CN1157848A - 制冷机油组合物及使用该组合物的压缩机 - Google Patents
制冷机油组合物及使用该组合物的压缩机 Download PDFInfo
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- CN1157848A CN1157848A CN95119851A CN95119851A CN1157848A CN 1157848 A CN1157848 A CN 1157848A CN 95119851 A CN95119851 A CN 95119851A CN 95119851 A CN95119851 A CN 95119851A CN 1157848 A CN1157848 A CN 1157848A
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- Prior art keywords
- compressor
- oil
- acid
- refrigeration agent
- ester
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- 239000000203 mixture Substances 0.000 title claims abstract description 36
- 239000010721 machine oil Substances 0.000 title claims abstract description 21
- -1 polyol ester Chemical class 0.000 claims abstract description 54
- 239000003921 oil Substances 0.000 claims abstract description 48
- 229920005862 polyol Polymers 0.000 claims abstract description 41
- 150000003014 phosphoric acid esters Chemical class 0.000 claims abstract description 29
- 239000002199 base oil Substances 0.000 claims abstract description 28
- OECTYKWYRCHAKR-UHFFFAOYSA-N 4-vinylcyclohexene dioxide Chemical compound C1OC1C1CC2OC2CC1 OECTYKWYRCHAKR-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000003795 chemical substances by application Substances 0.000 claims description 65
- 238000005057 refrigeration Methods 0.000 claims description 56
- 150000004767 nitrides Chemical class 0.000 claims 1
- 239000010802 sludge Substances 0.000 abstract description 22
- 239000003507 refrigerant Substances 0.000 abstract description 5
- 230000000052 comparative effect Effects 0.000 description 28
- 238000012360 testing method Methods 0.000 description 22
- 239000004593 Epoxy Substances 0.000 description 17
- 239000002253 acid Substances 0.000 description 14
- 239000000654 additive Substances 0.000 description 13
- 150000001875 compounds Chemical class 0.000 description 12
- 230000000996 additive effect Effects 0.000 description 11
- 150000002148 esters Chemical class 0.000 description 11
- LVGUZGTVOIAKKC-UHFFFAOYSA-N 1,1,1,2-tetrafluoroethane Chemical compound FCC(F)(F)F LVGUZGTVOIAKKC-UHFFFAOYSA-N 0.000 description 10
- VOPWNXZWBYDODV-UHFFFAOYSA-N Chlorodifluoromethane Chemical compound FC(F)Cl VOPWNXZWBYDODV-UHFFFAOYSA-N 0.000 description 10
- 238000005121 nitriding Methods 0.000 description 10
- 239000004215 Carbon black (E152) Substances 0.000 description 9
- 150000004996 alkyl benzenes Chemical class 0.000 description 9
- 229930195733 hydrocarbon Natural products 0.000 description 9
- 150000002430 hydrocarbons Chemical class 0.000 description 9
- OHMHBGPWCHTMQE-UHFFFAOYSA-N 2,2-dichloro-1,1,1-trifluoroethane Chemical compound FC(F)(F)C(Cl)Cl OHMHBGPWCHTMQE-UHFFFAOYSA-N 0.000 description 7
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- 230000015572 biosynthetic process Effects 0.000 description 7
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- 239000003963 antioxidant agent Substances 0.000 description 6
- 230000003078 antioxidant effect Effects 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 229910019142 PO4 Inorganic materials 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 125000001309 chloro group Chemical group Cl* 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- 239000002480 mineral oil Substances 0.000 description 5
- 235000010446 mineral oil Nutrition 0.000 description 5
- 235000021317 phosphate Nutrition 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
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- 229910052801 chlorine Inorganic materials 0.000 description 4
- RWGFKTVRMDUZSP-UHFFFAOYSA-N isopropyl-benzene Natural products CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 4
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- 238000000034 method Methods 0.000 description 4
- FBUKVWPVBMHYJY-UHFFFAOYSA-N nonanoic acid Chemical compound CCCCCCCCC(O)=O FBUKVWPVBMHYJY-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 4
- 239000010452 phosphate Substances 0.000 description 4
- 238000005096 rolling process Methods 0.000 description 4
- 238000010998 test method Methods 0.000 description 4
- BGHCVCJVXZWKCC-UHFFFAOYSA-N tetradecane Chemical compound CCCCCCCCCCCCCC BGHCVCJVXZWKCC-UHFFFAOYSA-N 0.000 description 4
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- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical group Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 2
- 239000012964 benzotriazole Substances 0.000 description 2
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- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 2
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- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- MNWFXJYAOYHMED-UHFFFAOYSA-N heptanoic acid Chemical compound CCCCCCC(O)=O MNWFXJYAOYHMED-UHFFFAOYSA-N 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- KQNPFQTWMSNSAP-UHFFFAOYSA-N isobutyric acid Chemical compound CC(C)C(O)=O KQNPFQTWMSNSAP-UHFFFAOYSA-N 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 229920013639 polyalphaolefin Polymers 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 2
- 239000006200 vaporizer Substances 0.000 description 2
- OBETXYAYXDNJHR-SSDOTTSWSA-M (2r)-2-ethylhexanoate Chemical compound CCCC[C@@H](CC)C([O-])=O OBETXYAYXDNJHR-SSDOTTSWSA-M 0.000 description 1
- UJPMYEOUBPIPHQ-UHFFFAOYSA-N 1,1,1-trifluoroethane Chemical compound CC(F)(F)F UJPMYEOUBPIPHQ-UHFFFAOYSA-N 0.000 description 1
- DSZTYVZOIUIIGA-UHFFFAOYSA-N 1,2-Epoxyhexadecane Chemical compound CCCCCCCCCCCCCCC1CO1 DSZTYVZOIUIIGA-UHFFFAOYSA-N 0.000 description 1
- XYHKNCXZYYTLRG-UHFFFAOYSA-N 1h-imidazole-2-carbaldehyde Chemical compound O=CC1=NC=CN1 XYHKNCXZYYTLRG-UHFFFAOYSA-N 0.000 description 1
- MLFLWIBXZIPYEI-UHFFFAOYSA-N 2,2,3-trimethylbutanoic acid Chemical compound CC(C)C(C)(C)C(O)=O MLFLWIBXZIPYEI-UHFFFAOYSA-N 0.000 description 1
- FCWBXMTVLZGVEG-UHFFFAOYSA-N 2,2,4-trimethylhexanoic acid Chemical compound CCC(C)CC(C)(C)C(O)=O FCWBXMTVLZGVEG-UHFFFAOYSA-N 0.000 description 1
- QRMMMWOSHHVOCJ-UHFFFAOYSA-N 2,2-dimethylheptanoic acid Chemical compound CCCCCC(C)(C)C(O)=O QRMMMWOSHHVOCJ-UHFFFAOYSA-N 0.000 description 1
- OHCXJEYTMCSTGI-UHFFFAOYSA-N 2,3-dimethylnonanoic acid Chemical compound CCCCCCC(C)C(C)C(O)=O OHCXJEYTMCSTGI-UHFFFAOYSA-N 0.000 description 1
- DKCPKDPYUFEZCP-UHFFFAOYSA-N 2,6-di-tert-butylphenol Chemical compound CC(C)(C)C1=CC=CC(C(C)(C)C)=C1O DKCPKDPYUFEZCP-UHFFFAOYSA-N 0.000 description 1
- YEVQZPWSVWZAOB-UHFFFAOYSA-N 2-(bromomethyl)-1-iodo-4-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=C(I)C(CBr)=C1 YEVQZPWSVWZAOB-UHFFFAOYSA-N 0.000 description 1
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 1
- WQIGUMGLMXARLE-UHFFFAOYSA-N 2-butyl-5-methylhexanoic acid Chemical compound CCCCC(C(O)=O)CCC(C)C WQIGUMGLMXARLE-UHFFFAOYSA-N 0.000 description 1
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- 238000005299 abrasion Methods 0.000 description 1
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- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- BAZMYXGARXYAEQ-UHFFFAOYSA-N alpha-ethyl valeric acid Chemical compound CCCC(CC)C(O)=O BAZMYXGARXYAEQ-UHFFFAOYSA-N 0.000 description 1
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- 229910052782 aluminium Inorganic materials 0.000 description 1
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- 230000000655 anti-hydrolysis Effects 0.000 description 1
- 238000013475 authorization Methods 0.000 description 1
- GWYFCOCPABKNJV-UHFFFAOYSA-N beta-methyl-butyric acid Natural products CC(C)CC(O)=O GWYFCOCPABKNJV-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
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- 239000010949 copper Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000012024 dehydrating agents Substances 0.000 description 1
- 125000003963 dichloro group Chemical group Cl* 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
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- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
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- 238000004821 distillation Methods 0.000 description 1
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 1
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- 229910000398 iron phosphate Inorganic materials 0.000 description 1
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical group [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- AFVFQIVMOAPDHO-UHFFFAOYSA-M methanesulfonate group Chemical class CS(=O)(=O)[O-] AFVFQIVMOAPDHO-UHFFFAOYSA-M 0.000 description 1
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- 238000012986 modification Methods 0.000 description 1
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- 231100000989 no adverse effect Toxicity 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
- 238000011084 recovery Methods 0.000 description 1
- 150000004671 saturated fatty acids Chemical class 0.000 description 1
- 235000003441 saturated fatty acids Nutrition 0.000 description 1
- RHHHGLCTQKINES-UHFFFAOYSA-M sodium;5-amino-2-methoxy-4-sulfobenzenesulfonate Chemical compound [Na+].COC1=CC(S(O)(=O)=O)=C(N)C=C1S([O-])(=O)=O RHHHGLCTQKINES-UHFFFAOYSA-M 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000005437 stratosphere Substances 0.000 description 1
- UAXOELSVPTZZQG-UHFFFAOYSA-N tiglic acid Natural products CC(C)=C(C)C(O)=O UAXOELSVPTZZQG-UHFFFAOYSA-N 0.000 description 1
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 1
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 1
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 1
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 1
- WTLBZVNBAKMVDP-UHFFFAOYSA-N tris(2-butoxyethyl) phosphate Chemical compound CCCCOCCOP(=O)(OCCOCCCC)OCCOCCCC WTLBZVNBAKMVDP-UHFFFAOYSA-N 0.000 description 1
- ZDPHROOEEOARMN-UHFFFAOYSA-N undecanoic acid Chemical compound CCCCCCCCCCC(O)=O ZDPHROOEEOARMN-UHFFFAOYSA-N 0.000 description 1
- 229940005605 valeric acid Drugs 0.000 description 1
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Abstract
本发明提供适宜于用HFC作制冷剂的压缩机用制冷机油组合物，它包括100重量份多元醇酯作为基油，7.0-15.0重量份磷酸酯，和总量为0.2-3.0重量份的1，2-环氧烷和/或二氧化乙烯基环己烯。使用该制冷机油组合物能改善压缩机的滑动部分的耐磨性，并且不会形成来自作为该油组合物的基油使用的多元醇酯的淤渣。本文还披露了使用该油组合物的旋转式压缩机。
Description
本发明涉及用于使用hydrofluorocarbon(HFC)作制冷剂的压缩机的制冷机油组合物及使用该制冷机油组合物的压缩机。更具体地讲，本发明涉及这样一种制冷机油组合物：它能抑制淤渣的形成，具有极佳的耐磨性、载荷能力、热稳定性、化学稳定性、低温流动性和与HFC制冷剂的相容性，并还可用于在严酷的条件例如高温和高压条件下使用的旋转式压缩机。本发明还涉及含有所述制冷机油组合物的具有滑动部分的压缩机、特别是旋转式压缩机。
1.所要求的制冷机油的性能：
冷冻机用压缩机的典型类型是往复式、涡杆式和旋转式。在这些类型中，旋转式压缩机可在严酷条件下象高温和高压条件下使用。
对于用在任何类型的压缩机中的制冷机油一般所考虑的重要性能是耐磨性、载荷能力、热稳定性、化学稳定性、低温流动性和与制冷剂的相容性。
需要具有以下功能的制冷机油：防止磨损压缩机并能冷却压缩机的滑动部分、释放在压缩制冷剂时产生的热量、在压缩制冷剂步骤起密封作用以及除去磨损的粉末和外来物质等。
因此，需要压缩机油不仅要具有极佳的润滑性能(例如耐磨性、载荷能力等)，而且还要在压缩机中具有高热和化学稳定性并对机器零件(例如金属等)无不利影响。
一部分制冷机油还与压缩的制冷剂一起循环通过冷冻机系统，并流入低温区例如蒸发器、毛细管、膨胀阀等。因此，为增强蒸发器的冷却性能和改善由低温区至压缩机的油的回收率，或者为在重新开始操作时能将油低温提供给压缩机的滑动部分，制冷机油需要具有良好的低温流动性和与制冷剂的良好的相容性。2.制冷剂与制冷机油的关系：
迄今为止，作为用于冷冻机的压缩机中的制冷剂，已单独使用Flon系列制冷剂例如含氯氟烃(CFC)系列制冷剂和hydrochloro-fluorocarbon(HCFC)系列制冷剂或使用它们的混合物。这些制冷剂由于极性弱，因此与非极性烃油具有良好的相容性。而且，Flon系列的制冷剂在分子中均具有氯原子，因此该氯与构成压缩机的滑动表面的材料反应形成起润滑剂作用的氯化物。此外，烃油还具有良好的润滑性能。
为此，烃油例如适当精制的环烷矿物油、链烷矿物油、烷基苯、聚-α-烯烃等被单独或以其混合物的形式用作使用Flon系列制冷剂的冷冻机用制冷机油的基油，一般向其中加入抗氧化剂、抗磨损剂、腐蚀抑制剂等。
在这方面，磷酸酯在烃油中具有低溶解性并在低浓度时能表现出耐磨损作用，因此，通常将磷酸酯以不高于1％(重量)的量加至基油(烃油)中。
在有报道同温层中的臭氧层被含氯原子的Flon破坏后，在世界范围内的控制使用CFC系列制冷剂和HCFC系列制冷剂变得严格起来。在此情况下，人们已经进行了替代这些制冷剂的深入细致的研究，已报道了Flon系列制冷剂(例如HCFC-22(R-22))的多种替代物，例如HFC系列混合的制冷剂，例如HFC-134a，HFC-143a，HFC-125，HFC-32等。
然而，由于HFC系列制冷剂极性大，因此它们与烃油的相容性差。因此需要适宜于HFC系列制冷剂的制冷机油。3. HFC系列制冷剂的制冷机油的常规技术
关于使用HFC系列制冷剂的冷冻机用润滑油，已知与HFC系列制冷剂有良好相容性的含氧合成烃油，例如酯系列合成油，聚醚系列合成油等。在这些合成油中，与聚醚系列合成油相比，酯系列合成油具较高的电绝缘性、良好的低温相容性和低吸湿性。
现已知由酯系列合成油构成的制冷机油，如例如以下文献中所披露的：JP-A-56-133241和JP-A-59-164393(此处“JP-A”是指“未审定的公开的日本专利申请”)；与制冷剂用氯代氟代烃或氟代烃一起使用的制冷机油，如JP-A-2-276894中所披露的；和与含氢Flon一同使用的制冷机油，如JP-A-3-88892、JP-A-3-128991和JP-A-3-128992中所披露的。
还有，在JP-A-55-92799、JP-A-56-36570、JP-A-56-125494、JP-A-62-156198、JP-A-3-24197和JP-A-5-59388中披露了包含酯系列合成油和磷酸酯或亚磷酸酯的制冷机油，以及在JP-B-57-43593(此处所用的“JP-B”是指“审定的日本专利申请”)中披露了加热泵用油。
尤其是，上述在JP-A-5-59388中披露的制冷机油还在美国申请专利，为美国专利第5342533号，它用于使用HFC系列制冷剂的冷冻机，基本上由100重量份二元酸二酯或多羟基醇的羧酸酯作基油和5.0-90.0重量份磷酸酯或亚磷酸酯组成。
此外，在JP-A-56-36569、JP-A-58-15592和JP-A-62-292895中还披露了含有硫代亚磷酸酯、环氧化合物和甲磺酸酯的制冷机油。在JP-A-5-17792中还披露了包含酯油、烷基苯或矿物油作基油和烷二醇缩水甘油醚或具有特定结构的脂环族环氧化合物的制冷机油。
多元醇酯(酯系列合成油)显示出极佳的电绝缘性、与HFC系列制冷剂在低温时的相容性和低吸湿性，因此，多元醇酯优选用于使用HFC系列制冷剂的冷冻机。
然而，与烃油相比，多元醇酯是化学活性的，因此在高温时多元醇酯易在压缩机中形成淤渣。而且，由于HFC系列制冷剂在分子中没有氯原子，在严酷条件下使用压缩机的情况下润滑性有时不足。迄今为止人们已采用添加剂来努力改善耐磨性和热稳定性，但还尚未开发出能抑制在使用酯系列合成油中所遇到的淤渣形成问题和预防所遇到的磨损问题的令人满意的添加剂。
特别是，旋转式压缩机在与使用往复式压缩机或涡杆式压缩机的情况相比严酷的条件下使用，因此旋转式压缩机中所使用的制冷机油需要同时具有较强的耐磨性和较高的热稳定性。因此，对于装配有旋转式压缩机的冷冻机，据认为难以使用多元醇酯，因此已有人试图改进压缩机的内部零件。
本发明的目的是提供作为使用HFC系列制冷剂的冷冻机的压缩机用润滑油的制冷机油，所述制冷机油具有良好的耐磨性、抗载荷能力、良好的相容性等性能，并能长期使用，同时能抑制淤渣形成。
本发明的另一个目的是提供具有滑动部分、特别是改进的叶片部分的使用上述制冷机油的旋转式压缩机。
为达到上述目的，本发明人进行了广泛的研究，结果从各种各样的添加剂中寻找到适宜于多元醇酯的添加剂，并发现了与多元醇酯的适当组合和基于多元醇酯的制冷机油的最佳组成比率。由此，本发明人成功地开发出适宜于旋转式压缩机的制冷机油，而制冷机油迄今为止仍被认为难以用多元醇酯作为基油。此外，还对压缩机进行了改进以提高本发明的制冷机油的作用。
也就是说，本发明提供使用HFC作制冷剂的压缩机用制冷机油组合物，它包括(i)100重量份多元醇酯作为基油，(ii)7.0-15.0重量份磷酸酯，和(iii)总量为0.2-3.0重量份的1，2-环氧烷和/或二氧化乙烯基环己烯。
本发明的制冷机油组合物可用在任何类型的具有滑动部分并使用HFC作制冷剂的压缩机中。在使用该制冷剂的旋转式压缩机的情况下，其叶片部分最好经受氮化处理，由此可增强该制冷机油的作用。
图1是实施例中所用的旋转式压缩机的纵截面图。
图2是实施例中所用的旋转式压缩机的横截面图。
在本发明中，多元醇酯被用作制冷机油组合物的基油。
可用在本发明中的多元醇酯是通过使至少一种多羟基醇(例如新戊二醇、三羟甲基丙烷、季戊四醇和二季戊四醇)与至少一种羧酸反应所获得的多元醇酯；所述羧酸有例如直链饱和脂肪酸如乙酸、丙酸、丁酸、戊酸、己酸、庚酸、辛酸、壬酸、癸酸、十一烷酸、十二烷酸等；一烷基支链脂肪酸如异丁酸、2-甲基丁酸、异戊酸、三甲基丙酸、2-甲基戊酸、3-甲基戊酸、4-异己酸、8-乙基己酸、4-丙基戊酸、4-乙基戊酸、2-甲基癸酸、3-甲基癸酸、4-甲基癸酸、5-甲基癸酸、6-甲基癸酸、6-乙基壬酸、5-丙基辛酸、3-甲基十一烷酸，6-丙基壬酸等；和多烷基支链脂肪酸如2，2-二甲基丁酸、2，2-二甲基戊酸、2，2，3-三甲基丁酸、2，2-二甲基己酸、2-甲基-3-乙基戊酸、2，2，3-三甲基戊酸、2，2-二甲基庚酸、2-甲基-3-乙基己酸、2，2，4-三甲基己酸、2，2-二甲基-3-乙基戊酸、2，2，3-三甲基戊酸、2，2-二甲基辛酸、2-丁基-5-甲基戊酸、2-异丁基-5-甲基戊酸、2，3-二甲基壬酸、4，8-二甲基壬酸、2-丁基-5-甲基己酸等。多元醇酯可单独使用或以其混合物的形式使用。
用在本发明中的多元醇酯一般粘度为5-150mm2/s(40℃)、酸值不超过1mg KOH/g、含水量至多500ppm。最好是在使用前将多元醇酯蒸馏、过滤并用吸附剂或脱水剂处理以除去能对制冷机油的热稳定性产生不利影响的杂质、外来物质和水。多元醇酯最好具有不高于0.01mg KOH/g的酸值和不高于100ppm的含水量。
已用于Flon系列制冷剂的环烷矿物油、链烷矿物油、烷基苯和聚-α-烯烃不能用作本发明的制冷机油组合物的基油，因为它们与HFC系列制冷剂的相容性差。
在本发明中，磷酸酯被用作主要成分。磷酸酯的实例包括磷酸三甲酯，磷酸三乙酯，磷酸三丁酯，磷酸三辛酯，磷酸三丁氧基乙酯，磷酸三苯酯，磷酸三甲苯酯，磷酸三二甲苯酯，磷酸甲基二苯酯，diphenylorthoxenyl phosphate，磷酸辛·二苯酯，磷酸苯·异丙·苯酯，磷酸二苯·异丙基苯酯，磷酸三(异丙基苯)酯，磷酸三(氯乙)酯和磷酸三(二氯丙)酯。其中，特别优选磷酸三甲苯酯、磷酸苯·异丙基苯酯、磷酸二苯·异丙基苯酯和磷酸三(异丙基苯)酯。然而本发明不限于这些磷酸酯。
磷酸酯在该油组合物中的含量，基于基油(即多元醇酯)的量计，为7.0-15.0％(重量)。磷酸酯能增进耐磨性。若磷酸酯的量低于7.0％(重量)或超过15.0％(重量)，则耐磨性降低。
在常规使用的HCFC系列制冷剂与烷基苯系列制冷机油配合的情况下，已证实在制冷机油中添加磷酸酯作为特压剂能通过吸附在压缩机滑动表面的金属(Fe)上并与之反应而生成磷酸铁，并还能通过包含在HCFC系列制冷剂中的氯原子在滑动表面上的反应形成氯化物，因而增强耐磨性。另一方面，用在本发明中的HFC系列制冷剂不含氯原子，因而耐磨性差。本发明人经深入细致的研究后发现了能使耐磨性增强的磷酸酯与多元醇酯的最佳用量，即磷酸酯相对于用于HCFC系列制冷剂的烷基苯系列制冷机油的量为约7-15倍。
在本发明中，还加入1，2-环氧烷和/或二氧化乙烯基环己烯作为制冷机油组合物的成分。它们可以单独使用或以其混合物的形式使用。1，2-环氧烷的实例包括1，2-环氧己烷，1，2-环氧庚烷，1，2-环氧辛烷，1，2-环氧癸烷，1，2-环氧十一烷，1，2-环氧十二烷，1，2-环氧十三烷，1，2-环氧十四烷，1，2-环氧十六烷，1，2-环氧十七烷和1，2-环氧十八烷。但本发明不受其限制。二氧化乙烯基环己烯包括各种异构体，其典型的实例具有下面的结构式：
1，2-环氧烷和/或二氧化乙烯基环己烯的总量为基油(即多元醇酯)重量的0.2-3.0％(重量)。若该量小于0.2％(重量)或大于3.0％(重量)，根据所用的压缩机的类型和操作条件，可能产生淤渣。
1，2-环氧烷和二氧化乙烯基环己烯具有抑制在用多元醇酯作基油时所遇到的淤渣形成的作用。尽管不期望受到约束，淤渣形成的机理解释如下。
即，当在高温和高压状态下含水时，多元醇酯易发生水解。由于水解，多元醇酯被分解成醇和酸，酸与压缩机的部件(例如滑动部件)的金属反应，而将该部件腐蚀，还形成淤渣。而且，由于多元醇酯与烃油相比是化学活性的，因此多元醇酯在高温时往往会被改性，形成淤渣。1，2-环氧烷和二氧化乙烯基环己烯能防止多元醇酯的水解和改性。
顺便提一下，除1，2-环氧烷和二氧化乙烯基环己烯外，苯基缩水甘油醚也被归为环氧化合物类，但它不具有抑制淤渣形成的作用。
然而对于可无需严格控制淤渣形成而使用的压缩机，则不必加入1，2-环氧烷和二氧化乙烯基环己烯，只要上述的磷酸酯的加入量为基油(即多元醇酯)重量为7.0-15.0％(重量)即可。
本发明的制冷机油组合物可含有通常用作常规制冷机油的添加剂的抗氧化剂、金属减活剂、消泡剂等。可用在本发明中的抗氧化剂有受阻酚系列抗氧化剂、胺系列抗氧化剂、硫系列抗氧化剂等，例如2，6-二叔丁基-4-甲基苯酚，4，4′-亚甲基二(2，6-二叔丁基苯酚)2，2′-硫基二(4-甲基-6-叔丁基苯酚)，三甲基二氢醌，p，p′-二辛基二苯基胺，3，7-二辛基吩噻嗪，吩噻嗪-1-羧酸烷基酯，苯基-2-萘胺，2，6-二叔丁基-2-二甲基对甲酚，5-ethyl-10，10′-diphenyl-phenazarine和烷基化二硫。金属减活剂的实例包括alizanin，quilizanin，苯并三唑和巯基苯并三唑。消泡剂的实例包括二甲基聚硅氧烷和金属羧酸盐。
本发明的制冷机油组合物可用在任何类型的具有滑动部分的压缩机(例如旋转式压缩机、往复式压缩机和涡杆式压缩机)并使用HFC作制冷剂的压缩机中。按照本发明的优选的实施方案，该油组合物被用在冷冻机中常规使用的旋转式压缩机中。图1和图2举例说明了典型的旋转式压缩机，这两幅图分别为旋转式压缩机的纵截面图和横截面图。
参考下图1和2解释旋转式压缩机。在屏蔽罩1中，装有发动机部分2，由发动机部分2驱动的具有偏心部分3的曲柄轴4由主轴承5和副轴承6支承。安装在曲柄轴4的偏心部分3的圆筒形滚动活塞7在气缸8中偏心滚动，在气缸8中，叶片9被保持与滚动活塞7接触以提供压缩室10。通过由于发动机部分2的旋转所致滚动活塞7的偏心运动，如此构造的旋转式压缩机由吸入孔11吸引制冷剂，在屏蔽罩1中压缩并排出，压缩的制冷剂通过排出管12排入冷却通道。
在极其严酷的条件下运转的压缩机的叶片部分最好由含Cr的铁基材料制成并经过氮化处理，由此，耐磨性和载荷能力被进一步增强。氮化处理可这样进行：将叶片材料置入真空室，向其中引入主要由NH3气体组成的氮化促进剂气体以处理叶片材料。由此，在该叶片的表面形成了耐磨性强的扩散层，取代脆性白色层(ε层)。
实施例
下面将参考下列实施例和对比例详细解释本发明。在实施例和对比例中所用的基油、添加剂和试验方法以及试验结果如下。1.基油：
(1)实施例和对比例1至9、11和12
使用的多元醇酯各具有不高于0.01mg KOH/g的酸值，含水量不超过100ppm，通过季戊四醇与具有7、8和9个碳原子的支链脂肪酸的混合物(C7脂肪酸为2-甲基己酸和2-乙基戊酸；C8脂肪酸为2-乙基己酸；和C9脂肪酸为3，5，5-三甲基己酸)反应合成。
(2)对比例10
使用烷基苯(“ABA-H”，硬型烷基苯的商品名，MitsubishiChemical Corporation制造)。
该烷基苯通常用作使用HCFC-22制冷剂的冷冻机用制冷机油的基油。2.添加剂：
使用磷酸三甲苯酯作为磷酸酯
作为环氧化合物，在实施例1至5、对比例2、4至7、11和12中使用二氧化乙烯基环己烯，而在实施例6中使用1，2-环氧烷(1，2-环氧十二烷和1，2-环氧十三烷和1，2-环氧十四烷的混合物)。
在对比例8和9中使用苯基缩水甘油醚作环氧化合物。
其组成比率(基于基油的量计)见下表1和2。3.试验方法：
(1)Falex试验(磨耗试验)：
在HFC-134a或HCFC-22制冷剂的气氛中，用钢环和钢块作试验材料，用Falex试验(ASTM D2714)在100℃温度和600千帕的气压下进行一小时磨耗试验。测定试验后钢块表面的磨损体积。
(2)屏蔽管试验法(热和化学稳定性试验：)
在HFC-134a或HCFC-22制冷剂的气氛中，用屏蔽管试验法进行热和化学稳定性试验，方法如下：将制冷剂、试验油、Fe、Cu和Al丝置于约1c.c.的玻璃容器中，接着在175℃加热14天，检查试验油的颜色变化与否和淤渣的形成情况。
(4)试验结果：
Falex试验和屏蔽管试验的结果见下表1。Falex试验结果是相对值，取对比例10(其中制冷剂是HCFC-22，基油是烷基苯)中的磨损体积为1.0。
表1(1)
| 组成与试验结果 | 实施例 | |||||
| 1 | 2 | 3 | 4 | 5 | 6 | |
| 制冷剂 | HFC-134a | |||||
| 基油 | 多元醇酯 | |||||
| 添加剂(wt.％)*磷酸酯环氧化合物二氧化乙烯基环己烯1，2-环氧烷 | 7.01.0- | 10.01.0- | 15.01.0- | 10.00.2- | 10.03.0- | 10.0-1.0 |
| Falex试验(磨损体积比)屏蔽管试验(淤渣形成) | 0.9无 | 0.5无 | 0.8无 | 0.5无 | 0.5无 | 0.5无 |
注：*基于基油的量计(下同)
表1(2)
| 组成与试验结果 | 对比例 | |||||
| 1 | 2 | 3 | 4 | 5 | 6 | |
| 制冷剂 | HFC-134a | |||||
| 基油 | 多元醇酯 | |||||
| 添加剂(wt％)磷酸酯环氧化合物二氧化乙烯基环己烯 | -- | -1.0 | 10.0- | 6.01.0 | 16.01.0 | 10.00.1 |
| Falex试验(磨损体积比)屏蔽管试验(淤渣形成) | 4.0观察到 | 4.0无 | 0.5观察到 | 1.6无 | 1.3无 | 0.5观察到 |
表1(3)
| 组成与试验结果 | 对比例 | |||
| 7 | 8 | 9 | 10 | |
| 制冷剂 | HFC-134a | HCFC-22 | ||
| 基油 | 多元醇酯 | 烷基苯 | ||
| 添加剂(wt％)磷酸酯环氧化合物二氧化乙烯基环己烯苯基缩水甘油醚 | 10.03.1- | 10.0-0.5 | 10.0-1.0 | 0.5-- |
| Falex试验(磨损体积比)屏蔽管试验(淤渣形成) | 0.5观察到 | 0.5观察到 | 0.5观察到 | 1.0无 |
(1)实施例1至6和对比例10：
在本发明的实施例中的所有试样中，耐磨性均优于使用HCFC-22制冷剂的对比例10(常规技术的组成)的试样，甚至当使用HFC-134a制冷剂时，亦未形成淤渣(由使用多元醇酯所致)。
(2)对比例1至3、8和9：
在未混有本发明的环氧化合物和磷酸酯的对比例1的试样中，耐磨性和热和化学稳定性差，有淤渣形成。
在未混有磷酸酯的对比例2的样品中，耐磨性差。
在未混有本发明的环氧化合物的对比例3的试样中，形成淤渣。
在混有代替本发明的环氧化合物的苯基缩水甘油醚的对比例8和9的样品中，Fe丝的表面在屏蔽管试验中黑化，明显形成淤渣。
由以上结果可知，要达到本发明的目的，本发明的环氧化合物和磷酸酯是不可缺少的因素。
(3)对比例4和5：
在磷酸酯的用量在本发明所规定的7.0-15.0％(重量)范围之外的对比例4和5的试样中，耐磨性比实施例1至3和6及对比例10的试样的差。
由此结果可知，要达到本发明的目的，磷酸酯的最佳用量为7.0-15.0％(重量)。
(4)对比例6和7：
在本发明的环氧化合物的用量在本发明所规定的0.2-3.0％(重量)范围之外的对比例6和7的试样中，有淤渣形成。
因此可知，要达到本发明的目的，本发明的环氧化合物的最佳用量为0.2-3.0％(重量)。5.实际试验和试验结果：
(1)涡杆式压缩机和旋转式压缩机的加速耐久性试验
通过在实施例2和对比例11和12中使用HFC-134a制冷剂及在对比例10中使用HCFC-22制冷剂，进行2000个小时的涡杆式压缩机或旋转式压缩机的加速耐久性试验。然后将压缩机分解，并观察滑动部分的磨损状况。在使用旋转式压缩机的试验中，使用具有经受氮化处理的叶片部分的表面的压缩机和具有未经氮化处理的叶片部分的压缩机。
试验结果见下表2。
表2
| 组成与试验结果 | 实施例 | 对比例 | ||
| 2 | 11 | 12 | 10 | |
| 制冷剂 | HFC-134a | HCFC-22 | ||
| 基油 | 多元醇酯 | 烷基苯 | ||
| 添加剂(wt.％)磷酸酯环氧化合物二氧化乙烯基环己烯 | 10.01.0 | 5.01.0 | 20.01.0 | 0.5- |
| 涡杆式压缩机加速耐久性试验(滑动部分的磨损状态) | 轻度 | 中度 | 中度 | 轻度 |
| 旋转式压缩机加速耐久性试验(叶片部分的磨损状态)氮化的叶片部分未氮化的叶片部分 | 轻度中度 | 磨损 | 磨损 | 轻度轻度 |
在对比例11(磷酸酯的量为5.0％(重量)和对比例12(磷酸酯的量为20.0％(重量))中，涡杆式压缩机的滑动部分的磨损量比实施例2和对比例10中的大。结果与表1中所示的Falex试验结果一致。
在对比例11和12中，即使经受了氮化处理，在叶片部分仍出现磨损，耐磨性差。
另一方面，在实施例2中，经受氮化处理的叶片部分的耐磨性比未经受氮化处理的叶片部分的好。
由此已经证实，在严酷条件下工作的旋转式压缩机中，本发明的作用可以通过将其叶片部分氮化处理得到增强。
如上所述，本发明是使用已被推荐作为HCFC系列制冷剂的替代物的HFC-134a制冷剂和其它HFC系列制冷剂的压缩机用制冷机油组合物。
本发明的制冷机油组合物基本上由多元醇酯作为基油和磷酸酯和特定的环氧化合物(即1，2-环氧烷和/或二氧化乙烯基环己烯)作为添加剂所组成。
此外，本发明的特征在于：含在基油中的各上述添加剂的量在特定范围内。
按照本发明，通过将多元醇酯与磷酸酯作特压剂或抗磨损剂以及1，2-环氧烷和/或二氧化乙烯基环己烯作防水解剂按最佳量混合，能够解决在使用多元醇酯的情况下所遇到的耐磨性不足和形成淤渣的问题，同时还能享有多元醇酯(酯系列合成油)的有益性能例如电绝缘性，与HFC制冷剂的相容性，低吸湿性。
通过使用本发明的制冷机油组合物，可以将各种压缩机的滑动部分的磨损降至最低，因此可以增加压缩机的可靠性。此外，同时配合在极严酷的条件下运转的旋转式压缩机的滑动部分的叶片部分的氮化处理，可进一步将叶片部分的磨损降至最低，并进一步增加旋转式压缩机的可靠性。
尽管已参考具体的实施方案详细描述了本发明，但显而易见的是，本领域技术人员可不背离本发明的精神和范围对其做出各种改变和改进。
Claims (3)
1.使用HFC作制冷剂的压缩机用制冷机油，它包括(i)100重量份多元醇酯作为基油，(ii)7.0-15.0重量份磷酸酯，和(iii)总量为0.2-3.0重量份的1，2-环氧烷和/或二氧化乙烯基环己烯。
2.具有滑动部分和引入其中的制冷剂HFC和制冷机油组合物的压缩机，所述制冷机油组合物包括(i)100重量份多元醇酯作为基油，(ii)7.0-15.0重量份磷酸酯，和(iii)总量为0.2-3.0重量份的1，2-环氧烷和/或二氧化乙烯基环己烯。
3.权利要求2的压缩机，它是具有表面经氮化处理的叶片部分的旋转式压缩机。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6319524A JPH08151590A (ja) | 1994-11-30 | 1994-11-30 | 冷凍機油組成物及び圧縮機 |
| JP319524/94 | 1994-11-30 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1157848A true CN1157848A (zh) | 1997-08-27 |
Family
ID=18111201
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN95119851A Pending CN1157848A (zh) | 1994-11-30 | 1995-11-30 | 制冷机油组合物及使用该组合物的压缩机 |
Country Status (9)
| Country | Link |
|---|---|
| US (1) | US5653909A (zh) |
| EP (1) | EP0714973A1 (zh) |
| JP (1) | JPH08151590A (zh) |
| KR (1) | KR0167847B1 (zh) |
| CN (1) | CN1157848A (zh) |
| BR (1) | BR9505561A (zh) |
| MY (1) | MY132059A (zh) |
| SG (1) | SG50375A1 (zh) |
| TW (1) | TW312704B (zh) |
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| CN109022105A (zh) * | 2018-06-13 | 2018-12-18 | 权家（厦门）新材料有限公司 | 一种水溶性氟碳石墨烯机油及其制备方法 |
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- 1995-06-06 US US08/468,754 patent/US5653909A/en not_active Expired - Fee Related
- 1995-10-16 MY MYPI95003097A patent/MY132059A/en unknown
- 1995-11-28 SG SG1995001948A patent/SG50375A1/en unknown
- 1995-11-29 BR BR9505561A patent/BR9505561A/pt active Search and Examination
- 1995-11-29 EP EP95308577A patent/EP0714973A1/en not_active Ceased
- 1995-11-30 CN CN95119851A patent/CN1157848A/zh active Pending
- 1995-11-30 KR KR1019950045156A patent/KR0167847B1/ko not_active IP Right Cessation
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| CN102958901B (zh) * | 2010-08-24 | 2015-02-18 | Kh新化株式会社 | 新戊二醇二酯 |
| CN109022105A (zh) * | 2018-06-13 | 2018-12-18 | 权家（厦门）新材料有限公司 | 一种水溶性氟碳石墨烯机油及其制备方法 |
| CN109022105B (zh) * | 2018-06-13 | 2021-09-17 | 权家（厦门）新材料有限公司 | 一种水溶性氟碳石墨烯机油及其制备方法 |
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Also Published As
| Publication number | Publication date |
|---|---|
| EP0714973A1 (en) | 1996-06-05 |
| KR0167847B1 (ko) | 1999-01-15 |
| SG50375A1 (en) | 1998-07-20 |
| BR9505561A (pt) | 1997-11-04 |
| KR960017827A (ko) | 1996-06-17 |
| JPH08151590A (ja) | 1996-06-11 |
| TW312704B (zh) | 1997-08-11 |
| MY132059A (en) | 2007-09-28 |
| US5653909A (en) | 1997-08-05 |
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