剤配合の後で、体積抵抗率が１０11Ω・cm以上であることが好ましい。 Since the refrigerant R32 is used in a room air conditioner or the like, it is also necessary to have characteristics of refrigeration oil suitable for a motor built-in type (sealed type) compressor, that is, high electrical insulation. Therefore, the refrigerating machine oil of the present invention preferably has a volume resistivity of 10 11 Ω · cm or more after the additive is blended.
以下、実施例により本発明を具体的に説明するが、本発明はこれに限定されるものではない。
（実施例の供試油）
次のエステルを実施例の基油として供した（いずれもエステルの混合物となっている）。
基油Ａ：ネオペンチルグリコール（ＮＰＧ）１モルとアジピン酸（ＡＡ）１.５モルとで反応させたエステル中間体に、さらに２‐エチルヘキサノールを過剰に（１.５モル）加えてエステル化し、残存したアルコールを蒸留で除去して得たエステル。
基油Ｂ：ネオペンチルグリコール１モルとアジピン酸０.５モルとで反応させたエステル中間体に、さらに３,５,５‐トリメチルヘキサン酸を１.１モル加えてエステル化し、残存した脂肪酸を蒸留で除去して得たエステル。
基油Ｃ：トリメチロールプロパン（ＴＭＰ）１モルとアジピン酸２モルとで反応させたエステル中間体に、さらにtert.‐ブタノールを過剰に（１.５モル）加えてエステル化し、残存したアルコールを蒸留で除去して得たエステル。
基油Ｄ：トリメチロールプロパン１モルとスベリン酸（ＳＡ）１モルとで反応させたエステル中間体に、さらに２‐エチルヘキサン酸を１.１モル加えてエステル化し、残存した脂肪酸を蒸留で除去して得たエステル。
なお、これらの供試エステルについては、最終工程で吸着処理（白土処理）を行い、微量の不純物を除去した。これらの供試エステルの全酸価は、全て０.０１mgKOH/g以下であった。
EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto.
(Test oil of Example)
The following esters were provided as base oils for the examples (both are mixtures of esters).
Base oil A: esterified by adding 2-ethylhexanol in excess (1.5 mol) to an ester intermediate reacted with 1 mol of neopentyl glycol (NPG) and 1.5 mol of adipic acid (AA) The ester obtained by removing the remaining alcohol by distillation.
Base oil B: An ester intermediate obtained by reacting 1 mol of neopentyl glycol and 0.5 mol of adipic acid was added with an additional 1.1 mol of 3,5,5-trimethylhexanoic acid to esterify the remaining fatty acid. Ester obtained by distillation.
Base oil C: ester intermediate obtained by reacting 1 mol of trimethylolpropane (TMP) with 2 mol of adipic acid and adding tert.-butanol in excess (1.5 mol) to esterify the remaining alcohol Ester obtained by distillation.
Base oil D: 1.1 mol of 2-ethylhexanoic acid was added to the ester intermediate reacted with 1 mol of trimethylolpropane and 1 mol of suberic acid (SA), and the remaining fatty acid was removed by distillation. The ester obtained.
In addition, about these test ester, the adsorption process (white clay process) was performed in the last process, and the trace amount impurity was removed. The total acid values of these test esters were all 0.01 mgKOH / g or less.
（添加剤）
添加剤としては次のものを用いた。
ヒンダードフェノール化合物：ジ‐tert.‐ブチル‐p‐クレゾール（ＤＢＰＣ）
芳香族アミン化合物：ジオクチル‐ジフェニルアミン（ＤＯＤＡ）
エポキシ化合物 ：２‐エチルヘキシルグリシジルエーテル（２‐ＥＨＧＥ）
カルボジイミド ：ジフェニルカルボジイミド（ＤＰＣＩ）
リン酸エステル ：トリクレジルフォスフェート（ＴＣＰ）
(Additive)
The following were used as additives.
Hindered phenol compounds: di-tert.-butyl-p-cresol (DBPC)
Aromatic amine compound: Dioctyl-diphenylamine (DODA)
Epoxy compound: 2-ethylhexyl glycidyl ether (2-EHGE)
Carbodiimide: Diphenylcarbodiimide (DPCI)
Phosphate ester: tricresyl phosphate (TCP)
（比較例の供試油）
次の油を比較例の基油として供した。
基油Ｅ：ペンタエリスリトール（ＰＥ）と３,５,５‐トリメチルヘキサン酸のエステル。
基油Ｆ：ペンタエリスリトール１モルとアジピン酸１.５モルとで反応させたエステル中間体に、さらに２‐エチルヘキサン酸を１.１モル加えてエステル化し、残存した脂肪酸を除去したエステル。
基油Ｇ：トリメチロールプロパンとオレイン酸のエステル。
基油Ｈ：ポリアルキレングリコール（PAG、末端がブチル基と水酸基であり骨格部がオキシプロピレン、平均分子量が１２００）、全酸価；０.０１mgKOH/g。
基油Ｉ：ポリアルファオレフィン（PAO、デセンの重合体）、全酸価；０.０１mgKOH/g。
なお、これらのうちエステルについては、最終工程で吸着処理（白土処理）を行い微量の不純物を除去した。これらのエステルの全酸価は、全て０.０１mgKOH/g以下であった。
(Test oil of comparative example)
The following oil was used as the base oil for the comparative example.
Base oil E: ester of pentaerythritol (PE) and 3,5,5-trimethylhexanoic acid.
Base oil F: An ester obtained by adding 1.1 mol of 2-ethylhexanoic acid to an ester intermediate obtained by reacting 1 mol of pentaerythritol and 1.5 mol of adipic acid to remove the remaining fatty acid.
Base oil G: ester of trimethylolpropane and oleic acid.
Base oil H: polyalkylene glycol (PAG, terminal is butyl group and hydroxyl group, skeleton is oxypropylene, average molecular weight is 1200), total acid value: 0.01 mgKOH / g.
Base oil I: polyalphaolefin (PAO, polymer of decene), total acid number; 0.01 mg KOH / g.
Of these, esters were subjected to adsorption treatment (white clay treatment) in the final step to remove a small amount of impurities. The total acid values of these esters were all 0.01 mg KOH / g or less.
各供試油の添加剤配合量ならびに性状を表１に示した。
なお、動粘度はJIS K2283に、全酸価及び水酸基価はJIS K2501に準拠し、測定した。
Table 1 shows the additive content and properties of each test oil.
The kinematic viscosity was measured according to JIS K2283, and the total acid value and hydroxyl value were measured according to JIS K2501.
上記供試油について、冷凍機油としての次の各性能を、次に示す条件の下で測定、評価し、その結果を表２に示した。
（相溶性）
JIS K2211の「冷媒との相溶性試験方法」に準じ、冷媒Ｒ３２との油分率１０質量％での二層分離温度を測定した。
（熱安定性）
ANSI/ASHRAE 97‐1983に準じ、供試油（２０g）と冷媒Ｒ３２（２０g）と触媒（鉄、銅、アルミニウムの各線）をステンレス製ボンベ（１００ml）に封入し、１７５℃に加熱して１４日間保持した後、供試油の色相（ASTM表示）および酸価を測定した。
（潤滑性）
ASTM D-3233-73に準拠し、ファレックス（Falex）焼付荷重を冷媒Ｒ３２の吹き込み制御雰囲気下（70ml／min）で測定した。
（電気絶縁性）
JIS C2101に基づき、８０℃における体積抵抗率を求めた。
About the said test oil, each following performance as refrigerating machine oil was measured and evaluated on the conditions shown next, and the result was shown in Table 2.
(Compatibility)
According to JIS K2211, “Testing method for compatibility with refrigerant”, the two-layer separation temperature at an oil content of 10% by mass with refrigerant R32 was measured.
(Thermal stability)
In accordance with ANSI / ASHRAE 97-1983, test oil (20 g), refrigerant R32 (20 g) and catalyst (iron, copper, and aluminum wires) are sealed in a stainless steel cylinder (100 ml), heated to 175 ° C., and 14 After holding for one day, the hue (ASTM display) and acid value of the test oil were measured.
(Lubricity)
In accordance with ASTM D-3233-73, the Falex seizure load was measured in a controlled atmosphere (70 ml / min) of refrigerant R32.
(Electrical insulation)
Based on JIS C2101, the volume resistivity at 80 ° C. was determined.
表１および表２から分かるように、本発明に係るエステルは冷媒Ｒ３２と広い温度範囲で相溶し、熱安定性を含めた冷凍機油としての特性が良好である。なかでも添加剤を配合した実施例４〜８は熱安定性試験後の全酸価の上昇が少なく、特にエポキシ化合物とカルボジイミドの両者を添加した実施例８では全酸価の上昇がなかった。比較例１〜３のエステルの場合、冷媒Ｒ３２と相溶せず、冷凍機油としての特性を満足していない。比較例４のエーテルは冷媒と相溶せず、また、体積抵抗率で示される電気特性が本発明のエステルより約１０００倍悪く、冷凍機油として適さないことが分かる。比較例５の合成炭化水素油であるＰＡＯは極性が無いためＲ３２とは全く相溶せず、使えない。 As can be seen from Tables 1 and 2, the ester according to the present invention is compatible with the refrigerant R32 in a wide temperature range, and has good characteristics as a refrigerating machine oil including thermal stability. In particular, Examples 4 to 8 in which additives were added had little increase in the total acid value after the thermal stability test, and in particular, in Example 8 in which both the epoxy compound and carbodiimide were added, there was no increase in the total acid value. In the case of the esters of Comparative Examples 1 to 3, they are not compatible with the refrigerant R32 and do not satisfy the characteristics as refrigerating machine oil. It can be seen that the ether of Comparative Example 4 is not compatible with the refrigerant, and the electrical properties indicated by volume resistivity are about 1000 times worse than the ester of the present invention, which is not suitable as a refrigerating machine oil. PAO, which is the synthetic hydrocarbon oil of Comparative Example 5, has no polarity and is therefore completely incompatible with R32 and cannot be used.
本発明の冷凍機油は、Ｒ３２を冷媒として用いる冷凍機の潤滑油として用いられ、特には、圧縮機、凝縮器、絞り装置（膨張弁またはキャピラリーチューブ等の冷媒流量制御部）、蒸発器等を有し、これらの間で冷媒を循環させる冷却効率の高い冷凍システムで、ロータリータイプ、スイングタイプ、スクロールタイプコンプレッサ等のコンプレッサを有する冷凍機における潤滑油として用いることができ、ルームエアコン、パッケージエアコン、産業用冷凍機等に好適に使用できる。 The refrigerating machine oil of the present invention is used as a lubricating oil for a refrigerating machine using R32 as a refrigerant. In particular, a compressor, a condenser, a throttle device (a refrigerant flow control unit such as an expansion valve or a capillary tube), an evaporator, etc. It is a refrigeration system with high cooling efficiency that circulates refrigerant between them, and can be used as lubricating oil in refrigerators having compressors such as rotary type, swing type, scroll type compressor, room air conditioner, packaged air conditioner, It can be suitably used for industrial refrigerators and the like.
Claims (6)
An ester intermediate obtained by reacting trimethylolpropane and / or neopentyl glycol with a dibasic acid having 2 to 12 carbon atoms is further converted to a monohydric alcohol having 1 to 12 carbon atoms or a monovalent fatty acid having 2 to 12 carbon atoms. A refrigerating machine oil for refrigerant R32 having a kinematic viscosity at 100 ° C. of 8 to 12 mm 2 / s based on an ester having an esterified acid value of 0.1 mgKOH / g or less as a base oil.
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| KR20160030998A (en) * | 2013-09-05 | 2016-03-21 | 도시바 캐리어 가부시키가이샤 | Compressor and refrigeration cycle device |
| CN106414681B (en) | 2014-01-21 | 2019-07-16 | 捷客斯能源株式会社 | Working fluid composition for refrigerating machine and refrigerator oil |
| WO2016002523A1 (en) * | 2014-07-04 | 2016-01-07 | Ｊｘ日鉱日石エネルギー株式会社 | Wear-resistance additive, refrigerator oil, and working fluid composition for refrigerator |
| CN107603719A (en) * | 2017-10-09 | 2018-01-19 | 佛山市顺德区孚延盛润滑油有限公司 | Refrigerator oil |
| WO2019087205A1 (en) * | 2017-11-03 | 2019-05-09 | Council Of Scientific & Industrial Research | Ecofriendly and biodegradable lubricant formulation and process for preparation thereof |
| CN109370703B (en) * | 2018-11-26 | 2021-07-20 | 珠海格力节能环保制冷技术研究中心有限公司 | Refrigerator oil base oil, preparation method thereof, refrigerator oil, working fluid composition for compressor and compressor |
| CN115466644B (en) * | 2022-09-16 | 2023-06-16 | 珠海格力电器股份有限公司 | Refrigerator oil and working fluid composition |
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| DE4006828A1 (en) * | 1990-03-05 | 1991-09-12 | Hoechst Ag | Use of ester lubricating oils |
| US5798319A (en) * | 1996-01-16 | 1998-08-25 | Exxon Chemical Patents Inc. | High stability and low metals esters based on 3,5,5-trimethyl-1-hexanol |
| KR20010029465A (en) * | 1996-09-06 | 2001-04-06 | 엑손 케미칼 패턴츠 인코포레이티드 | High Viscosity Complex Alcohol Esters |
| JPH10298572A (en) * | 1997-02-13 | 1998-11-10 | Japan Energy Corp | Compression type freezer and refrigerator oil used therefor |
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