CN1205357A - 冷冻机油组合物 - Google Patents
冷冻机油组合物 Download PDFInfo
- Publication number
- CN1205357A CN1205357A CN98107731A CN98107731A CN1205357A CN 1205357 A CN1205357 A CN 1205357A CN 98107731 A CN98107731 A CN 98107731A CN 98107731 A CN98107731 A CN 98107731A CN 1205357 A CN1205357 A CN 1205357A
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- group
- oil composition
- carbon atoms
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- ether
- Prior art date
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- 239000000203 mixture Substances 0.000 title claims abstract description 75
- 239000010721 machine oil Substances 0.000 title abstract description 8
- 239000003921 oil Substances 0.000 claims abstract description 86
- 229920001515 polyalkylene glycol Polymers 0.000 claims abstract description 28
- 239000002199 base oil Substances 0.000 claims abstract description 24
- 150000002334 glycols Chemical class 0.000 claims abstract description 20
- 239000000126 substance Substances 0.000 claims abstract description 12
- 125000004432 carbon atom Chemical group C* 0.000 claims description 125
- 150000001875 compounds Chemical class 0.000 claims description 42
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 38
- 125000001931 aliphatic group Chemical group 0.000 claims description 32
- 125000002947 alkylene group Chemical group 0.000 claims description 28
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 27
- 150000005846 sugar alcohols Polymers 0.000 claims description 18
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 16
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 13
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims description 12
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 claims description 12
- 125000002252 acyl group Chemical group 0.000 claims description 12
- 229920005862 polyol Polymers 0.000 claims description 12
- 239000000600 sorbitol Substances 0.000 claims description 12
- GPLRAVKSCUXZTP-UHFFFAOYSA-N diglycerol Chemical compound OCC(O)COCC(O)CO GPLRAVKSCUXZTP-UHFFFAOYSA-N 0.000 claims description 11
- AGNTUZCMJBTHOG-UHFFFAOYSA-N 3-[3-(2,3-dihydroxypropoxy)-2-hydroxypropoxy]propane-1,2-diol Chemical compound OCC(O)COCC(O)COCC(O)CO AGNTUZCMJBTHOG-UHFFFAOYSA-N 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- 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 claims description 9
- PTJWCLYPVFJWMP-UHFFFAOYSA-N 2-[[3-hydroxy-2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)COCC(CO)(CO)CO PTJWCLYPVFJWMP-UHFFFAOYSA-N 0.000 claims description 8
- 150000003077 polyols Chemical class 0.000 claims description 6
- 125000005156 substituted alkylene group Chemical group 0.000 claims description 5
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 4
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 claims description 3
- HEBKCHPVOIAQTA-QWWZWVQMSA-N D-arabinitol Chemical compound OC[C@@H](O)C(O)[C@H](O)CO HEBKCHPVOIAQTA-QWWZWVQMSA-N 0.000 claims description 3
- 239000004386 Erythritol Substances 0.000 claims description 3
- UNXHWFMMPAWVPI-UHFFFAOYSA-N Erythritol Natural products OCC(O)C(O)CO UNXHWFMMPAWVPI-UHFFFAOYSA-N 0.000 claims description 3
- 229930195725 Mannitol Natural products 0.000 claims description 3
- UNXHWFMMPAWVPI-ZXZARUISSA-N erythritol Chemical compound OC[C@H](O)[C@H](O)CO UNXHWFMMPAWVPI-ZXZARUISSA-N 0.000 claims description 3
- 235000019414 erythritol Nutrition 0.000 claims description 3
- 229940009714 erythritol Drugs 0.000 claims description 3
- 239000000594 mannitol Substances 0.000 claims description 3
- 235000010355 mannitol Nutrition 0.000 claims description 3
- HEBKCHPVOIAQTA-UHFFFAOYSA-N meso ribitol Natural products OCC(O)C(O)C(O)CO HEBKCHPVOIAQTA-UHFFFAOYSA-N 0.000 claims description 3
- 239000003507 refrigerant Substances 0.000 abstract description 45
- 238000002156 mixing Methods 0.000 abstract description 11
- 239000000463 material Substances 0.000 abstract description 10
- 229910000831 Steel Inorganic materials 0.000 abstract description 7
- 229910052782 aluminium Inorganic materials 0.000 abstract description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 7
- 239000010959 steel Substances 0.000 abstract description 7
- 230000001050 lubricating effect Effects 0.000 abstract description 6
- 238000003912 environmental pollution Methods 0.000 abstract description 5
- KYKAJFCTULSVSH-UHFFFAOYSA-N chloro(fluoro)methane Chemical compound F[C]Cl KYKAJFCTULSVSH-UHFFFAOYSA-N 0.000 abstract description 4
- -1 polyol ester Chemical class 0.000 description 147
- 150000002430 hydrocarbons Chemical class 0.000 description 72
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 64
- 235000019198 oils Nutrition 0.000 description 59
- 125000000217 alkyl group Chemical group 0.000 description 32
- 229920001289 polyvinyl ether Polymers 0.000 description 29
- 239000000178 monomer Substances 0.000 description 24
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 22
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 21
- 239000001301 oxygen Substances 0.000 description 21
- 229910052760 oxygen Inorganic materials 0.000 description 21
- 239000000470 constituent Substances 0.000 description 18
- 238000006116 polymerization reaction Methods 0.000 description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 14
- 229910052799 carbon Inorganic materials 0.000 description 14
- 150000001735 carboxylic acids Chemical class 0.000 description 14
- 229920001451 polypropylene glycol Polymers 0.000 description 14
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 12
- VOPWNXZWBYDODV-UHFFFAOYSA-N Chlorodifluoromethane Chemical compound FC(F)Cl VOPWNXZWBYDODV-UHFFFAOYSA-N 0.000 description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 12
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 12
- 235000011187 glycerol Nutrition 0.000 description 12
- 229930195733 hydrocarbon Natural products 0.000 description 12
- 229920000642 polymer Polymers 0.000 description 12
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 11
- 229920005604 random copolymer Polymers 0.000 description 11
- 239000004215 Carbon black (E152) Substances 0.000 description 10
- 150000001298 alcohols Chemical class 0.000 description 10
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 10
- 229920002554 vinyl polymer Polymers 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 9
- 125000003118 aryl group Chemical group 0.000 description 9
- 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 9
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 9
- 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 9
- 239000000047 product Substances 0.000 description 9
- 239000002253 acid Substances 0.000 description 8
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 8
- 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 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 8
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 8
- 125000005702 oxyalkylene group Chemical group 0.000 description 8
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 8
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 7
- 150000001241 acetals Chemical class 0.000 description 7
- 239000000654 additive Substances 0.000 description 7
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 7
- 125000003710 aryl alkyl group Chemical group 0.000 description 7
- 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
- 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 7
- 230000000694 effects Effects 0.000 description 7
- 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 7
- 150000002989 phenols Chemical class 0.000 description 7
- 125000003944 tolyl group Chemical group 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 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
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 6
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 6
- 239000002480 mineral oil Substances 0.000 description 6
- 229920000515 polycarbonate Polymers 0.000 description 6
- 239000004417 polycarbonate Substances 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 238000005057 refrigeration Methods 0.000 description 6
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 5
- 239000002202 Polyethylene glycol Substances 0.000 description 5
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 5
- 238000005299 abrasion Methods 0.000 description 5
- 125000003158 alcohol group Chemical group 0.000 description 5
- 125000002723 alicyclic group Chemical group 0.000 description 5
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 5
- 229920001400 block copolymer Polymers 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 230000006835 compression Effects 0.000 description 5
- 238000007906 compression Methods 0.000 description 5
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 5
- 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 5
- 150000002148 esters Chemical class 0.000 description 5
- 150000002170 ethers Chemical class 0.000 description 5
- 239000010687 lubricating oil Substances 0.000 description 5
- 235000010446 mineral oil Nutrition 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
- 229920000728 polyester Polymers 0.000 description 5
- 229920001223 polyethylene glycol Polymers 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- 125000004079 stearyl 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])C([H])([H])C([H])([H])[H] 0.000 description 5
- 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 5
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 4
- BCXIOLDAECLTCX-UHFFFAOYSA-N 1-methoxy-2-nonylbenzene Chemical compound CCCCCCCCCC1=CC=CC=C1OC BCXIOLDAECLTCX-UHFFFAOYSA-N 0.000 description 4
- WMYINDVYGQKYMI-UHFFFAOYSA-N 2-[2,2-bis(hydroxymethyl)butoxymethyl]-2-ethylpropane-1,3-diol Chemical compound CCC(CO)(CO)COCC(CC)(CO)CO WMYINDVYGQKYMI-UHFFFAOYSA-N 0.000 description 4
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical group CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 4
- SZNYYWIUQFZLLT-UHFFFAOYSA-N 2-methyl-1-(2-methylpropoxy)propane Chemical compound CC(C)COCC(C)C SZNYYWIUQFZLLT-UHFFFAOYSA-N 0.000 description 4
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 4
- 125000004122 cyclic group Chemical group 0.000 description 4
- RWRIWBAIICGTTQ-UHFFFAOYSA-N difluoromethane Chemical compound FCF RWRIWBAIICGTTQ-UHFFFAOYSA-N 0.000 description 4
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 4
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 4
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 4
- KQNPFQTWMSNSAP-UHFFFAOYSA-N isobutyric acid Chemical compound CC(C)C(O)=O KQNPFQTWMSNSAP-UHFFFAOYSA-N 0.000 description 4
- FGKJLKRYENPLQH-UHFFFAOYSA-N isocaproic acid Chemical compound CC(C)CCC(O)=O FGKJLKRYENPLQH-UHFFFAOYSA-N 0.000 description 4
- 125000002960 margaryl 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])C([H])([H])[H] 0.000 description 4
- 125000006178 methyl benzyl group Chemical group 0.000 description 4
- FBUKVWPVBMHYJY-UHFFFAOYSA-N nonanoic acid Chemical compound CCCCCCCCC(O)=O FBUKVWPVBMHYJY-UHFFFAOYSA-N 0.000 description 4
- 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 4
- 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 4
- 125000002889 tridecyl 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])[H] 0.000 description 4
- ZDPHROOEEOARMN-UHFFFAOYSA-N undecanoic acid Chemical compound CCCCCCCCCCC(O)=O ZDPHROOEEOARMN-UHFFFAOYSA-N 0.000 description 4
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 4
- OBETXYAYXDNJHR-SSDOTTSWSA-M (2r)-2-ethylhexanoate Chemical compound CCCC[C@@H](CC)C([O-])=O OBETXYAYXDNJHR-SSDOTTSWSA-M 0.000 description 3
- LTYFSBBFLJKQRQ-UHFFFAOYSA-N 1,2-di(butan-2-yl)-3-methoxybenzene Chemical compound CCC(C)C1=CC=CC(OC)=C1C(C)CC LTYFSBBFLJKQRQ-UHFFFAOYSA-N 0.000 description 3
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 3
- 229940035437 1,3-propanediol Drugs 0.000 description 3
- MQGIBEAIDUOVOH-UHFFFAOYSA-N 1-[2-[2-[2-(2-butoxyethoxy)ethoxy]ethoxy]ethoxy]butane Chemical compound CCCCOCCOCCOCCOCCOCCCC MQGIBEAIDUOVOH-UHFFFAOYSA-N 0.000 description 3
- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-heptanol Chemical class CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 description 3
- BRIKTKRHROTQFO-UHFFFAOYSA-N 1-methoxynonane Chemical compound CCCCCCCCCOC BRIKTKRHROTQFO-UHFFFAOYSA-N 0.000 description 3
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 3
- OILUAKBAMVLXGF-UHFFFAOYSA-N 3,5,5-trimethyl-hexanoic acid Chemical compound OC(=O)CC(C)CC(C)(C)C OILUAKBAMVLXGF-UHFFFAOYSA-N 0.000 description 3
- AWQSAIIDOMEEOD-UHFFFAOYSA-N 5,5-Dimethyl-4-(3-oxobutyl)dihydro-2(3H)-furanone Chemical compound CC(=O)CCC1CC(=O)OC1(C)C AWQSAIIDOMEEOD-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- 239000007848 Bronsted acid Substances 0.000 description 3
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 239000002841 Lewis acid Substances 0.000 description 3
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical class CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 3
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 3
- 239000007983 Tris buffer Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 description 3
- 125000005037 alkyl phenyl group Chemical group 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
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Classifications
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Abstract
本发明的冷冻机油组合物是在(A)合成油构成的基油中配入(B)数均分子量200~3000的化学式为R1-(OR2)m-(OR3)n-OR4的聚亚烷基二醇衍生物而构成。式中R1、R2、R3、R4、m和n的含义如说明书所述。本发明的冷冻机油组合物可以代替造成环境污染的含氯氟烃制冷剂,具有良好的润滑性能,尤其可以改善铝和钢材之间的润滑性,减小磨损并且不易造成毛细管堵塞。
Description
本发明是关于冷冻机油组合物,更具体地说,本发明是关于在使用可以可以替代造成环境污染的含氯氟烃制冷剂的氢氟碳系、氟碳系、烃系、醚系、二氧化碳系或氨系制冷剂等时,具有良好的润滑性能,尤其可以改善铝和钢材之间的润滑性,减小磨损并且不易造成毛细管堵塞的冷冻机油组合物。
一般地说,压缩式冷冻机至少由压缩机、冷凝器、膨胀机构(膨胀阀)、蒸发器或者还有干燥器构成,制冷剂与润滑油的混合液体在该密闭的系统内循环。以往,压缩式冷冻机、特别是空调器的制冷剂大多使用氯二氟甲烷(以下简称R22)或氯二氟甲烷与氯五氟乙烷的48.8∶51.2(重量比)的混合物(以下简称R502),另外,润滑油使用满足上述要求特性的各种矿物油或合成油。但是,R22和R502有可能破坏平流层中的臭氧,造成环境污染,因此,最近在全世界范围内受到越来越严格的限制。鉴于上述情况,作为新的制冷剂,以1,1,1,2-四氟乙烷、二氟甲烷、五氟乙烷、1,1,1-三氟乙烷(以下分别简称为R134a、R32、R125、R143a)为代表的氢氟碳受到人们的关注。该氢氟碳特别是R134a、R32、R125、R143a不会破坏臭氧层,适合作为压缩式冷冻机的制冷剂。但是,在单独使用上述氢氟碳的场合,例如如同“エ礻ルギ-·资源”第16卷,第5号,第474页中所述,存在下列问题:(1)将R134a代替R22用于空调器时,运转压力低,与R22相比,能力低约40%,效率低约5%;(2)R32虽然比R22效率好,但运转压力高,并且具有轻微的可燃性;(3)R125不可燃,但临界压力低,效率也低。另外,R134a与R32同样具有可燃性的问题。
作为压缩式冷冻机用制冷剂,希望在不改变现有的冷冻装置的情况下直接使用,但由于上述问题,实际上必须使用将上述氢氟碳混合成的制冷剂。即,为了代替现有的R22和R502制冷剂,从效率的角度考虑,使用可燃性的R32、R143a,为了不使制冷剂整体具有可燃性,希望在前者中混合R125、R134a。在The International Symposium on R22&R502 AlternativeRefrigerants,1994,166页中指出,在使用R32/R134a混合物的场合,R32含量在56%以上时具有可燃性。虽然对于不同制冷剂组成来说不能一概而论,但从不可燃的角度考虑,最好是含有45%(重量)以上R125或R134a等不燃性氢氟碳。
另外,制冷剂是在冷冻系统中各种不同的条件下使用的,因此,混合的氢氟碳的组成在冷冻系统内各部位不应有很大的差别。在冷冻系统内,制冷剂形成气体和液体两种状态,因此混合的氢氟碳彼此的沸点相差较大时,由于上述原因,混合制冷剂的组成在冷冻系统内各部位有可能形成较大的差异。
R32、R143a、R125和134a的沸点分别为-51.7℃、-47.4℃、-48.5℃和-26.3℃,在氢氟碳混合制冷剂中使用R134a时,这一点特别需要注意。因此,在使用R125的混合制冷剂中,其含量为20~80%(重量),优选的是40~70%(重量)。含量低于20%(重量)时,为了使其具有不燃性,需要大量R134a等沸点差异很大的制冷剂,因而不可取。另外,R125的含量超过80%(重量)时,效率低下,也不可取。
考虑到上述情况,迄今为止作为R22制冷剂的替代物比较适宜的有R32/R125/R134a的重量比为23∶25∶52的混合物(以下简称R407C),重量比25∶15∶60的混合物,R32/R125的重量比为50∶50的混合物(以下简称R410A),R32/R125的重量比为45∶55的混合物(以下简称R410B),另外,作为R502制冷剂的替代物比较适宜的是R125/R143a/R134a的重量比为44∶52∶4的混合物(以下简称R404A)或R125/R143a的重量比为50∶50的混合物(以下简称R507)。
这种氢氟碳系制冷剂的性质与以往的制冷剂不同,与其一起使用的冷冻机油例如可以使用以具有特定结构的聚亚烷基二醇、聚酯、多元醇酯、聚碳酸酯、聚乙烯醚等作为基础油在其中添加防氧化剂、耐特压添加剂、消泡剂、水解抑制剂等各种添加剂而得到的冷冻机油。
但是,这些冷冻机油在上述制冷剂氛围下润滑性能恶化,特别是汽车空调器、电冰箱、室内空调器等的冷冻机,铝材与钢材的磨损增大,在实用上有很大问题。铝材与钢材相互磨擦的部分,在往复式压缩机(特别是斜板式)中是活塞与活塞瓦、斜板与滑瓦部分等,在旋转式压缩机中是液轮与机座部分等,在涡旋式压缩机中是欧式环与回转涡形管等,这些部位对于润滑来说都是非常重要的。
另外,冷冻机中在制冷回路内配备有被称为毛细管的膨胀阀。该毛细管是直径0.7mm的细管,容易堵塞。毛细管的堵塞是制约制冷循环寿命的最主要的因素。
因此,在使用可以替代含氯氟烃的氢氟碳系制冷剂的场合,希望具有良好润滑性能、特别是可以改善铝与钢材之间的润滑性、减小磨损并且毛细管不宜堵塞的冷冻机油。
本发明就是基于上述需要而完成的。本发明的目的是,提供在使用可以替代造成环境污染的含氯氟烃制冷剂的氢氟碳系、烃系、醚系、二氧化碳系或氨系制冷剂等时,具有良好的润滑性能,尤其可以改善铝和钢材之间的润滑性,减小磨损并且不易造成毛细管堵塞的冷冻机油组合物。
本发明人经过反复研究,结果发现,在由合成油构成的基础油中配入特定的聚亚烷基二醇衍生物或特定的醚化物、即脂肪族多元醇的醚化物、或者该多元醇的二分子缩合物或三分子缩合物的醚化物,可以有效地实现上述本发明的目的,从而完成了本发明。
即,本发明提供了一种冷冻机油组合物,该冷冻机油组合物是在(A)由合成油构成的基础油中配入(B)数均分子量200~3000的由下述(I)式表示的聚亚烷基二醇衍生物而构成。
R1-(OR2)m-(OR3)n-OR4 (I)式中,R1和R4分别表示1~30个碳原子的烃基或酰基或者氢,R2表示2~4个碳原子的亚烷基,R3表示2~30个碳原子的亚烷基或取代的亚烷基,m和n表示满足上述分子量的数,n有时是0。R1、R3和R4中至少有1个具有6个碳原子以上的烃基。
或者,本发明提供了由该聚亚烷基二醇衍生物(最好是0.1~30%(重量))与其它合成油构成的冷冻机油组合物。或者,本发明提供了由配入该聚亚烷基二醇衍生物(最好是0.1~30%(重量))的合成油构成的冷冻机油组合物。或者,本发明提供了含有上述(I)式表示的聚亚烷基二醇衍生物(最好是0.1~30%(重量))的冷冻机油组合物。
另外,本发明提供了一种冷冻机油组合物,它是在(A)由合成油构成的基础油中配入(C)选自(c-1)3~6元的脂肪族多元醇的醚化物和(c-2)3~6元的脂肪族多元醇的二分子缩合物或三分子缩合物的醚化物、且在40℃下的运动粘度是5~200mm2/s的至少一种醚化物而构成的。
或者,本发明提供了由该醚化物(最好是0.1~30%(重量))与其它合成油构成的冷冻机油组合物。或者,本发明提供了由配入上述的至少一种醚化物(最好是0.1~30%(重量))的合成油构成的冷冻机油组合物。或者,本发明提供了由含有上述的至少一种醚化物(最好是0.1~30%(重量))的合成油构成的冷冻机油组合物。
下面说明本发明的实施方案。
本发明的冷冻机油组合物,是在由合成油构成的基础油中配入特定的聚亚烷基二醇衍生物或特定的醚化物而得到的。即,本发明的冷冻机油组合物是由特定的聚亚烷基二醇衍生物和特定的醚化物与其它合成油构成的。
下面详细说明构成本发明的冷冻机油的各种成分。
首先说明(B)聚亚烷基二醇衍生物。
本发明中使用的聚亚烷基二醇衍生物由(I)式表示。
R1-(OR2)m-(OR3)n-OR4 (I)式中,R1和R4分别表示1~30个碳原子的烃基或酰基或者氢,R2表示2~4个碳原子的亚烷基,R3表示2~30个碳原子的亚烷基或取代的亚烷基,m和n表示满足上述分子量的数,n有时是0。R1、R3和R4中至少有1个具有6个碳原子以上的烃基。
(I)式中R1和R4表示的1~30个碳原子的烃基可以具体举例如下。
①表示饱和或不饱和的、直链或支链的脂肪族烃基,由脂肪族一元醇衍生的烷基,具体地可以举出甲基、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、各种十一烷基、中种十二烷基、各种十三烷基、各种十四烷基、各种十五烷基、各种十六烷基、各种十七烷基、各种十八烷基、各种十九烷基;
②取代或未取代的芳香族烃基,优选的是苯基或烷基苯基,具体地可以举出甲基苯基、乙基苯基、丙基苯基、丁基苯基、戊基苯基、己基苯基、庚基苯基、辛基苯基、壬基苯基、癸基苯基、十二烷基苯基、十五烷基苯基、十六烷基苯基、二壬基苯基。
另外,R1和R4是酰基,优选的是由羧酸、特别是饱和一元羧酸或不饱和一元羧酸衍生的,具体地可以举出乙酸、丙酸、丁酸、月桂酸、肉豆蔻酸、棕榈酸、硬脂酸、油酸等。
另外,R2是2~4个碳原子的亚烷基,作为重复单元的氧亚烷基基(-OR2)可以举出氧亚乙基、氧亚丙基、氧亚丁基。
另外,在上述(I)式中,R3是2~30个碳原子的亚烷基或取代的亚烷基,取代的亚烷基的取代基可以举出烷基、苯基、烷基苯基。
另外,OR2和OR3的共聚合的形态可以是无规共聚物或嵌段共聚物,从分子量的角度考虑优先选用嵌段共聚物。
此外,R1、R3、R4中至少有一个必须具有6个碳原子以上的烃基。该烃基可以是苯基或烷基苯基。
上述(I)式所示的聚亚烷基二醇衍生物的具体例子可以举出:聚乙二醇二-仲丁基苯基·甲基醚、聚丙二醇二-仲丁基苯基·甲基醚、聚乙二醇聚丙二醇二-仲丁基苯基·甲基醚、聚乙二醇壬基·甲基醚、聚丙二醇壬基·甲基醚、聚乙二醇聚丙二醇壬基·甲基醚、聚乙二醇壬基苯基·甲基醚、聚丙二醇壬基苯基·甲基醚、聚乙二醇聚丙二醇壬基苯基·甲基醚、聚乙二醇聚壬二醇二甲基醚、聚丙二醇聚壬二醇二甲基醚等。
在本发明中,上述(I)式所示的聚亚烷基二醇衍生物的数均分子量是200~3000。数均分子量低于200时,改善润滑性和防止毛细管堵塞的效果较小,超过3000时,与制冷剂的相溶性(二层分离温度)降低,都不可取。
另外,上述聚亚烷基二醇衍生物在40℃下的运动粘度是5~200mm2/s,优选的是10~100mm2/s。
在本发明的冷冻机油组合物中,上述的聚亚烷基二醇衍生物可以是1种,也可以2种以上组合使用。相对于组合物总量来说,其配入量在0.1~30%(重量)的范围内为宜。配入量低于0.1%(重量)时,不能充分实现本发明的目的,超过30%(重量)时,所产生的效果与配入量不成比例,另外,有时对于基础油的溶解性降低。优选的配入量是0.1~15%(重量),最好是0.5~10%(重量)。
其次,在本发明中,作为(C)成分的特定醚化合物是选自(c-1)3~6元的脂肪族多元醇的醚化物和(c-2)该多元醇的二分子缩合物或三分子缩合物的醚化物中的至少一种。下面说明这些化合物。
(c-1)成分的3~6元的脂肪族多元醇的醚化物,例如可以由下面的化学式(I-a)~(I-f)表示。
(I-a)~(I-f)各式中,R5~R10分别表示氢或1~18个碳原子的直链或支链的烷基、烯丙基、芳烷基,可以是相同的,也可以是不同的。另外,表示由-(RaO)n-Rb(Ra表示2~6个碳原子的亚烷基,Rb表示1~20个碳原子的烷基、烯丙基、芳烷基,n表示1~10的正数)表示的乙二醇醚残基。R5~R10中至少有一个不是氢。
上述(I-a)~(I-f)中的R5~R10例如可以举出甲基、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、各种十一烷基、各种十二烷基、各种十三烷基、各种十四烷基、各种十五烷基、各种十六烷基、各种十七烷基、各种十八烷基、苯基、苄基等。另外,还包括R5~R10的一部分是氢的场合,即部分醚化物。
在本发明中,作为3~6元的脂肪族多元醇,例如可以举出丙三醇、三羟甲基丙烷、赤藓醇、季戊四醇、阿拉伯糖醇、山梨糖醇、甘露糖醇等。在本发明中,作为(c-2)成分的3~6元的脂肪族多元醇的二分子缩合物或三分子缩合物的醚化物,例如与(I-a)式对应的醇的醚化物由(I-g)和(I-h)式表示,与(I-d)式对应的醇的醚化物可以由(I-i)和(I-j)式表示。
(I-g)~(I-j)各式中,R5~R12分别表示氢或1~18个碳原子的直链或支链的烷基、烯丙基、芳烷基,可以是相同的,也可以是不同的。另外,表示由-(RaO)n-Rb(Ra表示2~6个碳原子的亚烷基,Rb表示1~20个碳原子的烷基、烯丙基、芳烷基,n表示1~10的正数)表示的乙二醇醚残基。R10~R18中至少有一个不是氢。
3~6元的脂肪族多元醇的二分子缩合物和三分子缩合物的具体例子可以举出双甘油、二(三羟甲基丙烷)、二(季戊四醇)、二(山梨糖醇)、三甘油、三(三羟甲基丙烷)、三(季戊四醇)、三(山梨糖醇)等。
上述(I-a)~(I-j)式中所示的(c-1)和(c-2)成分的具体例子可以举出:丙三醇的三己基醚、丙三醇的二甲基辛基三醚、丙三醇的二(甲氧基异亚丙基)十二烷基三醚、丙三醇的二苯基辛基三醚、丙三醇的二(苯氧基异亚丙基)十二烷基三醚、三羟甲基丙烷的三己基醚、三羟甲基丙烷的二甲基辛基三醚、三羟甲基丙烷的二(甲氧基异亚丙基)十二烷基三醚、季戊四醇的四己基醚、季戊四醇的三甲基辛基四醚、季戊四醇的三(甲氧基异亚丙基)十二烷基四醚、山梨糖醇的六丙基醚、山梨糖醇的四甲基辛基五醚、山梨糖醇的六(甲氧基异亚丙基)醚、双甘油的四丁基醚、双甘油的二甲基二辛基四醚、双甘油的三(甲氧基异亚丙基)十二烷基四醚、三甘油的五乙基醚、三甘油的三甲基二辛基五醚、三甘油的四(甲氧基异亚丙基)癸基五醚、二(三羟甲基丙烷)的四丁基醚、二(三羟甲基丙烷)的二甲基二辛基四醚、二(三羟甲基丙烷)的三(甲氧基异亚丙基)十二烷基四醚、三(三羟甲基丙烷)的五乙基醚、三(三羟甲基丙烷)的三甲基二辛基五醚、三(三羟甲基丙烷)的四(甲氧基异亚丙基)癸基五醚、二季戊四醇的六丙基醚、二季戊四醇的五甲基辛基六醚、二季戊四醇的六(甲氧基异亚丙基)醚、三季戊四醇的八丙基醚、三季戊四醇的五甲基辛基六醚、三季戊四醇的六(甲氧基异亚丙基)醚、二山梨糖醇的八甲基二辛基十醚、二山梨糖醇的十(甲氧基异亚丙基)醚等。其中,优选的是丙三醇的二苯基辛基三醚、三羟甲基丙烷的二(甲氧基异亚丙基)十二烷基三醚、季戊四醇的四己基醚、山梨糖醇的六丙基醚、双甘油的二甲基二辛基四醚、三甘油的四(甲氧基异亚丙基)癸基五醚、二季戊四醇的六丙基醚、三季戊四醇的五甲基辛基六醚。
另外,作为(c-1)、(c-2)成分的醚化物在40℃下的运动粘度是5~200mm2/s,优选的是10~100mm2/s。低于5mm2/s时,改善润滑性和防止毛细管堵塞的效果较小,超过200mm2/s时,与制冷剂的相溶性(二层分离温度)降低,因而都不可取。
在本发明的冷冻机油组合物中,(C)成分可以使用上述醚化物中的1种,也可以2种以上组合使用。相对于组合物总量来说,其配入量在0.1~30%(重量)有范围内为宜。配入量低于0.1%(重量)时,不能充分实现本发明的目的,超过30%(重量)时,所产生的效果与配入量不成比例,而且有时对于基础油的溶解性会降低。优选的配入量是0.1~15%(重量),最好是0.5~10%(重量)。
其次,说明在本发明的冷冻机油组合物中用来作为(A)成分即基础油的合成油。
该合成油只要是一般用来作为冷冻机油的基础油即可,没有特别的限制,通常在40℃下的运动粘度是2~500mm2/s,优选的是5~200mm2/s,最好是10~100mm2/s。另外,该基础油的低温流动性指标即流动点没有特别的限制,一般是-10℃以下。
这样的合成油有许多种,可以根据用途适当选择,举例来说可以使用含氧有机化合物和烃系合成油等。
在合成油中,含氧有机化合物可以举出分子中含有醚基、酮基、酯基、碳酸酯基、羟基等的合成油,以及除了这些基团外还含有杂原子(S、P、F、Cl、Si、N等)的合成油,具体地可以举出①聚乙烯醚、②聚酯、③多元醇酯、④碳酸酯衍生物、⑤聚醚酮、⑥氟化油、⑦聚亚烷基二醇等。
上述①的聚乙烯醚例如可以举出具有由(II)式表示的构成单元的聚乙烯醚系化合物(1)(式中,R13~R15分别表示氢原子或1~8个碳原子的烃基,它们可以是相同的,也可以是不同的,R16表示1~10个碳原子的二价的烃基或2~20个碳原子的二价的醚键键合的含氧烃其,R17表示1~20个碳原子的烃基,a表示其平均值为0~10的数,R13~R17的每个构成单元可以是相同的,也可以是不同的,R16O基有多个时,多个R16O基可以是相同的,也可以是不同的)。另外,还可以使用由具有上述(II)式表示的构成单元和上面的(III)式(式中,R18~R21分别表示氢原子或1~20个碳原子的烃基,可以是相同的,也可以是不同的,R18~R21每个构成单元可以是相同的,也可以是不同的)表示的构成单元的嵌段共聚物或无规共聚物构成的聚乙烯醚化合物(2)。此外,还可以使用由上述聚乙烯醚系化合物(1)和聚乙烯醚系化合物(2)的混合物构成的聚乙烯醚系化合物(3)。
上述(II)式中的R13~R15分别表示氢原子或1~8个碳原子、最好是1~4个碳原子的烃基。所述的烃基具体地可以举出甲基、乙基、正丙基、异丙基、各种丁基、各种戊基、各种己基、各种庚基、各种辛基等烷基,环戊基、环己基、各种甲基环己基、各种乙基环己基、各种二甲基环己基等环烷基,苯基、各种甲基苯基、各种乙基苯基、各种二甲基苯基等芳基,苄基、各种苯基乙基、各种甲基苄基、等芳基烷基。这些R13~R15特别优先选用氢原子。
另外,(II)式中的R16表示1~10个碳原子、最好是2~10个碳原子的二价烃基或2~20个碳原子的二价醚键键合含氧烃基,1~10个碳原子的二价烃基具体地可以举出: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、各种亚癸基等二价脂肪族基;环己烷、甲基环己烷、乙基环己烷、二甲基环己烷、丙基环己烷等脂环式烃中具有2个键合部位的脂环式基;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、各种亚萘基等二价的芳香族烃基、甲苯、二甲苯、乙苯等烷基芳香族烃的烷基部分和芳香族部分分别具有一价的键合部位的烷基芳香族基;二甲苯、二乙苯等聚烷基芳香族烃的烷基部分具有键合部位的烷基芳香族基等。其中,优先选用2~4个碳原子的脂肪族基。
另外,2~20个碳原子的二价醚键键合含氧烃基的具体例子可以举出甲氧基亚甲基、甲氧基亚乙基、甲氧基甲基亚乙基、1,1-二甲氧基甲基亚乙基、1,2-二甲氧基甲基亚乙基、乙氧基甲基亚乙基、(2-甲氧基乙氧基)甲基亚乙基、(1-甲基-2-甲氧基)甲基亚乙基等。(II)式中的a表示R16O基的重复次数,其平均值是0~10,最好是0~5的数。在具有多个R16O基的场合,多个R16O基可以是相同的,也可以是不同的。
另外,(II)式中的R17表示1~20个碳原子、优选的是1~10个碳原子的烃基,所述的烃基具体地可以举出甲基、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、各种癸基等烷基;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、各种二甲基环己基等环烷基;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、各种萘基等芳基;苄基、各种苯基乙基、各种甲基苄基、各种苯基丙基、各种苯基丁基等芳烷基等。
聚乙烯醚系化合物(1)是具有上述(II)式所示构成单元的化合物,其重复次数(聚合度)可以根据所希望的动力粘度适当选择,通常在选择时应使40℃下的运动粘度是2~500mm2/s。另外,该聚乙烯醚系化合物的碳/氧摩尔比在4.2~7.0的范围内为宜,低于4.2时,吸湿性有时升高,反之,超过7.0时,与制冷剂的相溶性有时降低。
另外,聚乙烯醚系化合物(2)是由具有上述(II)式所示的构成单元和上述(III)式所示的构成单元的嵌段共聚物或无规共聚物构成,在(III)式中,R18~R21分别表示氢原子或1~20个碳原子的烃基,它们可以相同也可以不同。其中,1~20个碳原子的烃基可以举出与在说明上述(II)式中的R17时例示的烃基。另外,R18~R21每个构成单元可以是相同的也可以是不同的。
由具有上述(II)式所示的构成单元和上述(III)所示的构成单元的嵌段共聚物或无规共聚物构成的聚乙烯醚系化合物(2)的聚合度,可以根据所希望的运动粘度适当选择,通常在选择时应使40℃下的运动粘度是2~200mm2/s。另外,该聚乙烯醚系化合物的碳/氧摩尔比在4.2~7.0的范围内为宜,低于4.2时,吸湿性有时升高,反之,超过7.0时,与制冷剂的相溶性有时降低。
此外,聚乙烯醚系化合物(3)是由上述聚乙烯醚系化合物(1)和上述聚乙烯醚系化合物(2)的混合物构成,其混合比例没有特别的限制。
本发明中使用的聚乙烯醚系化合物(1)和(2),可以分别通过相应的乙烯基醚系单体的聚合以及相应的具有烯烃性双键的烃单体与相应的乙烯基醚系单体的共聚来制造。可以使用的乙烯基醚系单体由下面的(IV)式表示式中,R13~R17和a的含义同上。
该乙烯基醚系单体与上述聚乙烯醚系化合物(1)、(2)相对应有各种不同的种类,例如可以举出:乙烯基甲基醚、乙烯基乙基醚、乙烯基正丙基醚、乙烯基异丙基醚、乙烯基正丁基醚、乙烯基异丁基醚、乙烯基仲丁基醚、乙烯基叔丁基醚、乙烯基正戊基醚、乙烯基正己基醚、乙烯基-2-甲氧基乙基醚、乙烯基-2-乙氧基乙基醚、乙烯基-2-甲氧基-1-甲基乙基醚、乙烯基-2-甲氧基-2-甲基醚、乙烯基-3,6-二氧杂庚基醚、乙烯基-3,6,9-三氧杂癸基醚、乙烯基-1,4-二甲基-3,6-二氧杂庚基醚、乙烯基-1,4,7-三甲基-3,6,9-三氧杂癸基醚、乙烯基-2,6-二氧杂-4-庚基醚、乙烯基-2,6,9-三氧杂-4-癸基醚、1-甲氧基丙烯、1-乙氧基丙烯、1-正丙氧基丙烯、1-异丙氧基丙烯、1-正丁氧基丙烯、1-异丁氧基丙烯、1-仲丁氧基丙烯、1-叔丁氧基丙烯、2-甲氧基丙烯、2-乙氧基丙烯、2-正丙氧基丙烯、2-异丙氧基丙烯、2-正丁氧基丙烯、2-异丁氧基丙烯、2-仲丁氧基丙烯、2-叔丁氧基丙烯、1-甲氧基-1-丁烯、1-乙氧基-1-丁烯、1-正丙氧基-1-丁烯、1-异丙氧基-1-丁烯、1-正丁氧基-1-丁烯、1-异丁氧基-1-丁烯、1-仲丁氧基-1-丁烯、1-叔丁氧基-1-丁烯、2-甲氧基-1-丁烯、2-乙氧基-1-丁烯、2-正丙氧基-1-丁烯、2-异丙氧基-1-丁烯、2-正丁氧基-1-丁烯、2-异丁氧基-1-丁烯、2-仲丁氧基-1-丁烯、2-叔丁氧基-1-丁烯、2-甲氧基-2-丁烯、2-乙氧基-2-丁烯、2-正丙氧基-2-丁烯、2-异丙氧基-2-丁烯、2-正丁氧基-2-丁烯、2-异丁氧基-2-丁烯、2-仲丁氧基-2-丁烯、2-叔丁氧基-2-丁烯等。这些乙烯基醚系单体可以用公知的方法制造。
另外,具有烯烃性双键的烃单体由下面的(V)式表示式中,R18~R21的含义同上。该单体例如可以举出乙烯、丙烯、各种丁烯、各种戊烯、各种己烯、各种庚烯、各种辛烯、二异丁烯、三异丁烯、苯乙烯、各种烷基取代的苯乙烯等。
本发明中使用的聚乙烯醚系化合物优先选用具有下面的未端结构的化合物,即其一端由(VI)或(VII)式表示(式中,R22~R24分别表示氢原子或1~8个碳原子的烃基,R22~R24可以彼此相同,也可以不同,R27~R30分别表示氢原子或1~20个碳原子的烃基,R27~R30可以彼此相同,也可以不同。R25表示1~10个碳原子的二价烃基或2~20个碳原子的二价醚键键合含氧烃基,R26表示1~20个碳原子的烃基,b表示平均值为0~10的数,在具有多个R25O基的场合,多个R25O基可以是相同的,也可以是不同的),另一端由(VIII)式或(IX)式表示(式中,R31~R33分别表示氢原子或1~8个碳原子的烃基,R31~R33可以彼此相同,也可以不同,R36~R39分别表示氢原子或1~20个碳原子的烃基,R36~R39可以彼此相同,也可以不同。R34表示1~10个碳原子的二价烃基或2~20个碳原子的二价醚键键合含氧烃基,R35表示1~20个碳原子的烃基,c表示平均值为0~10的数,在具有多个R34O基的场合,多个R34O基可以是相同的,也可以是不同的),以及其一端由上述(VI)或(VII)式表示,另一端由(X)式表示(式中,R40~R42分别表示氢原子或1~8个碳原子的烃基,它们可以彼此相同,也可以是不同的。)的结构。
在这样的聚乙烯醚系化合物中,特别适合作为本发明的冷冻机油组合物的基础油的化合物可以举出如下:
(1)具有其一端由(VI)或(VII)式表示、另一端由(VIII)或(IX)表示的结构,(II)式中的R13~R15都是氢原子,a是0~4的数,R16是2~4个碳原子的二价烃基,R17是1~20个碳原子的烃基。
(2)只具有由(II)式表示的构成单元,具有其一端由(VI)式表示、另一端由(VIII)表示的结构,(II)式中的R13~R15都是氢原子,a是0~4的数,R16是2~4个碳原子的二价烃基,R9是1~20个碳原子的烃基。
(3)具有其一端由(VI)或(VII)式表示、另一端由(X)表示的结构,(II)式中的R13~R15都是氢原子,a是0~4的数,R16是2~4个碳原子的二价烃基,R17是1~20个碳原子的烃基。
(4)只具有由(II)式表示的构成单元,具有其一端由(VI)式表示、另一端由(IX)表示的结构,(II)式中的R13~R15都是氢原子,a是0~4的数,R16是2~4个碳原子的二价烃基,R17是1~20个碳原子的烃基。
另外,在本发明中,还可以使用具有由上述(II)式表示的构成单元,其一端由(VI)式表示、另一端由(XI)式表示的结构的聚乙烯醚系化合物(式中,R43~R45分别表示氢原子或1~8个碳原子烃基,它们可以相同也可以不同,R46和R48分别表示2~10个碳原子的二价烃基,它们可以相同也可以不同,R47和R49分别表示1~10个碳原子的烃基,它们可以相同也可以不同,d和e分别表示平均值0~10的数,它们可以相同也可以不同,在有多个R46O基的情况下,多个R46O基可以相同也可以不同,在有多个R48O基的情况下,多个R48O基可以相同也可以不同。)
另外,在本发明中,还可以使用特愿平8-18837的说明书中记载的聚乙烯醚系化合物,其中,也可以使用由具有下列结构的烷基乙烯基醚的均聚物或共聚物构成的聚乙烯醚系化合物,它由(XII)或(XIII)式表示的构成单元构成,(式中,R50表示1~8个碳原子的烃基),并且重均分子量是300~3000(优选的是300~2000),一方的末端由(XIV)或(XV)式表示。(式中,R51表示1~3个碳原子的烷基,R52表示1~8个碳原子的烃基。)
另外,可以使用具有由(XVI)式(式中,R53表示1~3个碳原子的分子内有或没有醚键的烃基)表示的构成单元(B)和由(XVII)式(式中,R54表示3~20个碳原子的分子内有或没有醚键的烃基)表示的构成单元(B)的聚乙烯醚系化合物[其中,构成单元(A)的R53和(B)的R54不相同],优先选用R53是甲基或乙基、R54是3~6个碳原子的烷基的聚乙烯醚系化合物,其中特别优先选用R53是乙基、R54是异丁基的聚乙烯醚化合物。在这种场合,构成单元(A)和构成单元(B)的比例在95∶5~50∶50(摩尔比)的范围为宜。
另外,上述聚乙烯醚系化合物也可以使用特开平6-128578、特开平6-234814、特开平6-234815、特开平8-193196的说明书中详细记载的任一种聚乙烯醚化合物。
该聚乙烯醚系化合物可以采用将上述单体自由基引发聚合、阳离子催化聚合、辐射引发聚合等进行制造。例如,对于乙烯基醚系单体采用下面所述的方法进行聚合,可以得到所希望粘度的聚合物。
为了引发聚合,对于布朗斯台德酸类、路易斯酸类或有机金属化合物类可以使用将水、醇类、酚类、缩醛类或乙烯醚类与羧酸的加成物组合的组合物。
布朗斯台德酸类例如可以举出氢氟酸、盐酸、氢溴酸、氢碘酸、硝酸、硫酸、三氯乙酸、三氟乙酸等。路易斯酸类例如可以举出三氟化硼、三氯化铝、三溴化铝、四氯化锡、二氯化锌、氯酸铁等,其中,优先选用三氟化硼。另外,有机金属化合物例如可以举出二乙基氯化铝、乙基氯化铝、二乙基锌等。与它们组合的水、醇类、酚类、缩醛类或乙烯醚类与羧酸的加成物可以任意选择。
醇类例如可以举出甲醇;乙醇、丙醇、异丙醇、丁醇、异丁醇、仲丁醇、叔丁醇、各种戊醇、各种己醇、各种庚醇、各种辛醇等1~20个碳原子的饱和脂肪族醇、烯丙醇等3~10个碳原子的不饱和脂肪族醇等。
乙烯醚类与羧酸的加成物中的羧酸,例如可以举出乙酸、丙酸、正丁酸、异丁酸、正戊酸、异戊酸、2-甲基丁酸、三甲基乙基、正己酸、2,2-二甲基丁酸、2-甲基戊酸、3-甲基戊酸、4-甲基戊酸、庚酸、2-甲基己酸、辛酸、2-乙基己酸、2-正丙基戊酸、正壬酸、3,5,5-三甲基己酸、辛酸、十一烷酸等。另外,乙烯醚类可以与聚合使用的相同,也可以不同。该乙烯醚类与该羧酸的加成物可以通过将两者混合、在0~100℃的温度下反应而得到,通过蒸馏等分离用于反应,也可以不经过分离直接用于反应。
聚合物的聚合开始端,在使用水、醇类、酚类的场合变成氢,在使用缩醛类的场合,变成氢或一方的烷氧基从所用的缩醛类中脱离的产物。另外,在使用乙烯基醚类与羧酸的加成物的场合,变成来源于羧酸部分的烷基羰氧基从乙烯基醚类与羧酸的加成物中脱离。
另外,终止端,在使用水、醇类、酚类、羧醛类的场合,变成乙缩醛、烯烃或乙醛。在乙烯基醚类与羧酸的加成物的场合变成半缩醛的羧酸酯。
这样得到的聚合物的末端,可以用公知的方法转变成所希望的基团。所希望的基团例如可以举出饱和的烃、醚、醇、酮、腈、酰胺等的残基,优选的是饱和的烃、醚和醇的残基。
(IV)式表示的乙烯基醚系单体的聚合取决于原料和引发剂的种类,可以在-80~150℃之间引发聚合,通常是在-80~50℃的温度下进行。聚合反应在反应开始后10秒至10小时结束。
至于聚合反应中分子量的调节,相对于上述(IV)式表示的乙烯基醚系单体增加水、醇类、酚类、缩醛类和乙烯基醚类与羧酸的加成物的量,可以得到平均分子量较低的聚合物。另外,增加上述布朗斯台德酸类或路易斯酸类的量,可以得到平均分子量低的聚合物。
聚合反应通常在溶剂存在下进行。该溶剂只要能溶解所需要量的反应原料并且对于反应是隋性的即可,没有特别的限制,例如可以使用己烷、苯、甲苯等烃类以及乙醚、1,2-二甲氧基乙烷、四氢呋喃等醚类的溶剂。通过添加碱可以终止聚合反应。聚合反应结束后,根据需要进行通常的分离、提纯,可以得到所要求的具有(II)式表示的构成单元的聚乙烯醚系化合物。
如上所述,本发明中使用的聚乙烯醚系化合物的碳/氧摩尔比在4.2~7.0的范围为宜,通过调节原料单体的碳/氧摩尔比,可以制造该摩尔比在上述范围内的聚合物。即,如果增加碳/氧摩尔比大的单体的比例,就可以得到碳/氧摩尔比大的聚合物。如果增加碳/氧摩尔比小的单体的比例,就能得到碳/氧的摩尔比小的聚合物。
另外,如同上述乙烯基醚系单体的聚合方法中所述,作为引发剂使用的水、醇类、酚类、缩醛类以及乙烯基醚类与羧酸的加成物也可以与单体组合。如果使用碳/氧摩尔比比聚合的单体大的醇类、酚类等作为引发剂,可以得到碳/氧摩尔比比原料单体大的聚合物。反之,如果使用甲醇或甲氧基乙醇等碳/氧摩尔比较小的醇类,可以得到碳/氧摩尔比比原料单体小的聚合物。
另外,在使乙烯基醚系单体与具有烯烃性双键的烃单体共聚时,可以得到碳/氧摩尔比比乙烯基醚系单体大的聚合物,其比例可以通过所使用的具有烯烃性双键的烃单体的比例或其碳原子数来调节。
上述②的聚酯,例如可以举出具有由(XVIII)式(式中,R55表示1~10个碳原子的亚烷基,R56表示2~10个碳原子的亚烷基或4~20个碳原子的氧杂亚烷基)表示的构成单元且分子量是300~2000的脂肪族聚酯衍生物。
(XVIII)中的R55表示1~10个碳原子的亚烷基,具体地说可以举出亚甲基、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、三亚甲基、四亚甲基、五亚甲基等,优选的是6个碳原子以下的亚烷基。另外,R56表示2~10个碳原子的亚烷基或4~20个碳原子的氧杂亚烷基。所述的亚烷基具体地说与R56的具体例子(亚甲基除外)相同,优选的是2~6个碳原子的亚烷基,氧杂亚烷基具体地可以举出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-1,1,1-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-1,2,4,5,7,8,10,11-六甲基-1,1,1-亚十一基、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-亚己基、4,8-二氧杂-2,2,6,6,10,10-六甲基-1,11-亚十一基等。R55和R56每个构成单元可以相同也可以不同。
上述(XVIII)式所示的脂肪族聚酯衍生物的分子量(用GPC测定的值)在300~2000范围为宜。分子量低于300时,运动粘度过低,反之超过2000时,变成蜡状,都不适于作为冷冻机油。
这样的聚酯可以使用WO91/07479中详细记载的化合物。
上述③的多元醇酯,可以使用至少含有2个羟基的多元醇(最好是2~6元的多元醇)与羧酸(最好是2~18个碳原子的一元羧酸)的1种或2种以上的酯化物,例如由(XIX)式表示的化合物
R57(OCOR58)f (XIX)
(式中,R57表示烃基,R58表示氢原子或1~22个碳原子的烃基,f表示2~6的整数,多个-OCOR58基可以是相同的,也可以是不同的。)
在上述(XIX)式中,R57表示烃基,可以是直链或支链的,最好是2~10个碳原子的烷基。R58是氢原子或1~22个碳原子的烃基,最好是2~16个碳原子的烷基。
上述(XIX)式所示的多元醇酯,可以通过使(XX)式
R57(OH)f (XX)(式中,R57和f同上)所示的多元醇与(XXI)式
R58COOH (XXI)
(式中,R58含义同上)所示的羧酸或其酯或酰基卤等反应性衍生物反应而得到。
上述(XX)式所示的多元醇,例如可以举出乙二醇、二乙二醇、丙二醇、二丙二醇、丁二醇、新戊二醇、三羟甲基乙烷、三羟甲基丙烷、丙三醇、赤藓醇、季戊四醇、二季戊四醇、阿拉伯糖醇、山梨糖醇、甘露糖醇等。另外,(XXI)式所示的羧酸可以是直链的或支链的,可以是饱和脂肪酸或不饱和脂肪酸,具体地可以举出乙酸、丙酸、异丙酸、丁酸、异丁酸、戊酸、异戊酸、庚酸、三甲基乙酸、己酸、己酸、异己酸、庚酸、异庚酸、辛酸、异辛酸、2-乙基己酸、壬酸、3,5,5-三甲基己酸、癸酸、十一烷酸、3-甲基己酸、2-乙基己酸、辛酸、癸酸、月桂酸、肉豆蔻酸、棕榈酸、棕榈烯酸、硬酯酸、异硬酯酸、油酸、亚油酸、亚麻酸等。另外,为了调节粘度,可以与一元脂肪酸一起使用琥珀酸、己二酸、戊二酸、癸二酸、马来酸等多元酸。上述多元醇酯可以根据所希望的运动粘度适当选择,通常应使40℃下的运动粘度是2~500mm2/s。
上述④的碳酸酯衍生物例如可以举出由(XXII)式(式中,R59和R61分别表示30个碳原子以下的烃基或2~30个碳原子的具有醚键的烃基,它们可以相同也可以不同,R60表示2~24个碳原子的亚烷基,g表示1~100的整数,h表示1~10的整数)所表示的聚碳酸酯。
在上述(XXII)式中,R59和R61分别表示30个碳原子以下的烃基或2~30个碳原子的具有醚基的烃基,30个碳原子以下的烃基的具体例子可以举出甲基、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、各种十一烷基、各种十二烷基、各种十三烷基、各种十四烷基、各种十五烷基、各种十六烷基、各种十七烷基、各种十八烷基、各种十九烷基、各种二十烷基等脂肪族烃基;环己基、1-环己烯基、甲基环己基、二甲基环己基、十氢萘基、三环癸基等脂环式烃基;苯基、各种甲苯基、各种二甲苯基、基、各种萘基等芳香族烃基;苄基、甲基苄基、苯基乙基、1-甲基-1-苯基乙基、苯乙烯基、肉桂基等芳香脂肪族烃基等。
另外,2~30个碳原子的具有醚键的烃基例如可以举出由(XXIII)式
-(R62-O)i-R63 (XXIII)(式中,R62表示2或3个碳原子的亚烷基(亚乙基、亚丙基、三亚甲基),R63表示28个碳原子以下的脂肪族、脂环式或芳香族烃基(与R59和R61的具体例子中举出的基团相同),i表示1~20的整数)表示的乙二醇醚基,具体的例子可以举出乙二醇-甲醚基、乙二醇-丁醚基、二乙二醇-正丁醚基、三乙二醇-乙基醚基、丙二醇-甲基醚基、二丙二醇-乙基醚基、三丙二醇-正丁醚基等。对于R62和R63来说,在这些当中,优先选择正丁基、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、2-乙基己基等;乙二醇一甲基醚基、乙二醇一丁基醚基、二乙二醇一甲基醚基、三乙二醇一甲基醚基、丙二醇一甲基醚基、丙二醇一丁基醚基、二丙二醇一丁基醚基、三丙二醇一正丁基醚基等亚烷基甘醇单烷基醚基。
另外,在上述(XXII)式中,R60是2~24个碳原子的亚烷基,具体地可以举出亚乙基、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、十亚甲基、十二亚甲基、十四亚甲基等。在有多个R60O基的场合,多个R60O基可以是相同的,也可以是不同的。
(XXII)式所示的聚碳酸酯,分子量(重均分子量)是300~3000,优选的是400~1500。分子量不足300时,运动粘度过低,不适合于用作润滑油,反之超过3000时,变成蜡状,作为润滑油使用有困难,也不可取。
该聚碳酸酯可以用各种方法制造,通常是用碳酸二酯或碳酰氯等可以形成碳酸酯的衍生物和脂肪族二元醇作为原料制造。
使用这些原料制造聚碳酸酯时,可以采用常规的聚碳酸酯制造方法,一般是采用酯交换法或光气法。
上述聚碳酸酯可以使用特开平3-217495中详细记载的任一种。
另外,碳酸酯衍生物可以使用(XXIV)式R64-O-(R66O)j-CO-(OR67)k-O-R65 (XXIV)(式中,R64和R65分别表示1~20个碳原子的脂肪族、脂环式、芳香族或芳香脂肪族烃基,它们可以相同也可以不同,R66和R67分别表示亚乙基或异亚丙基,它们可以相同也可以不同,j和k分别表示1~100的数)所表示的乙二醇醚碳酸酯。
在上述(XXIV)式中,R64和R65中的脂肪族烃基的具体例子可以举出甲基、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、各种十一烷基、各种十二烷基、各种十三烷基、各种十四烷基、各种十五烷基、各种十六烷基、各种十七烷基、各种十八烷基、各种十九烷基、各种二十烷基等。脂环式烃基的具体例子可以举出环己基、1-环己烯基、甲基环己基、二甲基环己基、十氢萘基、三环癸基等。芳香族烃的具体例子可以举出苯基、各种烯丙基、各种二甲苯基、各种米基、各种萘基等。芳香脂肪族烃基的具体例子可以举出苄基、甲基苄基、苯基乙基、苯乙烯基、肉桂基等。
上述(XXIV)式所示的乙二醇醚碳酸酯,例如可以通过在过量的低沸点醇的碳酸酯存在下使聚亚烷基二醇单烷基醚进行酯交换来制造。
上述的乙二醇醚碳酸酯,可以使用特开平3-149295中详细记载的任一种。
另外,碳酸酯衍生物可以使用(XXV)式(式中,R68和R69分别表示1~15个碳原子的烷基或2~12个碳原子的一元醇残基,它们可以相同也可以不同,R70表示2~12个碳原子的亚烷基,p表示0~30的整数)所示的碳酸酯。
在上述(XXV)式中,R68和R69分别表示1~15个碳原子、最好是2~9个碳原子的烷基或2~12个碳原子、最好是2~9个碳原子的一元醇残基,R70表示2~12个碳原子、最好是2~9个碳原子的亚烷基,p表示0~30、最好是1~30的整数。如果使用不满足上述条件的碳酸酯,与制冷剂的相溶性等各种性能就会恶化,因而不可取。R68和R69中的1~15个碳原子的烷基,具体地可以举出甲基、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、叔丁基、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、异十五烷基等。
另外,2~12个碳原子的二元醇残基具体地可以举出乙二醇、1,3-丙二醇、丙二醇、1,4-丁二醇、1,2-丁二醇、8-甲基-1,3-丙二醇、1,5-戊二醇、新戊二醇、1,6-己二醇、2-乙基-2-甲基-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、1,11-十一烷基二醇、1,12-十二烷基二醇等的残基。
另外,R70所示的2~12个碳原子的亚烷基,具体地可以举出亚乙基、三亚甲基、亚丙基、四亚甲基、亚丁基、2-甲基三亚甲基、五亚甲基、2,2-二甲基三亚甲基、六亚甲基、2-乙基-2-甲基三亚甲基、七亚甲基、2-甲基-2-丙基三亚甲基、2,2-二乙基三亚甲基、八亚甲基、九亚甲基、十亚甲基、十一亚甲基、十二亚甲基等具有直链或支链结构的亚烷基。
上述碳酸酯的分子量没有特别的限制,不过从提高压缩机密封性的角度考虑,优先选用数均分子量200~3000、特别是数均分子量300~2000的碳酸酯。
上述碳酸酯可以使用特开平4-63893中详细记载的任一种。
上述⑤的聚醚酮,例如可以举出(XXVI)式(式中、Q是1~8元醇残基,R71是2~4个碳原子的亚烷基,R72是甲基或乙基,R73和R75分别表示氢原子、20个碳原子以下的脂肪族、芳香族或芳香脂肪族烃基,它们可以相同也可以不同,R74表示20个碳原子以下的脂肪族、芳香族或芳香脂肪族烃基,r和s是0~30的数,u是1~8的数,v是0~7的数,并且满足u+v=1~8,t表示0或1)所示的化合物。
上述(XXVI)式中,Q是1~8元醇残基,以Q作为残基的醇,作为一元醇,例如可以举出甲醇、乙醇、直链或支链的丙醇、直链或支链的丁醇、直链或支链的戊醇、直链或支链的己醇、直链或支链的庚醇、直链或支链的辛醇、直链或支链的壬醇、直链或支链的癸醇、直链或支链的十一烷醇、直链或支链的十二烷醇、直链或支链的十三烷醇、直链或支链的十四烷醇、直链或支链的十五烷醇、直链或支链的十六烷醇、直链或支链的十七烷醇、直链或支链的十八烷醇、直链或支链的十九烷醇、直链或支链的二十烷醇等脂肪族一元醇,苯酚、甲基苯酚、壬基苯酚、辛基苯酚、萘酚等芳香族醇,苄醇、苯乙基醇等芳香脂肪族醇,以及它们的部分醚化物;作为二元醇,例如可以举出乙二醇、丙二醇、丁二醇、新戊二醇、丁二醇等直链或支链的脂肪族醇、儿茶酚、间苯二酚、双酚A、双苯基二醇等芳香族醇,以及它们的部分醚化物;作为三元醇,例如可以举出丙三醇、三羟甲基乙烷、三羟甲基丙烷、三羟甲基丁烷、1,3,5-戊三醇等直链或支链的脂肪族醇,焦倍酚、甲基焦倍酚、5-仲丁基焦倍酚等芳香族醇以及它们的部分醚化物;作为4~8元醇,例如可以举出季戊四醇、双甘油、脱水山梨糖醇、三甘油、山梨糖醇、二季戊四醇、四甘油、五甘油;六甘油、三季戊四醇等脂肪族醇以及它们的部分醚化物等。
另外,上述(XXVI)式中,R71表示的2~4个碳原子的亚烷基可以是直链或支链的,具体的例子可以举出亚乙基、亚丙基、乙基亚乙基、1,1-二甲基亚乙基、1,2-二甲基亚乙基等。另外,R73~R75表示的20个碳原子以下的脂肪族、芳香族或芳香脂肪族烃基,例如可以举出甲基、乙基、丙基、丁基、戊基、己基、庚基、辛基、壬基、癸基、十一烷基、十二烷基、十四烷基、十六烷基、十八烷基等直链烷基,异丙基、异丁基、异戊基、2-乙基己基、异十八烷基、2-庚基十一烷基等支链烷基,苯基、甲基苯基等芳基,苄基等芳烷基等。
在(XXVI)式中,r和s表示0~30的数,r、s超过30时,分子内的醚基的作用增大,对于与制冷剂的相溶性、电绝缘性和吸湿性不利。另外,u是1~8的数,v是0~7的数,u+v满足1~8的关系,这些数表示平均值,不限于整数。t是0或1。此外,r×u个R71可以相同也可以不同,s×u个R72可以相同也可以不同。u是2以上时,u个r、s、t、R73和R74可以相同也可以不同,v是2以上时,v个R75可以相同也可以不同。
上述(XXVI)式所示的聚醚酮可以采用公知的方法制造。例如,用次亚氯酸盐和醋酸将二级的烷氧基醇氧化的方法(特开平4-126716),或者用氢氧化锆和酮将二级的烷氧基醇氧化的方法(特开平3-167149)。
上述⑥的氟化油,例如可以举出氟化硅油、全氟聚醚、链烷烃与全氟烷基乙烯醚的反应化物等。链烷烃与全氟烷基乙烯醚的反应化物的例子可以举出将(XXVI)式所示的链烷烃
CnH2n+2 (XXVII)(式中,n表示6~20的整数)与(XXVIII)式所示的全氟烷基乙烯基醚
CnH(2n+2-w)(CF2-CFHOCmF2m+1)w (XXIX)(式中,w表示1~4的整数,n和m同上)。
上述(XXVII)式表示的链烷烃可以是直链的、支链的或环状的,其具体例子可以举出正辛烷、正癸烷、正十二烷、环辛烷、环十二烷、2,2,4-三甲基戊烷等。(XXVIII)式所示的全氟烷基乙烯醚的具体例子可以举出全氟甲基乙烯醚、全氟乙基乙烯醚、全氟正丙基乙烯醚、全氟正丁基乙烯醚等。
上述⑦的聚亚烷基二醇可以举出下面的(XXX)式
R76-[(OR77)m-OR78]n (XXX)(式中,R76表示氢原子、1~10个碳原子的烷基、2~10个碳原子的酰基或具有2~6个键合部位的1~10个碳原子的脂肪族烃基,R77表示2~4个碳原子的亚烷基,R78表示氢原子、1~10个碳原子的烷基或2~10个碳原子的酰基,n表示1~6的整数,m表示m×n的平均值为6~80的数)表示的化合物。
上述(XXX)式中,R76和R78中的烷基可以是直链、支链的或环状的。该烷基的具体例子可以举出甲基、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、环己基等。该烷基的碳原子数超过10时,与制冷剂的相溶性降低,有时会产生相分离。优选的烷基碳原子数是1~6。
另外,R76、R78中的酰基的烷基部分可以是直链、支链或环状的,该酰基的烷基部分的具体例子与上述烷基的具体例子中举出的1~9个碳原子的各种基团相同。该酰基的碳原子数超过10时,与制冷剂的相溶性降低,有时会产生相分离。优选的酰基碳原子数是2~6。
R76和R78都是烷基或酰基的场合,R76和R78可以彼此相同也可以不同。
在n>2时,1个分子中的多个R70可以相同也可以不同。
R76是具有2~6个键合部位的1~10个碳原子的脂肪族烃基的场合,该脂肪族烃基可以是链状的,也可以是环状的。具有2个键合部位的脂肪族烃基例如可以举出亚乙基、亚丙基、亚丁基、亚戊基、亚己基、亚庚基、亚辛基、亚壬基、亚癸基、环戊基、环己基等。另外,具有3~6个键合部位的脂肪族烃基例如可以举出从三羟甲基丙烷、丙三醇、季戊四醇、山梨糖醇、1,2,3-三羟基环己烷、1,3,5-三羟基环己烷等多元醇中除去羟基的残基。
该脂肪族羟基的碳原子数超过10个时,与制冷剂的相溶性降低,有时会发生相分离。优选的碳原子数是2~6。
上述(XXX)式中的R77是2~4个碳原子的亚烷基,作为重复单元的氧亚烷基可以举出氧亚乙基、氧亚丙基、氧亚丁基。1个分子中的氧亚烷基可以是相同的,也可以含有2个以上的氧亚烷基,优选的是1个分子中至少含有氧亚丙基单元,最好是氧亚烷基单元中含有50%(摩尔)以上的氧亚丙基单元。另外,在含有2个以上氧亚烷基单元的场合,可以是无规共聚物,也可以是嵌段共聚物。
上述(XXX)式中的n是1~6的整数,根据R76的键合部位的数确定。例如在R76是烷基或酰基的场合,n是1,R76是具有2,3,4,5和6个键合部位的脂肪族烃基的场合,n分别是2,3,4,5和6。另外,m是m×n的平均数为6~80的数,m×n的平均值超出上述范围时,有时不能充分实现本发明的目的。
上述(XXX)式所示的聚亚烷基二醇,包括末端具有羟基的聚亚烷基二醇,相对于全部端基来说,该羟基的含量为50%(摩尔)以下即可,只要含有一些就可以起作用。该羟基的含量超过50%(摩尔)时,吸湿性增大,粘度指数有时会降低。
(XXX)式所示的聚亚烷基二醇,从经济性和效果的角度考虑,优先选用聚丙二醇二甲醚、聚氧乙烯聚丙二醇二甲醚以及聚丙二醇一丁醚、另外还有聚丙二醇二乙酸酯等。
上述(XXX)式所表示的聚亚烷基二醇,可以使用特开平2-305893中记载的任一种。
另外,作为烃系合成油例如可以举出聚-α-烯烃等烯烃系聚合物、烷基苯、烷基萘等。
在本发明的冷冻机油组合物中,作为基础油可以使用上述合成油中的1种,也可以2种以上组合使用。
用来作为基础油的合成油,在上述各种合成油中,含氧有机化合物与制冷剂的相溶性好,并且具有良好的润滑性,因而优先加以选用,特别优选的是聚乙烯基醚、多元醇酯。
本发明中用于基础油的合成油不限于上述具体例子,在配入(B)成分聚亚烷基二醇衍生物的场合,这些化合物不包括在本发明的基础油中。在使用(C)成分特定的醚化物的场合,这些化合物也不包括在本发明的基础油中。
另外,在不损害本发明目的的限度内,可以根据需要将矿物油混合物作为基础油,所述的矿物油例如可以举出石蜡类矿物油、环烷烃类矿物油、中间基类矿物油等。
在本发明的冷冻机油组合物中,可以根据需要适当配入各种公知的添加剂,例如磷酸酯、亚磷酸酯等耐特压添加剂,酚系、胺系防氧化剂,苯基缩水甘油醚、环己烯化氧、环氧化大豆油等环氧化合物稳定剂,苯并三唑、苯并三唑衍生物等铜钝化剂,硅油、氟化硅油等消泡剂等。
在本发明的冷冻机油组合物适用的冷冻机中使用的制冷剂,可以采用氢氟碳系、氟碳系、烃系、醚系、二氧化碳系或氨系制冷剂,其中优先选用氢氟碳系制冷剂。氢氟碳系制冷剂例如有1,1,1,2-四氟乙烷(R134a)、二氟甲烷(R32)、五氟乙烷(R125)和1,1,1-三氟乙烷(R143a),可以使用1种,也可以2种以上组合使用。这些氢氟碳不会破坏臭氧层,适合用作压缩冷冻机的制冷剂。另外,混合制冷剂的例子可以举出:R32/R125/R134a的23∶25∶52(重量比)的混合物(以下简称R407C)、25∶15∶60(重量比)的混合物、R32/R125的50∶50(重量比)的混合物(以下简称R410A)、R32/R125的45∶55(重量比)的混合物(以下简称R410B)、R125/R143a/R134a的44∶52∶4(重量比)的混合物(以下简称R404A)、R125/R143a的50∶50(重量比)的混合物(以下简称R507)等。
实施例
下面通过实施例更详细地说明本发明,但本发明不受这些实施例的限制。
实施例1~10和参考例1、2
在表1所示种类的基础油中,配入表1所示数量(以组合物总重量计算)和种类的添加剂,制成冷冻机油组合物。按以下所述的要领对该组合物进行封闭管试验、磨损试验和实机试验后的毛细管堵塞评价试验,结果示于表2中。
(1)封闭管试验
在玻璃管中装入催化剂Fe/Cu/Al,按R410A/试料油/水=1g/4g/2000wtppm的比例填充、封管。在175℃下保持10天,观察、测定油外观、催化剂外观、总酸值增加量和有无油泥。
(2)磨损试验
使用密闭的block on ring试验机,块/环材料为A4032/SUJ2。将块/环安装固定,在试验容器内填充100g试料油和10gR410A,然后进行磨损试验,试验条件为0.3MPa加压下、转速500rpm、油温50℃、载荷80kg、试验时间60分钟,测定块的磨损幅度。
(3)实机试验
使用空调机用涡卷压缩机的耐久试验机,对添加了1%(重量)防锈油(ォイルコ-トZ5,出光兴产(株)制造)的各种冷冻机油组合物进行6个月的耐久试验,测定毛细管的压损(%:与新品对比)。
[注]·基础油的种类1:聚乙烯基乙醚(A)·聚乙烯基异丙醚(B)无规共聚物,A单元/B单元(摩尔比)=9/1运动粘度68mm2/s(40℃),数均分子量7202:聚乙烯基乙醚(A)·聚乙烯基异丙醚(B)无规共聚物,A单元/B单元(摩尔比)=7/3运动粘度68mm2/s(40℃),数均分子量7103:聚乙烯基乙醚(A)·聚乙烯基异丙醚(B)无规共聚物,A单元/B单元(摩尔比)=5/5运动粘度32mm2/s(40℃),数均分子量4304:季戊四醇与3,3,5-三甲基己酸/异辛酸的混合酸(摩尔比5/5)的酯,运动粘度68mm2/s(40℃)5:三羟甲基丙烷的3,3,5-三甲基己酸酯运动粘度56mm2/s(40℃)·添加剂的种类A1:聚丙二醇壬基·甲基醚运动粘度20mm2/s(40℃),数均分子量400A2:聚丙二醇二仲丁基苯基·甲基醚运动粘度30mm2/s(40℃),数均分子量500A3:聚丙二醇壬基苯基·甲基醚运动粘度10mm2/s(40℃),数均分子量250A4:聚丙二醇·聚壬二醇二甲基醚运动粘度43mm2/s(40℃),数均分子量700
[注]:*)总酸值的增加量mgKOH/g
实施例11~30和参考例3、4
在表3所示种类的基础油中,以组合物总重量计算配入表3所示量的表3所示种类添加剂,制成冷冻机油组合物。对该组合物进行实施例1所述的封闭管试验、磨损试验和实机试验后的毛细管堵塞评价试验,结果示于表4中。表3
[注]·基础油的种类1:聚乙烯基乙醚(A)·聚乙烯基异丁醚(B)无规共聚物,A单元/B单元(摩尔比)=9/1运动粘度68mm2/s(40℃),数均分子量7202:聚乙烯基乙醚(A)·聚乙烯基异丁醚(B)无规共聚物,A单元/B单元(摩尔比)=5/5运动粘度32mm2/s(40℃),数均分子量4303:聚丙二醇二甲基醚运动粘度41mm2/s(40℃),数均分子量10504:聚氧丙烯(A)·聚氧乙烯(B)二醇一丁基醚无规共聚物,A单元/B单元(摩尔比)=9/1运动粘度56mm2/s(40℃),数均分子量10005:三羟甲基丙烷的3,5,5-三甲基己酸三酯运动粘度56mm2/s(40℃),数均分子量5426:三羟甲基丙烷与己二酸的混合酯运动粘度68mm2/s(40℃),数均分子量820·添加剂的种类A1:山梨糖醇的六正丙基醚运动粘度32mm2/s(40℃)A2:季戊四醇的四正己基醚运动粘度38mm2/s(40℃)A3:丙三醇的二苯基辛基三醚运动粘度25mm2/s(40℃)A4:三羟甲基丙烷的二(甲氧基异亚丙基)十二烷基三醚运动粘度33mm2/s(40℃)A5:双甘油的二甲基二辛基四醚运动粘度30mm2/s(40℃)A6:三甘油的四(甲氧基异亚丙基)癸基五醚运动粘度60mm2/s(40℃)A7:二季戊四醇的六丙基醚运动粘度43mm2/s(40℃)A8:三季戊四醇的五甲基辛基六醚运动粘度56mm2/s(40℃)
表4-2
发明的效果
本发明的冷冻机油组合物具有良好的润滑性能,特别是可以提高铝材与钢材之间的润滑性,抑制磨损,适合用来作为使用不造成环境污染的制冷剂的冷冻机的润滑油。
因此,本发明的冷冻机油组合物在用于汽车空调、室内空调、冰箱等时效果特别好,工业上的利用价值非常高。
Claims (17)
1.冷冻机油组合物,其特征是,该冷冻机油组合物是在(A)由合成油构成的基础油中配入(B)数均分子量200~3000的由下述(I)式表示的聚亚烷基二醇衍生物而构成
R1-(OR2)m-(OR3)n-OR4 (I)式中,R1和R4分别表示1~30个碳原子的烃基或酰基或者氢,R2表示2~4个碳原子的亚烷基,R3表示2~30个碳原子的亚烷基或取代的亚烷基,m和n表示满足上述分子量的数,n有时是0,R1、R3和R4中至少有1个具有6个碳原子以上的烃基。
2.权利要求1所述的冷冻机油组合物,其中,聚亚烷基二醇衍生物的配入量是0.1~30%(重量)。
3.由含有0.1~30%(重量)的权利要求1中所述的聚亚烷基二醇衍生物的合成油构成的冷冻机油组合物。
4.由权利要求1中所述的聚亚烷基二醇衍生物和其它合成油构成的冷冻机油组合物。
5.由0.1~30%(重量)权利要求1中所述的聚亚烷基二醇衍生物和70~99.9%(重量)其它合成油构成的冷冻机油组合物。
6.冷冻机油组合物,其特征是,它是在(A)由合成油构成的基础油中配入(C)选自(c-1)3~6元的脂肪族多元醇的醚化物和(c-2)3~6元的脂肪族多元醇的二分子缩合物或三分子缩合物的醚化物、且在40℃下的运动粘度是5~200mm2/s的至少一种醚化物而构成的。
7.权利要求6所述的冷冻机油组合物,其中,醚化物的配入量是0.1~30%(重量)。
8.由含有0.1~30%(重量)权利要求6中所述的醚化物的合成油构成的冷冻机油组合物。
9.由权利要求6中所述的醚化物和其它合成油构成的冷冻机油组合物。
10.由0.1~30%(重量)权利要求6中所述的醚化物和70~99.9%(重量)其它合成油构成的冷冻机油组合物。
11.权利要求6所述的冷冻机油组合物,其中,醚化物是(c-1)3~6元的脂肪族多元醇的醚化物。
12.权利要求11所述的冷冻机油组合物,其中,(c-1)成分的多元醇是丙三醇、三羟甲基丙烷、赤藓醇、季戊四醇、阿拉伯糖醇、山梨糖醇、甘露糖醇。
13.权利要求6所述的冷冻机油组合物,其中,多元醇的二分子缩合物或三分子缩合物是双甘油或二季戊四醇、三甘油或三季戊四醇。
14.权利要求6所述的冷冻机油组合物,其中,醚化物是3~6元的脂肪族多元醇的二分子缩合物的醚化物。
15.权利要求14所述的冷冻机油组合物,其中,多元醇的二分子缩合物是双甘油或二季戊四醇。
16.权利要求6所述的冷冻机油组合物,其中,醚化物是3~6元的脂肪族多元醇的三分子缩合物的醚化物。
17.权利要求16所述的冷冻机油组合物,其中,多元醇的三分子缩合物是三甘油或三季戊四醇。
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JP4410997A JP4856296B2 (ja) | 1997-02-27 | 1997-02-27 | 冷凍機油組成物 |
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JP72909/97 | 1997-03-26 | ||
JP7290997A JP4024899B2 (ja) | 1997-03-26 | 1997-03-26 | 冷凍機油組成物 |
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- 2005-08-30 KR KR1020050079826A patent/KR100622190B1/ko not_active IP Right Cessation
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8715522B2 (en) | 2007-06-15 | 2014-05-06 | Idemitsu Kosan Co., Ltd. | Refrigerator oil composition |
TWI617658B (zh) * | 2015-03-02 | 2018-03-11 | Jx Nippon Oil & Energy Corp | 冷凍機油及冷凍機用作動流體組合物 |
US10494585B2 (en) | 2015-03-02 | 2019-12-03 | Jxtg Nippon Oil & Energy Corporation | Refrigerator oil and working fluid composition for refrigerators |
CN107849475A (zh) * | 2015-07-31 | 2018-03-27 | Jxtg能源株式会社 | 冷冻机油和冷冻机用工作流体组合物 |
CN107849475B (zh) * | 2015-07-31 | 2021-03-12 | Jxtg能源株式会社 | 冷冻机油和冷冻机用工作流体组合物 |
CN108350384A (zh) * | 2015-11-06 | 2018-07-31 | 瑞孚化工产品公司 | 油溶性聚醚及其应用 |
Also Published As
Publication number | Publication date |
---|---|
KR19980071797A (ko) | 1998-10-26 |
US20010011716A1 (en) | 2001-08-09 |
KR100622190B1 (ko) | 2006-09-08 |
KR20060086809A (ko) | 2006-08-01 |
CN1096497C (zh) | 2002-12-18 |
CN1208440C (zh) | 2005-06-29 |
EP0861883B1 (en) | 2015-12-23 |
EP0861883A2 (en) | 1998-09-02 |
KR100579349B1 (ko) | 2006-09-22 |
CN1434106A (zh) | 2003-08-06 |
US6193906B1 (en) | 2001-02-27 |
EP0861883A3 (en) | 1998-12-09 |
TW385332B (en) | 2000-03-21 |
US6322719B2 (en) | 2001-11-27 |
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