CN1055964C - 一种制冷机油和采用该制冷机油的润滑方法 - Google Patents
一种制冷机油和采用该制冷机油的润滑方法 Download PDFInfo
- Publication number
- CN1055964C CN1055964C CN96195430A CN96195430A CN1055964C CN 1055964 C CN1055964 C CN 1055964C CN 96195430 A CN96195430 A CN 96195430A CN 96195430 A CN96195430 A CN 96195430A CN 1055964 C CN1055964 C CN 1055964C
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- China
- Prior art keywords
- oil
- alkyl
- refrigerator
- refrigerator oil
- general formula
- 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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- 238000000034 method Methods 0.000 title abstract description 15
- 230000001050 lubricating effect Effects 0.000 title abstract description 10
- 239000010721 machine oil Substances 0.000 title abstract description 5
- 239000003921 oil Substances 0.000 claims abstract description 90
- 238000005057 refrigeration Methods 0.000 claims abstract description 43
- 239000003507 refrigerant Substances 0.000 claims abstract description 39
- 229920002545 silicone oil Polymers 0.000 claims abstract description 27
- 239000001301 oxygen Substances 0.000 claims abstract description 20
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 20
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229920001515 polyalkylene glycol Polymers 0.000 claims abstract description 14
- 239000002199 base oil Substances 0.000 claims abstract description 13
- 150000002894 organic compounds Chemical class 0.000 claims abstract description 10
- 229920000728 polyester Polymers 0.000 claims abstract description 4
- 230000006835 compression Effects 0.000 claims abstract description 3
- 238000007906 compression Methods 0.000 claims abstract description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 79
- 125000004432 carbon atom Chemical group C* 0.000 claims description 70
- 229910052799 carbon Inorganic materials 0.000 claims description 57
- 150000001875 compounds Chemical class 0.000 claims description 40
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 30
- 239000003795 chemical substances by application Substances 0.000 claims description 28
- 229920001774 Perfluoroether Polymers 0.000 claims description 26
- 229930195733 hydrocarbon Natural products 0.000 claims description 25
- 239000004215 Carbon black (E152) Substances 0.000 claims description 23
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical class CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 18
- RWRIWBAIICGTTQ-UHFFFAOYSA-N difluoromethane Chemical compound FCF RWRIWBAIICGTTQ-UHFFFAOYSA-N 0.000 claims description 8
- 150000002430 hydrocarbons Chemical class 0.000 claims description 6
- LVGUZGTVOIAKKC-UHFFFAOYSA-N 1,1,1,2-tetrafluoroethane Chemical compound FCC(F)(F)F LVGUZGTVOIAKKC-UHFFFAOYSA-N 0.000 claims description 5
- 150000004651 carbonic acid esters Chemical class 0.000 claims description 5
- 229920001643 poly(ether ketone) Polymers 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- XPDWGBQVDMORPB-UHFFFAOYSA-N Fluoroform Chemical compound FC(F)F XPDWGBQVDMORPB-UHFFFAOYSA-N 0.000 claims description 4
- KLZDCUBZWUSEGO-UHFFFAOYSA-N CC.F.F.F.F.F Chemical compound CC.F.F.F.F.F KLZDCUBZWUSEGO-UHFFFAOYSA-N 0.000 claims description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 3
- WXGNWUVNYMJENI-UHFFFAOYSA-N 1,1,2,2-tetrafluoroethane Chemical compound FC(F)C(F)F WXGNWUVNYMJENI-UHFFFAOYSA-N 0.000 claims description 2
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- 229960003132 halothane Drugs 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 2
- 238000005461 lubrication Methods 0.000 claims description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 claims 1
- 239000001569 carbon dioxide Substances 0.000 claims 1
- 239000002826 coolant Substances 0.000 claims 1
- 238000005187 foaming Methods 0.000 abstract description 19
- 238000009835 boiling Methods 0.000 abstract description 8
- -1 isobutyl- Chemical group 0.000 description 122
- 235000019198 oils Nutrition 0.000 description 76
- 150000001721 carbon Chemical group 0.000 description 50
- 125000001118 alkylidene group Chemical group 0.000 description 23
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 17
- 239000000203 mixture Substances 0.000 description 16
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 15
- 229920000515 polycarbonate Polymers 0.000 description 14
- 239000004417 polycarbonate Substances 0.000 description 14
- 229920001289 polyvinyl ether Polymers 0.000 description 14
- 125000001931 aliphatic group Chemical group 0.000 description 13
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 13
- 125000002704 decyl group Chemical group [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])C([H])([H])C([H])([H])* 0.000 description 13
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 12
- 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 12
- VOPWNXZWBYDODV-UHFFFAOYSA-N Chlorodifluoromethane Chemical compound FC(F)Cl VOPWNXZWBYDODV-UHFFFAOYSA-N 0.000 description 11
- 125000002948 undecyl 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])C([H])([H])C([H])([H])[H] 0.000 description 11
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 10
- 125000003118 aryl group Chemical group 0.000 description 10
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 10
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 9
- YCOZIPAWZNQLMR-UHFFFAOYSA-N heptane - octane Natural products CCCCCCCCCCCCCCC YCOZIPAWZNQLMR-UHFFFAOYSA-N 0.000 description 9
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical group CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 8
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 8
- 125000003710 aryl alkyl group Chemical group 0.000 description 8
- 125000000753 cycloalkyl group Chemical group 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 8
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 7
- 125000003438 dodecyl group Chemical group [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])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- RJWUMFHQJJBBOD-UHFFFAOYSA-N 2-methylheptadecane Chemical compound CCCCCCCCCCCCCCCC(C)C RJWUMFHQJJBBOD-UHFFFAOYSA-N 0.000 description 6
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 6
- 125000002252 acyl group Chemical group 0.000 description 6
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 6
- 235000011187 glycerol Nutrition 0.000 description 6
- 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 6
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 6
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 6
- 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 6
- 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 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 6
- 229920005862 polyol Polymers 0.000 description 6
- 230000000452 restraining effect Effects 0.000 description 6
- BGHCVCJVXZWKCC-UHFFFAOYSA-N tetradecane Chemical compound CCCCCCCCCCCCCC BGHCVCJVXZWKCC-UHFFFAOYSA-N 0.000 description 6
- IIYFAKIEWZDVMP-UHFFFAOYSA-N tridecane Chemical compound CCCCCCCCCCCCC IIYFAKIEWZDVMP-UHFFFAOYSA-N 0.000 description 6
- UXFQFBNBSPQBJW-UHFFFAOYSA-N 2-amino-2-methylpropane-1,3-diol Chemical group OCC(N)(C)CO UXFQFBNBSPQBJW-UHFFFAOYSA-N 0.000 description 5
- 239000004148 curcumin Substances 0.000 description 5
- 239000013530 defoamer Substances 0.000 description 5
- 239000010696 ester oil Substances 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 5
- 125000006178 methyl benzyl group Chemical group 0.000 description 5
- 125000001421 myristyl 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])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 5
- 125000003944 tolyl group Chemical group 0.000 description 5
- LEEDMQGKBNGPDN-UHFFFAOYSA-N 2-methylnonadecane Chemical compound CCCCCCCCCCCCCCCCCC(C)C LEEDMQGKBNGPDN-UHFFFAOYSA-N 0.000 description 4
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 4
- 229920003232 aliphatic polyester Polymers 0.000 description 4
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 4
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 4
- 150000002191 fatty alcohols Chemical class 0.000 description 4
- 239000006260 foam Substances 0.000 description 4
- NDJKXXJCMXVBJW-UHFFFAOYSA-N heptadecane Chemical compound CCCCCCCCCCCCCCCCC NDJKXXJCMXVBJW-UHFFFAOYSA-N 0.000 description 4
- 239000000314 lubricant Substances 0.000 description 4
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 4
- 125000001624 naphthyl group Chemical group 0.000 description 4
- RZJRJXONCZWCBN-UHFFFAOYSA-N octadecane Chemical compound CCCCCCCCCCCCCCCCCC RZJRJXONCZWCBN-UHFFFAOYSA-N 0.000 description 4
- 229940059574 pentaerithrityl Drugs 0.000 description 4
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 4
- XOJVVFBFDXDTEG-UHFFFAOYSA-N pristane Chemical compound CC(C)CCCC(C)CCCC(C)CCCC(C)C XOJVVFBFDXDTEG-UHFFFAOYSA-N 0.000 description 4
- MEIRRNXMZYDVDW-MQQKCMAXSA-N (2E,4E)-2,4-hexadien-1-ol Chemical compound C\C=C\C=C\CO MEIRRNXMZYDVDW-MQQKCMAXSA-N 0.000 description 3
- VKPSKYDESGTTFR-UHFFFAOYSA-N 2,2,4,6,6-pentamethylheptane Chemical compound CC(C)(C)CC(C)CC(C)(C)C VKPSKYDESGTTFR-UHFFFAOYSA-N 0.000 description 3
- AIDLAEPHWROGFI-UHFFFAOYSA-N 2-methylbenzene-1,3-dicarboxylic acid Chemical compound CC1=C(C(O)=O)C=CC=C1C(O)=O AIDLAEPHWROGFI-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000005840 aryl radicals Chemical class 0.000 description 3
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 150000002009 diols Chemical class 0.000 description 3
- 150000002170 ethers Chemical class 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- GOQYKNQRPGWPLP-UHFFFAOYSA-N heptadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 description 3
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 description 3
- 239000002480 mineral oil Substances 0.000 description 3
- 235000010446 mineral oil Nutrition 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 3
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 3
- 125000005702 oxyalkylene group Chemical group 0.000 description 3
- 125000002958 pentadecyl 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])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 125000000286 phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 3
- 229920013639 polyalphaolefin Polymers 0.000 description 3
- 229920001451 polypropylene glycol Polymers 0.000 description 3
- 238000012797 qualification Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- RSJKGSCJYJTIGS-UHFFFAOYSA-N undecane Chemical compound CCCCCCCCCCC RSJKGSCJYJTIGS-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- QEGNUYASOUJEHD-UHFFFAOYSA-N 1,1-dimethylcyclohexane Chemical compound CC1(C)CCCCC1 QEGNUYASOUJEHD-UHFFFAOYSA-N 0.000 description 2
- KVNYFPKFSJIPBJ-UHFFFAOYSA-N 1,2-diethylbenzene Chemical compound CCC1=CC=CC=C1CC KVNYFPKFSJIPBJ-UHFFFAOYSA-N 0.000 description 2
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- RWNUSVWFHDHRCJ-UHFFFAOYSA-N 1-butoxypropan-2-ol Chemical group CCCCOCC(C)O RWNUSVWFHDHRCJ-UHFFFAOYSA-N 0.000 description 2
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical group COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 2
- 125000001637 1-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C(*)=C([H])C([H])=C([H])C2=C1[H] 0.000 description 2
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical group COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 2
- JDSQBDGCMUXRBM-UHFFFAOYSA-N 2-[2-(2-butoxypropoxy)propoxy]propan-1-ol Chemical group CCCCOC(C)COC(C)COC(C)CO JDSQBDGCMUXRBM-UHFFFAOYSA-N 0.000 description 2
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 2
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical group CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 2
- WRMNZCZEMHIOCP-UHFFFAOYSA-N 2-phenylethanol Chemical compound OCCC1=CC=CC=C1 WRMNZCZEMHIOCP-UHFFFAOYSA-N 0.000 description 2
- NZQMQVJXSRMTCJ-UHFFFAOYSA-N 3-Methyl-hexanoic acid Chemical compound CCCC(C)CC(O)=O NZQMQVJXSRMTCJ-UHFFFAOYSA-N 0.000 description 2
- 125000003469 3-methylhexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 2
- UQRONKZLYKUEMO-UHFFFAOYSA-N 4-methyl-1-(2,4,6-trimethylphenyl)pent-4-en-2-one Chemical group CC(=C)CC(=O)Cc1c(C)cc(C)cc1C UQRONKZLYKUEMO-UHFFFAOYSA-N 0.000 description 2
- 125000000590 4-methylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- 239000005632 Capric acid (CAS 334-48-5) Substances 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- 150000004996 alkyl benzenes Chemical class 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 150000001733 carboxylic acid esters Chemical class 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 125000000490 cinnamyl group Chemical group C(C=CC1=CC=CC=C1)* 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 2
- 150000005690 diesters Chemical class 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 2
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 125000001033 ether group Chemical group 0.000 description 2
- HNRMPXKDFBEGFZ-UHFFFAOYSA-N ethyl trimethyl methane Natural products CCC(C)(C)C HNRMPXKDFBEGFZ-UHFFFAOYSA-N 0.000 description 2
- IIEWJVIFRVWJOD-UHFFFAOYSA-N ethylcyclohexane Chemical compound CCC1CCCCC1 IIEWJVIFRVWJOD-UHFFFAOYSA-N 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 125000004407 fluoroaryl group Chemical group 0.000 description 2
- 239000003205 fragrance Substances 0.000 description 2
- MNWFXJYAOYHMED-UHFFFAOYSA-N heptanoic acid Chemical compound CCCCCCC(O)=O MNWFXJYAOYHMED-UHFFFAOYSA-N 0.000 description 2
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 2
- CBFCDTFDPHXCNY-UHFFFAOYSA-N icosane Chemical compound CCCCCCCCCCCCCCCCCCCC CBFCDTFDPHXCNY-UHFFFAOYSA-N 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
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- 239000010687 lubricating oil Substances 0.000 description 2
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- 125000000913 palmityl 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])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
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 1
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- JYVLIDXNZAXMDK-UHFFFAOYSA-N pentan-2-ol Chemical compound CCCC(C)O JYVLIDXNZAXMDK-UHFFFAOYSA-N 0.000 description 1
- RFPMGSKVEAUNMZ-UHFFFAOYSA-N pentylidene Chemical group [CH2+]CCC[CH-] RFPMGSKVEAUNMZ-UHFFFAOYSA-N 0.000 description 1
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- 125000004344 phenylpropyl group Chemical group 0.000 description 1
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- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
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Classifications
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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
- C10M155/00—Lubricating compositions characterised by the additive being a macromolecular compound containing atoms of elements not provided for in groups C10M143/00 - C10M153/00
- C10M155/02—Monomer containing silicon
-
- 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
- C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
- C10M105/08—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen
- C10M105/32—Esters
- C10M105/36—Esters of polycarboxylic acids
-
- 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
- C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
- C10M105/08—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen
- C10M105/32—Esters
- C10M105/38—Esters of polyhydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
- C10M105/08—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen
- C10M105/32—Esters
- C10M105/48—Esters of carbonic acid
-
- 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
- C10M107/00—Lubricating compositions characterised by the base-material being a macromolecular compound
- C10M107/20—Lubricating compositions characterised by the base-material being a macromolecular compound containing oxygen
- C10M107/22—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C10M107/24—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an alcohol, aldehyde, ketonic, ether, ketal or acetal radical
-
- 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
- C10M107/00—Lubricating compositions characterised by the base-material being a macromolecular compound
- C10M107/20—Lubricating compositions characterised by the base-material being a macromolecular compound containing oxygen
- C10M107/30—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C10M107/32—Condensation polymers of aldehydes or ketones; Polyesters; Polyethers
-
- 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
- C10M107/00—Lubricating compositions characterised by the base-material being a macromolecular compound
- C10M107/20—Lubricating compositions characterised by the base-material being a macromolecular compound containing oxygen
- C10M107/30—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C10M107/32—Condensation polymers of aldehydes or ketones; Polyesters; Polyethers
- C10M107/34—Polyoxyalkylenes
-
- 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
- C10M169/041—Mixtures of base-materials and additives the additives being macromolecular compounds only
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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Abstract
本发明公开了一种制冷机油,特别是用于氢氟烃制冷剂的制冷机油,它含有由含氧有机化合物、例如聚亚烷基二醇和聚酯构成的基油和25℃下运动粘度为500毫米2/秒或更高的氟化硅油。同时也公开了一种包括采用该制冷机油润滑压缩式制冷系统的制冷系统的润滑方法。采用这种制冷机油能够有效地抑制溶于制冷机油中的制冷剂在沸腾时的起泡现象。在制冷系统中采用这种制冷机油能够达到良好的润滑效果。
Description
技术领域
本发明涉及一种制冷机油,特别是一种用于与氢氟烃制冷剂混合的制冷机油,以及采用该制冷机油对制冷系统的润滑方法。更具体地说,本发明涉及一种能够有效地抑制溶于制冷机油中的制冷剂在沸腾时起泡现象的制冷机油,以及采用该制冷机油对制冷系统进行润滑以保持压缩式制冷系统极佳功能的润滑方法。
背景技术
压缩式制冷机一般都由压缩机、冷凝器、膨胀阀和蒸发器组成,在其结构中由制冷剂和润滑油组成的混合液体在一密闭系统中循环。到目前为止,在压缩式制冷机中主要采用的制冷剂为一氟二氯甲烷(R12)、一氯二氟甲烷(R22)或类似物,润滑油则为各种矿物油和合成油。
然而,由于对环境造成的污染如对臭氧层的破坏,世界范围内对氯氟烃如上述的R12和R22正在进行更严格的限制。正因如此,含氢Flon化合物(“Flon化合物”一般是指氯氟烃、氢氟烃和氢氯氟烃)如氢氟烃和氢氯氟烃作为新型制冷剂正引起人们的注意。含氢氟烃特别是氢氟烃,如1,1,1,2-四氟乙烷(Flon 134a),由于它们对臭氧层造成破坏的可能性小,而且对目前所用的制冷机在结构上稍许变动就能够替代Flon 12,因而是压缩式冰箱优选的制冷剂。
但是,当使用上述的氢氟烃制冷剂时,溶于制冷机油中的制冷剂在沸腾时会大量起泡。尤其是当采用两种或多种氢氟烃的混合制冷剂时,这种起泡现象更为剧烈。起泡现象发生剧烈时,有大量的制冷机油流到制冷系统中,使制冷能力降低,而且由于在需要润滑的地方制冷机油量的降低,也无法达到足够的润滑效果。特别是对于目前推出的带有转换器的制冷机,由于其启动时要求更高的转速,这种问题就显得更为突出。因此,这种新型制冷机比以前型号的制冷机更需要一种能够防止这种起泡现象的制冷机油。
以前类型的制冷剂也有同样的现象发生。从经验已知以前类型制冷剂的起泡现象可通过添加普通硅油而得到抑制。然而在目前采用氢氟烃制冷剂的情况下,添加普通硅油对起泡现象的抑制作用有限,达不到任何实际效果。
发明公开
本发明的一个目标是提供一种制冷机油,特别是一种用于与氢氟烃制冷剂混合、能够有效地抑制溶于制冷机油中的制冷剂在沸腾时起泡现象的制冷机油。
本发明的另一个目的是提供一种采用上述制冷机油以保持压缩式制冷系统极佳功能的制冷系统的润滑方法。
为达到上述目标,本发明人进行了广泛的研究。研究结果发现,在特定制冷机油中添加氟化硅油,能够有效地抑制溶于制冷机油中的制冷剂在沸腾时的起泡现象。同时也发现,在压缩式制冷系统中,用含有上述氟化硅油的制冷机油来润滑制冷系统,能够使制冷系统保持极佳的功能。本发明基于这些发现而得以完成。
因此,本发明提供一种含有由含氧有机化合物构成的基油和25℃下运动粘度为500毫米2/秒或更高的氟化硅油的制冷机油。本发明也提供一种制冷系统的润滑方法,包括采用上述制冷机油来润滑压缩式制冷系统。最优选的实施方案
在通式(I)中,R1至R6可以相同或不同,各自代表氢原子、烃基或氟化烃基。R7和R8各自代表烃基或氟化烃基,且R7和R8中至少一个为氟化烃基。R1至R8所表示的烃基的例子包括含有1至20个碳原子的烷基、含有5至20个碳原子的环烷基、含有6至20个碳原子的芳基和含有7至20个碳原子的芳烷基。氟化烃基的例子包括含有1至20个碳原子的氟化烷基、含有5至20个碳原子的氟化环烷基、含有6至20个碳原子的氟化芳基和含有7至20个碳原子的氟化芳烷基。特别地,优选的烃基和氟化烃基分别是含有1至20个碳原子的烷基和含有1至20个碳原子的氟化烷基,这样氟化硅油在制冷机油中的溶解度低,对起泡现象的抑制作用大。
在多个重复单元中的R7和R8可以相同或不同。n表示一整数,其取值大小应使氟化硅油在25℃下的运动粘度为500毫米2/秒或更高。
上述含有1至20个碳原子的烷基可以是线型或支链烷基。含有1至20个碳原子的烷基的具体例子包括甲基、乙基、正丙基、异丙基、正丁基、异丁基、二级丁基、三级丁基、各种戊基、各种己基、各种辛基、各种癸基和各种十二烷基。含有5至20个碳原子的环烷基的例子包括环戊基、环己基和甲基环己基。含有6至20个碳原子的芳基的例子包括苯基、甲苯基、二甲苯基和萘基。含有7至20个碳原子的芳烷基的例子包括苄基、苯乙基和萘甲基。含有1至20个碳原子的氟化烷基、含有5至20个碳原子的氟化环烷基、含有6至20个碳原子的氟化芳基和含有7至20个碳原子的氟化芳烷基的例子包括用氟原子分别取代上述烷基、环烷基、芳基和芳烷基中的一个或多个氢原子而得到的基团。
当通式(I)所示的氟化硅油在25℃下的运动粘度小于500毫米2 /秒时,它对起泡现象的抑制作用不足,不在本发明所优选的氟化硅油之列。要达到对起泡现象足够的抑制效果,氟化硅油在25℃下的运动粘度优选为1000毫米2/秒或更高,尤其9000毫米2/秒或更高(n一般大于100)。
对氟化硅油的含量不做特别的限定。当制冷剂采用氢氟烃制冷剂时,其含量范围优选使得制冷机油和制冷剂的相容性不受负面影响。更具体地说,其含量优选为1至6000ppm(百万分之一,重量),特别是10至3000ppm(重量)。当含量小于1ppm时,对起泡现象的抑制作用有时显得不足。当含量大于6000ppm时,制冷机油有时会变得浑浊。从抑制起泡现象的效果和稳定性来看,优选氟化硅油的含量使得氟化硅油在25℃下的运动粘度(毫米2/秒)和氟化硅油在制冷机油中的含量(重量百万分之一)的乘积为50000至3000000,特别是100000至2000000。当乘积小于50000时,对起泡现象的抑制作用就不足。当乘积超过3000000时,就有制冷机油变得浑浊的可能。
本发明的制冷机油可与各种制冷剂混合使用,优选与氢氟烃制冷剂混合使用。当制冷剂选用氢氟烃制冷剂时,只要基油与氢氟烃制冷剂有良好的相容性,对制冷机油中的基油的种类不作特别的限定。具体地说,由于与氢氟烃制冷剂有良好的相容性,含氧有机化合物为优选的基油。
含氧有机化合物的例子包括(1)聚亚烷基二醇,(2)聚酯,(3)多元醇酯,(4)聚醚酮,(5)聚乙烯基醚和(6)碳酸酯衍生物。
作为上述(1)聚亚烷基二醇,例如可选用通式(II)所示的化合物:
R9-[(OR10)m-OR11]k …(II)(其中:R9代表氢原子,含有1至10个碳原子的烷基,含有2至10个碳原子的酰基,或含有1至1O个碳原子和2至6个结合键的脂肪烃基;R10代表含有2至4个碳原子的亚烷基;R11代表氢原子,含有1至10个碳原子的烷基,或含有2至10个碳原子的酰基;k代表1至6的整数;和m代表一数,其取值应使m×k的平均值为6至80。)
在上面通式(II)中,R9和R11所代表的烷基可以是线型、支链或环状烷基。该烷基的具体例子包括甲基、乙基、正丙基、异丙基、各种丁基、各种戊基、各种己基、各种庚基、各种辛基、各种壬基、各种癸基、环戊基和环己基。当烷基中的碳原子数超过10时,含氧有机化合物与氢氟烃制冷剂的相容性下降,并可能产生相分离。烷基中优选的碳原子数为1至6。
R9和R11所代表的酰基中的烷基可以是线型、支链或环状烷基。该烷基的具体例子包括含有1至9个碳原子、选自上述烷基例子中的烷基。当酰基中的碳原子数超过10时,含氧有机化合物与氢氟烃制冷剂的相容性下降,并可能产生相分离。烷基中优选的碳原子数为2至6。
当R9和R11同为烷基或酰基时,R9和R11可以相同或不同。
当k大于或等于2时,在同一分子中的多个R11可以相同或不同。
当R9为含有1至10个碳原子和2至6个结合键的脂肪烃基时,脂肪烃基可以是开链或环状烃基。含有2个结合键的脂肪烃基的例子包括亚乙基、亚丙基、亚丁基、亚戊基、亚己基、亚庚基、亚辛基、亚壬基、亚癸基、亚环戊基和亚环己基。含有3至6个结合键的脂肪烃基的例子包括下述多元醇脱羟基后的残留基团,多元醇如三甲基丙烷、甘油、季戊四醇、山梨醇、1,2,3-三羟基环己烷和1,3,5-三羟基环己烷。
当该脂肪烃基中的碳原子数超过10时,含氧有机化合物与氢氟烃制冷剂的相容性下降,并可能产生相分离。该烷基中优选的碳原子数为2至6。
在上面通式(II)中的R10代表含有2至4个碳原子的亚烷基。作为重复单元的氧亚烷基的例子包括氧亚乙基、氧亚丙基和氧亚丁基。在一个分子中可以含有一种氧亚烷基或两种或多种氧亚烷基。优选每分子中至少含有氧亚丙基。特别优选在氧亚烷基单元中含有50%或更多(摩尔)的氧亚丙基单元。
在上面通式(II)中k代表1至6的一个整数,与R9中结合键的数目相匹配。例如,当R9代表烷基或酰基时,k代表1。当R9代表含有2、3、4、5或6个结合键的脂肪烃基时,k则分别代表2、3、4、5或6。m代表一数,其取值应使m×k的平均值为6至80,优选为10至70。当m×k的平均值不在此范围时,就不能完全达到本发明的目的。
由通式(II)所示的聚亚烷基二醇包括含有羟端基的聚亚烷基二醇。当所有端基中羟端基的含量为50%(摩尔)或低于此值时,选用含有羟端基的聚亚烷基二醇有利。但是,当羟端基的含量超过50%(摩尔)时,并不优选此聚亚烷基二醇,因为此时聚亚烷基二醇变得更易吸湿,其粘度指数降低。
从成本和效果看,上述聚亚烷基二醇优选下面通式所示的聚氧丙烯二醇的二甲醚:(其中x为6至80的数),下面通式所示的聚氧乙烯聚氧丙烯二醇的二甲醚:(其中a和b各自为1或大于1的数,且a和b之和为6至80),下面通式所示的聚氧丙烯二醇的单丁基醚:(其中x为6至80的数),以及聚氧丙烯二醇的二乙酸酯。
作为通式(II)所示的聚亚烷基二醇,也可选用日本专利申请公报(Japanese Patent Application Laid-Open)No.平成2(1990)-305893中详细介绍的化合物。
作为前述的(2)聚酯,可选用分子量为300至2000、含有由通式(III)所示组成单元的脂肪族聚酯衍生物:(其中R12代表含有1至10个碳原子的亚烷基和R13代表含有2至10个碳原子的亚烷基或含有4至20个碳原子的氧杂亚烷基)。
在通式(III)中,R12代表含有1至10个碳原子的亚烷基。具体的亚烷基的例子包括亚甲基、亚乙基、亚丙基、乙基亚甲基、1,1-二甲基亚乙基、1,2-二甲基亚乙基、正丁基亚乙基、异丁基亚乙基、1-乙基-2-甲基亚乙基、1-乙基-1-甲基-亚乙基、1,3-亚丙基、1,4-亚丁基和1,5-亚戊基。优选含有6个或低于6个碳原子的亚烷基。R13代表含有2至10个碳原子的亚烷基或含有4至20个碳原子的氧杂亚烷基。亚烷基的具体例子包括上述R12所示的亚烷基的具体例子(除亚甲基外)。优选含有2至6个碳原子的亚烷基。氧杂亚烷基的具体例子包括3-氧杂-1,5-亚戊基、3,6-二氧杂-1,8-亚辛基、3,6,9-三氧杂-1,11-亚十一烷基、3-氧杂-1,4-二甲基-1,5-亚戊基、3,6-二氧杂-1,4,7-三甲基-1,8-亚辛基、3,6,9-三氧杂-1,4,7,10-四甲基-1,11-亚十一烷基、3-氧杂-1,4-二乙基-1,5-亚戊基、3,6-二氧杂-1,4,7-三乙基-1,8-亚辛基、3,6,9-三氧杂-1,4,7,10-四乙基-1,11-亚十一烷基、3-氧杂-1,1,4,4-四甲基-1,5-亚戊基、3,6-二氧杂-1,1,4,4,7,7-六甲基-1,8-亚辛基、3,6,9-三氧杂-1,1,4,4,7,7,10,10-八甲基-1,11-亚十一烷基、3-氧杂-1,2,4,5-四甲基-1,5-亚戊基、3,6-二氧杂-1,2,4,5,7,8-六甲基-1,8-亚辛基、3,6,9-三氧杂-1,2,4,5,7,8,10,11-八甲基-1,11-亚十一烷基、3-氧杂-1-甲基-1,5-亚戊基、3-氧杂-1-乙基-1,5-亚戊基、3-氧杂-1,2-二甲基-1,5-亚戊基、3-氧杂-1-甲基-4-乙基-1,5-亚戊基、4-氧杂-2,2,6,6-四甲基-1,7-亚庚基和4,8-二氧杂-2,2,6,6,10,10-六甲基-1,11-亚十一烷基。在多个组成单元中的R12和R13可以相同或不同。
上面通式(III)所示的脂肪族聚酯衍生物优选其分子量(由凝胶渗透色谱GPC测量)为300至2000。当分子量小于300时,其运动粘度低于所需的范围。当分子量大于2000时,则脂肪族聚酯衍生物呈蜡状。因此,分子量最好不要超出所限定的范围。
作为上述脂肪族聚酯衍生物,也可选用国际专利申请公开WO91/07479中详细介绍的化合物。
作为前述(3)多元醇酯,可选用含有至少两个羟基的多羟基化合物的羧酸酯。例如,可选用通式(IV)所示的化合物:
R14[OCOR15]e …(IV)
在上面通式(IV)中,R14代表线型或支链的烃基,优选为含有2至10个碳原子的烷基。R15代表氢原子或含有1至22个碳原子的烃基,优选为含有2至16个碳原子的烷基。e代表2至6的一个整数。多个-OCOR15可以相同或不同。
通式(IV)所示的多元醇酯可通过通式(V)所示的多羟基化合物:
R14(OH)e … (V)(其中R14和e的含义与上面所述相同)与通式(VI)所示的羧酸:
R15COOH … (VI)(其中R15的含义与上面所述相同)或其反应性衍生物如酯或酰氯进行反应而得到。
上面通式(V)所示的多元醇的例子包括乙二醇、丙二醇、丁二醇、新戊二醇、三羟甲基乙烷、三羟甲基丙烷、甘油、季戊四醇、二季戊四醇和山梨醇。通式(VI)所示羧酸的例子为丙酸、丁酸、新戊酸、戊酸、己酸、庚酸、3-甲基己酸、2-乙基己酸、癸酸、癸酸、月桂酸、十四酸和十六酸。
作为前述(4)聚醚酮,例如可选用通式(VII)所示的化合物:(其中Q代表具有1至8个官能团的醇的残基;R16代表含有2至4个碳原子的亚烷基;R17代表甲基或乙基;R18和R20各自代表氢原子,含有小于或等于20个碳原子的脂肪族、芳香族或芳香脂肪族烃基,可以相同或不同;R19代表含有小于或等于20个碳原子的脂肪族、芳香族或芳香脂肪族烃基;s和t各自代表0至30的数;v代表1至8的数,w代表0至7的数,且v+w的和在1至8的范围内;以及u代表0或1)。
在通式(VII)中,Q代表具有1至8个官能团的醇的残基。含有Q残基的醇的例子包括一元醇,例如一元脂肪醇如甲醇、乙醇、线型或支链丙醇、线型和支链丁醇、线型和支链戊醇、线型和支链己醇、线型和支链庚醇、线型和支链辛醇、线型和支链壬醇、线型和支链癸醇、线型和支链十一烷醇、线型和支链十二烷醇、线型和支链十三烷醇、线型和支链十四烷醇、线型和支链十五烷醇、线型和支链十六烷醇、线型和支链十七烷醇、线型和支链十八烷醇、线型和支链十九烷醇、线型和支链二十烷醇,芳香醇如苯酚、甲苯酚、壬基苯酚、辛基苯酚和萘酚,芳香脂肪醇如苄醇和苯乙醇,以及这些醇的部分醚化产物;二元醇,例如线型和支链脂肪醇如乙二醇、丙二醇、丁二醇、新戊二醇和四亚甲基二醇,芳香醇如邻苯二酚、间苯二酚、双酚A和联苯二酚,以及这些化合物的部分醚化产物;三元醇,例如线型和支链脂肪醇如甘油、三羟甲基丙烷、三羟甲基乙烷、三羟甲基丁烷和1,3,5-戊三醇,芳香醇如1,2,3-苯三酚、甲基-1,2,3-苯三酚和5-二级丁基-1,2,3-苯三酚,以及这些醇的部分醚化产物;和具有4至8个官能团的醇,例如季戊四醇、双甘油、脱水山梨醇、三甘油、山梨醇、二季戊四醇、四甘油、五甘油、六甘油、三季戊四醇,以及这些醇的部分醚化产物。
在上述通式(VII)中,R16所示的含有2至4个碳原子的亚烷基可以是线型或支链亚烷基。亚烷基的具体例子包括亚乙基、亚丙基、乙基亚乙基、1,1-二甲基亚乙基和1,2-二甲基亚乙基。R18至R20所示的含有小于或等于20个碳原子的脂肪族、芳香族或芳香脂肪族烃基包括线型烷基,如甲基、乙基、丙基、丁基、戊基、庚基、辛基、壬基、癸基、十一烷基、十二烷基、十四烷基、十六烷基和十八烷基;支链烷基,如异丙基、异丁基、异戊基、2-乙基己基、异十八烷基和2-庚基十一烷基;芳基,如苯基和甲苯基;以及芳烷基,如苄基。
在通式(VII)中,s和t各自为0至30的数。当s或t大于30时,分子中醚键成分的贡献增加,所得的聚醚酮从其与氢氟烃制冷剂的相容性、电绝缘性和吸湿性考虑均不利。v代表1至8的数,w代表0至7的数。v和w的取值满足v+w的和在1至8范围内。这些数是平均数,并不限于整数。u代表0或1。以s×v表示的多个R16之间可以相同或不同。以t×v表示的多个R17之间可以相同或不同。当v大于或等于2时,v数字所示的多个s、t、u、R18和R19之间可以相同或不同。当w大于或等于2时,w数字所示的多个R20之间可以相同或不同。
作为通式(VII)所示的聚醚酮的制备方法,可选用公知的方法。例如,可选用将二级烷氧基醇用次氯酸盐和乙酸氧化的方法(日本专利申请公报No.平4(1992)-126716)或二级烷氧基醇用氢氧化锆和酮氧化的方法(日本专利申请公报No.平3(1991)-167149)。
作为前述的聚乙烯基醚,例如可选用含有通式(VIII)所示组成单元的聚乙烯基醚化合物:(其中:R21、R22和R23可以相同或不同,各自代表氢原子或含有1至8个碳原子的烃基;R24代表含有1至10个碳原子的二价烃基或含有2至20个碳原子和一个醚键氧原子的二价烃基;R25代表含有1至20个碳原子的烃基;c表示重复单元的数目,其平均值为0至10;多个组成单元中的R21至R25之间可以相同或不同;以及当含有多个R24O时,R24O之间可以相同或不同)。
也可选用由上述通式(VIII)所示组成单元和通式(IX)所示组成单元的嵌段或无规共聚物构成的聚乙烯基醚化合物:(其中R26至R29可以相同或不同,各自代表氢原子或含有1至20个碳原子的烃基;并且多个组成单元中的R26至R29之间可以相同或不同)。
在上述通式(VIII)中,R21、R22和R23可以相同或不同,各自代表氢原子或含有1至8个碳原子的烃基,优选为含有1至4个碳原子的烃基。具体的烃基的例子包括烷基,例如甲基、乙基、正丙基、异丙基、正丁基、异丁基、二级丁基、三级丁基、各种戊基、各种己基、各种庚基和各种辛基;环烷基,例如环戊基、环己基、各种甲基环己基、各种乙基环己基和各种二甲基环己基;芳基,例如苯基、各种甲苯基、各种乙苯基和各种二甲苯基;以及芳烷基,例如苄基、各种苯基乙基和各种甲基苄基。特别优选R21、R22和R23为氢原子。
在通式(VIII)中,R24代表含有1至10个碳原子,优选2至10个碳原子的二价烃基,或含有2至20个碳原子和一个醚键氧原子的二价烃基。含有1至10个碳原子的二价烃基的具体例子包括二价脂肪烃基,例如亚甲基、亚乙基、苯基亚乙基、1,2-亚丙基、2-苯基-1,2-亚丙基、1,3-亚丙基、各种亚丁基、各种亚戊基、各种亚己基、各种亚庚基、各种亚辛基、各种亚壬基和各种亚癸基;在脂环烃如环己烷、甲基环己烷、乙基环己烷、二甲基环己烷和丙基环己烷中形成两个价键而得到的亚脂环烃基;二价芳烃基,例如各种亚苯基、各种甲基亚苯基、各种乙基亚苯基、各种二甲基亚苯基和各种亚萘基;在烷基和芳基上各有一个价键的烷基芳烃例如甲苯、二甲苯和乙苯;以及在多个烷基中含有多个价键的多烷基芳烃例如二甲苯和二乙苯。在这些化合物中,特别优选含有2至4个碳原子的脂肪基。
含有2至20个碳原子和一个醚键氧原子的二价烃基的具体例子优选包括甲氧基亚甲基、甲氧基亚乙基、甲氧基甲基亚乙基、1,1-双甲氧基甲基亚乙基、1,2-双甲氧基甲基亚乙基、乙氧基甲基亚乙基、(2-甲氧基乙氧基)-甲基亚乙基和(1-甲基-2-甲氧基)甲基亚乙基。在通式(VIII)中,c表示重复单元R25O的数目,其平均值为0至10,优选为0至5。当含有多个R24O时,R24O之间可以相同或不同。
在通式(VIII)中,R25代表含有1至20个碳原子、优选1至10个碳原子的烃基。烃基的具体例子包括烷基,例如甲基、乙基、正丙基、异丙基、正丁基、异丁基、二级丁基、三级丁基、各种戊基、各种己基、各种庚基、各种辛基、各种壬基和各种癸基;环烷基,例如环戊基、环己基、各种甲基环己基、各种乙基环己基、各种丙基环己基和各种二甲基环己基;芳基,例如苯基、各种甲基苯基、各种乙基苯基、各种二甲基苯基、各种丙基苯基、各种三甲基苯基、各种丁基苯基和各种萘基;以及芳烷基,例如苄基、各种苯基乙基、各种甲基苄基、各种苯基丙基和各种苯基丁基。
多个组成单元中的R21至R25之间可以相同或不同。
含有上述通式(VIII)所示组成单元的聚乙烯基醚(1)优选的碳/氧摩尔比为4.2至7.0。当碳/氧摩尔比小于4.2时,聚乙烯基醚化合物的吸湿性过大。当碳/氧摩尔比大于7.0时,其与氢氟烃制冷剂的相容性有时会降低。
在上述通式(IX)中,R26至R29可以相同或不同,各自代表氢原子或含有1至20个碳原子的烃基。含有1至20个碳原子的烃基的例子包括那些在上述通式(VIII)中的R25的例子中所述的基团。多个组成单元中的R26至R29之间可以相同或不同。
由含有上述通式(VIII)所示组成单元和上述通式(IX)所示组成单元的嵌段或无规共聚物而构成的聚乙烯基醚化合物(2)优选其碳/氧摩尔比为4.2至7.0。当碳/氧摩尔此小于4.2时,聚乙烯基醚化合物的吸湿性过大。当碳/氧摩尔比大于7.0时,其与氢氟烃制冷剂的相容性有时会降低。
在本发明中,也可选用上述聚乙烯基醚化合物(1)和上述聚乙烯基醚化合物(2)的混合物。
本发明所用的聚乙烯基醚化合物(1)和聚乙烯基醚化合物(2)可分别通过相应的乙烯基醚单体的聚合和相应的含有烯类双键的烃类单体与相应的乙烯基醚单体的共聚合而制备。
优选下面的化合物作为本发明所用的聚乙烯基醚化合物。一种优选的化合物含有一种由通式(X)或(XI)所示的端基:(其中:R30、R31和R32可以相同或不同,各自代表氢原子或含有1至8个碳原子的烃基;R35、R36、R37和R38可以相同或不同,各自代表氢原子或含有1至20个碳原子的烃基;R33代表含有1至10个碳原子的二价烃基或含有2至20个碳原子和一个醚键氧原子的二价烃基;R34代表含有1至20个碳原子的烃基;p表示重复单元的数目,其平均值为0至10;以及当含有多个R33O时,R33O之间可以相同或不同)和另一种由通式(XII)或(XIII)所示的端基:(其中R39、R40和R41可以相同或不同,各自代表氢原子或含有1至8个碳原子的烃基;R44、R45、R46和R47可以相同或不同,各自代表氢原子或含有1至20个碳原子的烃基;R42代表含有1至10个碳原子的二价烃基或含有2至20个碳原子和一个醚键氧原子的二价烃基;R43代表含有1至20个碳原子的烃基;q表示重复单元的数目,其平均值为0至10;以及当含有多个R42O时,R42O之间可以相同或不同)。
在上述聚乙烯基醚化合物中,特别优选下面的化合物作为本发明制冷机油的基油。
(1)一个端基具有通式(X)或(XI)所示的结构,另一个端基具有通式(XII)或(XIII)所示的结构,以及在通式(VIII)中,R21、R22和R23都代表氢原子,c代表0至4的数,R24代表含有2至4个碳原子的二价烃基,和R25代表含有1至20个碳原子的烃基的化合物。
(2)含有仅由通式(VIII)所示组成单元的化合物,其中一个端基具有通式(X)所示的结构,另一个端基具有通式(XII)所示的结构,以及在通式(VIII)中,R21、R22和R23都代表氢原子,c代表0至4的数,R24代表含有2至4个碳原子的二价烃基,和R25代表含有1至20个碳原子的烃基的化合物。
(3)一个端基具有通式(X)或(XI)所示的结构,另一个端基具有通式(XIV)所示的结构,以及在通式(VIII)中,R21、R22和R23都代表氢原子,c代表0至4的数,R24代表含有2至4个碳原子的二价烃基,和R25代表含有1至20个碳原子的烃基的化合物。
(4)含有仅由通式(VIII)所示组成单元的化合物,其中一个端基具有通式(X)所示的结构,另一个端基具有通式(XIII)所示的结构,以及在通式(VIII)中,R21、R22和R23都代表氢原子,c代表0至4的数,R24代表含有2至4个碳原子的二价烃基,和R25代表含有1至20个碳原子的烃基的化合物。
在本发明中,也可选用含有上述通式(VIII)所示组成单元,通式(X)所示的一个端基,和通式(XV)所示的另一个端基的聚乙烯基醚化合物:(其中:R51、R52和R53可以相同或不同,各自代表氢原子或含有1至8个碳原子的烃基;R54和R56可以相同或不同,各自代表含有2至10个碳原子的二价烃基;R55和R57各自代表含有1至10个碳原子的烃基;d和y可以相同或不同,各自表示重复单元的数目,其平均值为0至10;当含有多个R54O时,R54O之间可以相同或不同;以及当含有多个R56O时,R56O之间可以相同或不同)。此外,在本发明中还可选用由含有通式(XVI)或(XVII)所示组成单元的烷基乙烯基醚的均聚物或共聚物所构成的聚乙烯基醚化合物:(其中R58代表含有1至8个碳原子的烃基),其分子量为300至1200,含有一个由通式(XVIII)或(XIX)所示的端基:
-CH=CHOR60 …(XIX)(其中R59代表含有1至3个碳原子的烷基,和R60代表含有1至8个碳原子的烃基)。
作为聚乙烯基醚化合物,也可选用下述专利申请中详细公开的化合物,如日本专利申请公报No.平成6(1994)-128578,日本专利申请No.平成5(1993)-125649(公报No.平成6(1994)-234814),日本专利申请No.平成5(1993)-125650(公报No.平成6(1994)234815),日本专利申请No.平成5(1993)-303736,日本专利申请No.平成6(1994)-280371,和日本专利申请No.平成6(1994)-283349。
作为前述碳酸酯衍生物,例如可选用通式(XX)所示的聚碳酸酯:(其中:R61和R63可以相同或不同,各自代表含有小于或等于30个碳原子的烃基或含有2至30个碳原子和一个醚键的烃基,R62代表含有2至24个碳原子的亚烷基,f代表1至100的整数,和g代表1至10的整数)。
在上面通式(XX)中,R61和R63各自代表含有小于或等于30个碳原子的烃基或含有2至30个碳原子和一个醚键的烃基。含有小于或等于30个碳原子的烃基的具体例子包括脂肪烃基,例如甲基、乙基、正丙基、异丙基、正丁基、异丁基、二级丁基、三级丁基、戊基、异戊基、新戊基、正己基、1,3-二甲基丁基、2,3-二甲基丁基、异己基、正庚基、异庚基、3-甲基己基、正辛基、2-乙基己基、异辛基、正壬基、异壬基、正癸基、异癸基、正十一烷基、异十一烷基、正十二烷基、异十二烷基、正十三烷基、异十三烷基、正十四烷基、异十四烷基、正十五烷基、异十五烷基、正十六烷基、异十六烷基、正十七烷基、异十七烷基、正十八烷基、异十八烷基、正十九烷基、异十九烷基、正二十烷基、异二十烷基和2-(4-甲基戊基);脂环烃基,例如环己基、1-环己烯基、甲基环己基、二甲基环己基、十氢萘基和三环癸基;芳香烃基,例如苯基、邻甲苯基、对甲苯基、间甲苯基、2,4-二甲苯基、2,4,6-三甲苯基和1-萘基;以及芳脂烃基,例如苄基、甲基苄基、β-苯基乙基(苯乙基)1-苯基乙基、1-甲基-1-苯基乙基、对甲基苄基、苯乙烯基和肉桂基。
作为含有2至30个碳原子和一个醚键的烃基,例如可包括通式(XXI)所示的二醇醚基:
-(R64-O)h-R65 …(XXI(其中:R64代表含有2或3个碳原子的亚烷基,例如亚乙基、亚丙基和1,3-亚丙基,R65代表含有小于或等于28个碳原子的脂肪、脂环或芳香烃基,例如上述R61和R63所代表的基团的例子,和h代表1至20的整数)。通式(XXI)所示的二醇醚基团的具体例子包括乙二醇单甲醚基团、乙二醇单丁醚基团、二乙二醇单正丁醚基团、三乙二醇单乙醚基团、丙二醇单甲醚基团、丙二醇单丁醚基团、二丙二醇单乙醚基团和三丙二醇单正丁醚基团。在上述基团中,优选烷基,例如正丁基、异丁基、异戊基、环己基、异庚基、3-甲基己基、1,3-二甲基丁基、己基、辛基和2-乙基己基;和亚烷基二醇单烷基醚基团,例如乙二醇单甲醚基团、乙二醇单丁醚基团、二乙二醇单甲醚基团、三乙二醇单甲醚基团、丙二醇单甲醚基团、丙二醇单丁醚基团、二丙二醇单乙醚基团和三丙二醇单正丁醚基团。
上述R68和R63可以是相同或不同。
在上述通式(XX)中,R62代表含有2至24个碳原子的亚烷基。亚烷基的具体例子包括亚乙基、亚丙基、亚丁基、亚戊基、甲基亚戊基、乙基亚戊基、亚己基、甲基亚己基、乙基亚己基、1,8-亚辛基、1,9-亚壬基、1,10-亚癸基、1,12-亚十二烷基和1,14-亚十四烷基。f代表1至100的整数,和g代表1至10的整数。当含有多个R62O时,R62O之间可以相同或不同。
通式(XX)所示的聚碳酸酯优选其分子量(重均分子量)为300至3000,特别是400至1500。当分子量低于300时,聚碳酸酯的运动粘度小于期望值,不能作为优选的润滑剂使用。当分子量超过3000时,聚碳酸酯呈蜡状,很难用作润滑剂。
可用多种方法来制备聚碳酸酯。一般可用碳酸二酯或可形成碳酸二酯的衍生物如光气与脂肪二元醇为原料来制备聚碳酸酯。
可选用通常制备聚碳酸酯的方法从上述原料制备聚碳酸酯。一般地,可选用酯基转移法或光气法。
作为聚碳酸酯,还可选用日本专利申请公报No.平成3(1991)-217495中详细公开的化合物。
作为碳酸酯衍生物,也可选用通式(XXII)所示的二醇醚碳酸酯:
R66-O-(R68O)i-CO-(OR69)j-O-R67 …(XXII)(其中:R66和R67可以相同或不同,各自代表含有1至20个碳原子的脂肪、脂环、芳香或芳脂烃基,R68和R69可以相同或不同,各自代表亚乙基或亚异丙基,以及i和j各自代表1至100的数)。
在上面通式(XXII)中,R66和R67代表的脂肪烃基的具体例子包括甲基、乙基、丙基、异丙基、异丁基、二级丁基、三级丁基、戊基、异戊基、新戊基、正己基、异己基、正庚基、异庚基、正辛基、异辛基、正壬基、异壬基、正癸基、异癸基、正十一烷基、异十一烷基、正十二烷基、异十二烷基、正十三烷基、异十三烷基、正十四烷基、异十四烷基、正十五烷基、异十五烷基、正十六烷基、异十六烷基、正十七烷基、异十七烷基、正十八烷基、异十八烷基、正十九烷基、异十九烷基、正二十烷基和异二十烷基。脂环烃基的具体的例子包括环己基、1-环己烯基、甲基环己基、二甲基环己基、十氢萘基和三环癸基。芳香烃基的具体的例子包括苯基、邻甲苯基、对甲苯基、间甲苯基、2,4-二甲苯基、2,4,6-三甲苯基和1-萘基。芳脂烃基的具体例子包括苄基、甲基苄基、苯基乙基、苯乙烯基和肉桂基。
上述通式(XXII)所示二醇醚碳酸酯例如可如下制备,使聚亚烷基二醇单烷基醚在过量的相对较低沸点醇的碳酸酯的存在下发生酯基转移反应。
作为上述二醇醚碳酸酯,也可选用日本专利申请公报No.平成3(1991)-149295中详细公开的化合物。
作为碳酸酯衍生物,还可选用由通式(XXIII)所示的碳酸酯:(其中:R70和R71可以相同或不同,各自代表含有1至15个碳原子的烷基或含有2至12个碳原子的二元醇的残基,R72代表含有2至12个碳原子的亚烷基,以及r代表0至30的整数)。
在上述通式(XXIII)中,R70和R71各自代表含有1至15个碳原子、优选2至9个碳原子的烷基,或含有2至12个碳原子、优选2至9个碳原子的二元醇的残基,R72代表含有2至12个碳原子、优选2至9个碳原子的亚烷基,以及r代表0至30、优选1至30的整数。不满足这些条件的碳酸酯不是优选的,因为所得的产品的各种性能较差,例如与氢氟烃的相容性差。R70和R71代表的含有1至15个碳原子的烷基的具体例子包括甲基、乙基、正丙基、正丁基、正戊基、正己基、正庚基、正辛基、正壬基、正癸基、正十一烷基、正十二烷基、正十三烷基、正十四烷基、正十五烷基、异丙基、异丁基、三级丁基、异戊基、异己基、异庚基、异辛基、异壬基、异癸基、异十一烷基、异十二烷基、异十三烷基、异十四烷基和异十五烷基。
含有2至12个碳原子的二元醇的残基的具体例子包括以下二元醇形成的残基:乙二醇、1,3-丙二醇、1,2-丙二醇、1,4-丁二醇、1,2-丁二醇、2-甲基-1,3-丙二醇、1,5-戊二醇、新戊二醇、1,6-己二醇、2-甲基-2-乙基-1,3-丙二醇、1,7-庚二醇、2-甲基-2-丙基-1,3-丙二醇、2,2-二乙基-1,3-丙二醇、1,8-辛二醇、1,9-壬二醇、1,10-癸二醇、1,11-十一烷二醇和1,12-十二烷二醇。
由R72代表的含有2至12个碳原子的亚烷基的具体例子包括线型或支链结构的亚烷基,例如亚乙基、1,3-亚丙基、1,2-亚丙基、1,4-亚丁基、1,2-亚丁基、2-甲基-1,3-亚丙基、1,5-亚戊基、2,2-二甲基-1,3-业丙基、1,6-亚己基、2-甲基-2-乙基-1,3-亚丙基、1,7-亚庚基、2-甲基-2-丙基-1,3-亚丙基、2,2-二乙基-1,3-亚丙基、1,8-亚辛基、1,9-亚壬基、1,10-亚癸基、1,11-亚十一烷基和1,12-亚十二烷基。
对上述碳酸酯的分子量不做特别地限定。优选数均分子量为200至3000的碳酸酯,因为其对压缩机有优良的密封性。特别优选数均分子量为300至2000的碳酸酯。
作为上述碳酸酯,也可选用日本专利申请公报No.平成4(1992)-63893中详细公开的化合物。
在上述含氧化合物中,特别优选聚亚烷基二醇、多元醇酯和聚乙烯基醚,因为它们具有与氢氟烃制冷剂优良的相容性和对起泡现象优良的抑制作用。含氧有机化合物可以单独使用,或两种或多种混合使用。
本发明的制冷机油可用于采用各种制冷剂的制冷机中,优选用于采用氢氟烃制冷剂的制冷机。氢氟烃制冷剂的例子包括1,1,1,2-四氟乙烷(R134a)、1,1,2,2-四氟乙烷(R134)、1,1,1-三氟乙烷(R143a)、1,1-二氟乙烷(R152a)、五氟乙烷(R125)、二氟甲烷(R32)、三氟甲烷(R23)以及这些化合物的混合物。当本发明的制冷机油用于采用1,1,1,2-四氟乙烷一种制冷剂、或含有二氟甲烷的混合制冷剂、或含有2-四氟乙烷的混合制冷剂的制冷体系时,能够获得对起泡现象特别好的抑制效果。混合制冷剂的具体例子包括R407c(R134a、R125和R32的混合物)、R404a(R134a、R125和R143a的混合物)、R410a(R32和R125的混合物),以及R32和R134a的混合物。
本发明的制冷机油也可用于采用上述氢氟烃制冷剂之外的制冷剂的制冷机中。非上述氢氟烃制冷剂的制冷剂的例子包括含有2至8个碳原子的醚(优选二甲醚、二乙醚和甲乙醚)、氨、二氧化碳,以及含有1至8个碳原子的烃例如烷烃和烯烃(优选含有3或4个碳原子的烃如丙烷和丁烷)。可将两种或两种以上的制冷剂混合使用。例如,可选用氢氟烃制冷剂与非氢氟烃制冷剂的制冷剂的混合物。也可能将两种或两种以上的非氢氟烃制冷剂混合使用。
在本发明的制冷机油中,根据需要可加入各种通常的添加剂,例如耐特压添加剂如磷酸酯和亚磷酸酯,酚类抗氧剂,胺类抗氧剂,稳定剂如苯基缩水甘油基醚、氧化环己烯、环氧化豆油和其它环氧化合物,以及对金属铜的非活性剂如苯并三唑和苯并三唑衍生物。
本发明也提供一种在压缩式制冷系统中采用含有前述氟化硅油的制冷机油来进行润滑的制冷系统的润滑方法,特别是在采用氢氟烃制冷剂的压缩式制冷系统中。根据上述方法,溶于制冷机油中的制冷剂在沸腾时的起泡现象能够得到抑制,从而防止制冷机油大量地流入制冷系统中,并能保持制冷系统良好的功效。
本发明通过实施例得到更为详细的说明。然而,本发明不受这些实施例的限制。实施例1至30和比较实施例1至18
在一内径为55毫米、高为30厘米的耐压玻璃容器中加入表1所列的制冷机油和制冷剂各75毫升。在室温和制冷剂的平衡压力下用叶片式搅拌器将混合物充分搅拌(每分钟1380转),容器内的压力很快降至大气压。测量由于减压而形成的泡沫的高度。根据下面的标准对实验结果进行评估。结果评估标准
◎:泡沫高度小于或等于5厘米。
○:泡沫高度大于5厘米但小于或等于10厘米。
△:泡沫高度大于10厘米但小于或等于20厘米。
×:泡沫高度大于20厘米。基油、消泡剂和制冷剂选用下列原料。(1)基油酯油:季戊四醇的羧酸酯(VG32和VG68)PVE油:聚乙烯基醚油(VG68)PAG油:主链含有氧亚丙基和氧亚乙基的改性聚亚烷基二醇(VG46)聚碳酸酯油:(VG56)烷基苯油:(VG56)PAO油:聚α-烯烃(VG68)矿物油:(VG32)
括号内符号数字表示根据日本工业标准的上述基油的等级。(2)消泡剂A:R1至R7:甲基,R8:氟化丙基
运动粘度:500毫米2/秒(25℃)B:R1至R7:甲基,R8:氟化丙基
运动粘度:1000毫米2/秒(25℃)C:R1至R7:甲基,R8:氟化丙基
运动粘度:10000毫米2/秒(25℃)D:R1至R6:甲基,R7和R8:氟化丙基
运动粘度:1000毫米2/秒(25℃)E:R1至R5:甲基,R6至R8:氟化丙基
运动粘度:1000毫米2/秒(25℃)F:R1至R3和R5至R7:甲基,R4:氟化己基,R8:氟化丙基
运动粘度:1000毫米2/秒(25℃)G:R1至R7:甲基,R8:氟化丙基
运动粘度:170毫米2/秒(25℃)
上述油为通式(I)所示的氟化硅油。II:硅油(二甲基硅氧烷)
运动粘度:10000毫米2/秒(25℃)I:硅油(二甲基硅氧烷)
运动粘度:100000毫米2/秒(25℃)(3)制冷剂R134a:1,1,1,2-四氟乙烷R407c:1,1,1,2-四氟乙烷、五氟乙烷和二氟甲烷的混合物R22:一氯二氟甲烷
表1-1
制冷机油实施例 基油 消泡剂 制冷剂 评价
类型 类型 ppm(重量) 类型 结果1 酯油(VG32) B 100 R134a ◎2 酯油(VG32) D 100 R134a ◎3 酯油(VG32) E 100 R134a ◎4 酯油(VG32) F 100 R134a ◎5 酯油(VG68) A 100 R407c ◎6 酯油(VG68) B 100 R407c ◎7 酯油(VG68) C 100 R407c ◎8 酯油(VG68) D 100 R407c ◎9 酯油(VG68) E 100 R407c ◎10 酯油(VG68) F 100 R407c ◎11 PVE油(VG68) B 100 R134a ◎12 PVE油(VG68) D 100 R134a ◎13 PVE油(VG68) E 100 R134a ◎14 PVE油(VG68) F 100 R134a ◎15 PVE油(VG68) C 100 R32 ◎16 PVE油(VG68) C 100 R32/R134a ◎
(3/7)
表1-2
制冷机油实施例 基油 消泡剂 制冷剂 评价
类型 类型 ppm(重量) 类型 结果17 PVE油(VG68) A 1000 R407c ◎18 PVE油(VG68) B 100 R407c ◎19 PVE油(VG68) C 10 R407c ◎20 PVE油(VG68) D 100 R407c ◎21 PVE油(VG68) E 100 R407c ◎22 PVE油(VG68) F 100 R407c ◎23 PAG油(VG46) B 100 R134a ◎24 PAG油(VG46) D 100 R134a ◎25 PAG油(VG46) E 100 R134a ◎26 PAG油(VG46) F 100 R134a ◎27 聚碳酸酯油 B 100 R134a ◎
(VG46)28 聚碳酸酯油 D 100 R134a ◎
(VG46)29 聚碳酸酯油 E 100 R134a ◎
(VG46)30 聚碳酸酯油 F 100 R134a ◎
(VG46)
表1-3
制冷机油比较实施例 基油 消泡剂 制冷剂 评价
类型 类型 ppm(重量) 类型 结果
1 PVE油(VG68) H 10 R22 ○
2 酯油(VG68) H 10 R22 ○
3 PVE油(VG68) - - R407c ×
4 PVE油(VG68) I 100 R407c ×
5 酯油(VG68) - - R407c ×
6 酯油(VG68) I 100 R407c ×
7 PAG油(VG46) I 100 R404c ×
8 聚碳酸酯油(VG56) I 100 R407c ×
9 PVE油(VG68) H 10 R134a ×
10 酯油(VG32) H 10 R134a ×
11 PVE油(VG68) G 100 R407c ×
12 PVE油(VG68) G 10000 R407c ×
13 烷基苯油(VG56) B 100 R407c ×
14 PAO油(VG68) B 100 R407c ×
15 PVE油(VG68) A 100 R22 △
16 PVE油(VG68) B 100 R22 △
17 PVE油(VG68) C 100 R22 △
18 矿物油 I 100 R22 ○
工业实用性
本发明的制冷机油能够有效地抑制溶于制冷机油中的制冷剂在沸腾时的起泡现象,可与各种制冷剂、特别是由单一氢氟烃构成的制冷剂或两种或两种以上的氢氟烃构成的混合制冷剂组合使用。采用本发明的制冷机油作为压缩式制冷系统的润滑剂,能够保持制冷系统良好的功效。
Claims (6)
1、一种制冷机油,它含有由含氧有机化合物构成的基油和25℃下运动粘度为不低于500毫米2/秒的氟化硅油,其中所述含氧有机化合物为聚亚烷基二醇、聚酯、聚醚酮、聚乙烯基醚或碳酸酯衍生物,所述氟化硅油为由通式(I)所示的化合物:其中:R1至R6可以相同或不同,各自代表氢原子或烃基;R7和R8各自代表烃基或氟化烃基,R7和R8中至少一个为氟化烃基,且多个重复单元中的R7和R8可以相同或不同;和n表示一整数,其取值大小使氟化硅油在25℃下的运动粘度为不低于500毫米2/秒;
并且其中氟化硅油在制冷机油中的含量为1至6000ppm(重量)。
2、根据权利要求1的制冷机油,其中氟化硅油在25℃下的运动粘度(毫米2/秒)与氟化硅油在制冷机油中的含量(ppm,重量)的乘积为50000至3000000。
3、根据权利要求1的制冷机油,其中制冷机油用于采用至少一种选自氢氟烃制冷剂、含有2至8个碳原子的醚制冷剂、氨制冷剂、含有1至8个碳原子的烃类制冷剂和二氧化碳制冷剂中的制冷剂的制冷机中。
4、根据权利要求1的制冷机油,其中制冷机油用于采用氢氟烃制冷剂作为制冷剂的制冷机中。
5、根据权利要求4的制冷机油,其中氢氟烃制冷剂为选自1,1,1,2-四氟乙烷、1,1,2,2-四氟乙烷、1,1,1-三氟乙烷、1,1-二氟乙烷、五氟乙烷、二氟甲烷和三氟甲烷中的至少一种化合物。
6、权利要求1所述的制冷机油用于润滑压缩式制冷系统的用途。
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- 1996-07-01 US US08/973,876 patent/US6013609A/en not_active Expired - Lifetime
- 1996-07-01 DE DE69630040T patent/DE69630040T2/de not_active Expired - Fee Related
- 1996-07-01 KR KR10-1998-0700154A patent/KR100433332B1/ko not_active IP Right Cessation
- 1996-07-01 RU RU98102354/04A patent/RU2161642C2/ru not_active IP Right Cessation
- 1996-07-01 AU AU62434/96A patent/AU704899B2/en not_active Ceased
- 1996-07-01 EP EP96921133A patent/EP0844299B1/en not_active Expired - Lifetime
- 1996-07-01 WO PCT/JP1996/001817 patent/WO1997003153A1/ja active IP Right Grant
- 1996-07-08 TW TW085108251A patent/TW460574B/zh not_active IP Right Cessation
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
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US4946611A (en) * | 1987-12-11 | 1990-08-07 | Idemitsu Kosan Co., Ltd. | Refrigerator oil containing fluorinated siloxane compounds |
US5084196A (en) * | 1988-01-29 | 1992-01-28 | Idemitsu Kosan Company Limited | Lubricating oil composition for flon atmosphere comprising a polysiloxane having epoxy structure |
CN1064884A (zh) * | 1991-03-15 | 1992-09-30 | 上海高桥石油化工公司炼油厂 | 双组分高效抗泡剂及其应用 |
CN1086536A (zh) * | 1992-10-29 | 1994-05-11 | 高翔 | 极压节能复合型纱锭专用油 |
Also Published As
Publication number | Publication date |
---|---|
US6013609A (en) | 2000-01-11 |
WO1997003153A1 (en) | 1997-01-30 |
BR9609579A (pt) | 1999-02-23 |
KR19990028853A (ko) | 1999-04-15 |
KR100433332B1 (ko) | 2004-08-12 |
TW460574B (en) | 2001-10-21 |
EP0844299A1 (en) | 1998-05-27 |
EP0844299B1 (en) | 2003-09-17 |
CN1190429A (zh) | 1998-08-12 |
DE69630040D1 (de) | 2003-10-23 |
AU704899B2 (en) | 1999-05-06 |
DE69630040T2 (de) | 2004-04-08 |
AU6243496A (en) | 1997-02-10 |
RU2161642C2 (ru) | 2001-01-10 |
EP0844299A4 (en) | 1999-11-17 |
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