CN1239687C - 用于二氧化碳致冷剂的致冷油组合物 - Google Patents
用于二氧化碳致冷剂的致冷油组合物 Download PDFInfo
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- CN1239687C CN1239687C CNB008116474A CN00811647A CN1239687C CN 1239687 C CN1239687 C CN 1239687C CN B008116474 A CNB008116474 A CN B008116474A CN 00811647 A CN00811647 A CN 00811647A CN 1239687 C CN1239687 C CN 1239687C
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- carbon atom
- expression
- carbon dioxide
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- acid
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 116
- 239000000203 mixture Substances 0.000 title claims abstract description 96
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 50
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 50
- 239000003507 refrigerant Substances 0.000 title claims abstract description 44
- 239000012530 fluid Substances 0.000 title 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 26
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052799 carbon Inorganic materials 0.000 claims description 122
- 125000000217 alkyl group Chemical group 0.000 claims description 66
- 239000010721 machine oil Substances 0.000 claims description 55
- 230000014509 gene expression Effects 0.000 claims description 47
- 239000002253 acid Substances 0.000 claims description 42
- 150000001875 compounds Chemical class 0.000 claims description 39
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 33
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 30
- 150000003839 salts Chemical class 0.000 claims description 29
- 239000005069 Extreme pressure additive Substances 0.000 claims description 28
- 229930195733 hydrocarbon Natural products 0.000 claims description 19
- 125000004429 atom Chemical group 0.000 claims description 18
- 239000004215 Carbon black (E152) Substances 0.000 claims description 17
- 235000011089 carbon dioxide Nutrition 0.000 claims description 17
- 239000002516 radical scavenger Substances 0.000 claims description 15
- 125000001118 alkylidene group Chemical group 0.000 claims description 14
- 125000004432 carbon atom Chemical group C* 0.000 claims description 14
- 125000002252 acyl group Chemical group 0.000 claims description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 239000003153 chemical reaction reagent Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229920001289 polyvinyl ether Polymers 0.000 abstract description 16
- 239000012298 atmosphere Substances 0.000 abstract description 9
- 239000010726 refrigerant oil Substances 0.000 abstract 1
- 150000001721 carbon Chemical group 0.000 description 104
- -1 hydrocarbon radical Chemical class 0.000 description 79
- 239000002826 coolant Substances 0.000 description 24
- 239000003921 oil Substances 0.000 description 23
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- 238000005057 refrigeration Methods 0.000 description 21
- 229910052751 metal Inorganic materials 0.000 description 14
- 239000002184 metal Substances 0.000 description 14
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 11
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 11
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- 150000001412 amines Chemical class 0.000 description 9
- 239000002199 base oil Substances 0.000 description 9
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- 239000002904 solvent Substances 0.000 description 9
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 239000000654 additive Substances 0.000 description 7
- 239000002585 base Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 150000002430 hydrocarbons Chemical class 0.000 description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- 238000004378 air conditioning Methods 0.000 description 6
- 239000003963 antioxidant agent Substances 0.000 description 6
- 230000003078 antioxidant effect Effects 0.000 description 6
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- 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 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 6
- 239000010687 lubricating oil Substances 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
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 5
- 230000000996 additive effect Effects 0.000 description 5
- 125000001931 aliphatic group Chemical group 0.000 description 5
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 5
- 125000004183 alkoxy alkyl group Chemical group 0.000 description 5
- 125000006267 biphenyl group Chemical group 0.000 description 5
- 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 5
- 235000014113 dietary fatty acids Nutrition 0.000 description 5
- 229930195729 fatty acid Natural products 0.000 description 5
- 239000000194 fatty acid Substances 0.000 description 5
- 150000004665 fatty acids Chemical class 0.000 description 5
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 5
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 5
- GBHRVZIGDIUCJB-UHFFFAOYSA-N hydrogenphosphite Chemical compound OP([O-])[O-] GBHRVZIGDIUCJB-UHFFFAOYSA-N 0.000 description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- 229920001515 polyalkylene glycol Polymers 0.000 description 5
- LVGUZGTVOIAKKC-UHFFFAOYSA-N 1,1,1,2-tetrafluoroethane Chemical compound FCC(F)(F)F LVGUZGTVOIAKKC-UHFFFAOYSA-N 0.000 description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 4
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- 229910019142 PO4 Inorganic materials 0.000 description 4
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 4
- 239000005864 Sulphur Substances 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 4
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 4
- 125000003710 aryl alkyl group Chemical group 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- KBPLFHHGFOOTCA-UHFFFAOYSA-N caprylic alcohol Natural products CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 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 4
- ZQPPMHVWECSIRJ-MDZDMXLPSA-N elaidic acid Chemical compound CCCCCCCC\C=C\CCCCCCCC(O)=O ZQPPMHVWECSIRJ-MDZDMXLPSA-N 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 125000000219 ethylidene group Chemical group [H]C(=[*])C([H])([H])[H] 0.000 description 4
- 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 4
- 229920001519 homopolymer Polymers 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- VKOBVWXKNCXXDE-UHFFFAOYSA-N icosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCC(O)=O VKOBVWXKNCXXDE-UHFFFAOYSA-N 0.000 description 4
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 4
- 150000002632 lipids Chemical class 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 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 4
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 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 4
- 239000010452 phosphate Substances 0.000 description 4
- 108010001861 pregnancy-associated glycoprotein 1 Proteins 0.000 description 4
- 239000004711 α-olefin Substances 0.000 description 4
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 3
- UUAMLBIYJDPGFU-UHFFFAOYSA-N 1,3-dimethoxypropane Chemical compound COCCCOC UUAMLBIYJDPGFU-UHFFFAOYSA-N 0.000 description 3
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 3
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 3
- 239000005642 Oleic acid Substances 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 3
- 150000001342 alkaline earth metals Chemical class 0.000 description 3
- 125000003342 alkenyl group Chemical group 0.000 description 3
- 125000002877 alkyl aryl group Chemical group 0.000 description 3
- 125000002947 alkylene group Chemical group 0.000 description 3
- 239000004411 aluminium Substances 0.000 description 3
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- 229910052728 basic metal Inorganic materials 0.000 description 3
- 150000003818 basic metals Chemical class 0.000 description 3
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 3
- 125000000753 cycloalkyl group Chemical group 0.000 description 3
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 3
- 230000007812 deficiency Effects 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
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- 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 3
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- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 3
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
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- GPOGLVDBOFRHDV-UHFFFAOYSA-N (2-nonylphenyl) dihydrogen phosphite Chemical compound CCCCCCCCCC1=CC=CC=C1OP(O)O GPOGLVDBOFRHDV-UHFFFAOYSA-N 0.000 description 2
- QEGNUYASOUJEHD-UHFFFAOYSA-N 1,1-dimethylcyclohexane Chemical compound CC1(C)CCCCC1 QEGNUYASOUJEHD-UHFFFAOYSA-N 0.000 description 2
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- 125000001624 naphthyl group Chemical group 0.000 description 2
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- 230000003647 oxidation Effects 0.000 description 2
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- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
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- C10M169/04—Mixtures of base-materials and additives
- C10M169/044—Mixtures of base-materials and additives the additives being a mixture of non-macromolecular and macromolecular compounds
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- C10M171/008—Lubricant compositions compatible with refrigerants
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Abstract
用于二氧化碳致冷剂的致冷油组合物,其含有作为主要成分的一种混合物,包括(A)一种聚乙烯基醚,在100℃运动粘度为3-50mm2/s,其量为大于40重量%且小于等于99.1重量%;和(B)一种聚氧化亚烷基二醇,在100℃运动粘度为3-50mm2/s,其量为大于等于0.1重量%且小于40重量%。该组合物表现出极好的润滑性和很大的粘度指数,即使在使用二氧化碳致冷剂时。在超临界条件下的二氧化碳气氛中该组合物表现出极好的稳定性和极好的润滑性,同时可保持上述有利的性质并可长期使用。
Description
发明领域
本发明涉及一种致冷油组合物,用于使用二氧化碳(CO2)致冷剂的冷冻设备。致冷油组合物可用于使用二氧化碳致冷剂的压缩型冷冻设备,其是致冷和空气调节设备,诸如汽车空调、冰箱、冰库、空调和热泵。
背景技术
通常,压缩型冷冻设备的致冷循环由压缩机、冷凝器、膨胀阀和蒸发器组成,其具有一种结构,其中致冷剂和润滑油的混合液体在封闭的体系中循环。迄今,氟氯烃,诸如二氯二氟甲烷(R-12)和氯二氟甲烷(R-22)已经作为致冷剂使用,并且已经生产了各种类型的润滑油并与致冷剂一起使用。但是,由于氯氟烃可能导致环境污染,诸如当这些物质释放到大气中时,破坏平流层中的臭氧层,因此对氯氟烃的管理在全球范围变得更加严格。由于这种情况,新的致冷剂引起了人们的注意,诸如氢氟烃和氟代烃,其典型的例子包括1,1,1,2-四氟乙烷(R-134a)。但是,由于氢氟烃和氟代烃在大气中长期存在,这些物质可能导致全球变暖,虽然这些物质不可能导致上述环境污染。因此,人们考虑用不会导致上述问题的天然物质衍生的致冷剂。
二氧化碳是有利的,因为其对于环境无毒,对人类安全,并且具有其它优点,因为其容易在任何需要的地方获得,无需循环,非常便宜。因此,在此以前,二氧化碳已经作为致冷剂用于冷冻设备。
在二氧化碳作为致冷剂的方面,公开了可通过使用聚乙烯醚作为致冷油组合物用于二氧化碳致冷剂提高密封性(日本专利申请公开No.平10(1998)-46169)。
但是,由于粘度指数小,被认为有效的作为致冷油组合物用于二氧化碳致冷剂的聚乙烯醚有一个问题,在高温下将粘度调节到确保表现出润滑性的适当值时,在低温下粘度增加并增加了功率损失。
因此,作为润滑油与二氧化碳致冷剂一起使用的致冷油在低温下表现出粘度略有增加,即,理想的是具有更大粘度指数的致冷油。在使用二氧化碳致冷剂的体系中,致冷油与在超临界条件下的二氧化碳接触,因为排放压力比使用R-134a或类似体系的更高并且温度更高。因此,当常规用于氯氟烃、氢氟烃或氟代烃致冷剂的润滑油用于润滑时,会产生其它问题,因为润滑稳定性变差和不可能实现长期稳定操作,还因为表现出差的润滑性,诸如耐磨性不足。
发明概述
本发明已经解决了上述问题。本发明的一个目的是提供一种致冷油组合物,即使当含有二氧化碳作为主成分的冷冻液作为冷冻液使用时,该组合物表现出极好的润滑性和很大的粘度指数。
本发明另一个目的是提供一种在超临界条件下的二氧化碳气氛中表现出极好稳定性和极好润滑性的致冷油组合物,同时保持上述有利的性质并可长期使用。
人们发现,当聚氧化亚烷基二醇与聚乙烯基醚结合使用时,聚乙烯基醚的粘度指数意想不到地增加并且可得到表现出极好润滑性和很大粘度指数的致冷油组合物,当特定的添加剂与致冷油组合物结合使用时,可提高稳定性和润滑性,即使在超临界条件的二氧化碳气氛下,同时保持粘度指数和极好的可溶混性。本发明基于上述认识完成。
本发明提供:
(1)用于二氧化碳致冷剂的致冷油组合物,其含有作为主要成分的一种混合物,包括(A)一种聚乙烯基醚,在100℃运动粘度为3-50mm2/s,其量为大于40重量%且小于等于99.1重量%;和(B)一种聚氧化亚烷基二醇,在100℃运动粘度为3-50mm2/s,其量为大于等于0.1重量%且小于40重量%;
(2)如(1)所述的用于二氧化碳致冷剂的致冷油组合物,其运动粘度在100℃为3-50mm2/s,并且粘度指数大于等于90;
(3)如(1)或(2)所述的用于二氧化碳致冷剂的致冷油组合物,其中聚氧化亚烷基二醇是通式(I)表示的化合物:
R1-[(OR2)m-OR3]n (I)
其中R1表示氢原子、有1-10个碳原子的烷基、有2-10个碳原子的酰基或有1-10个碳原子和2-6个结合部位的脂族烃基;R2表示有2-4个碳原子的亚烷基;R3表示氢原子、有1-10个碳原子的烷基或有2-10个碳原子的酰基;n表示1-6的整数;m表示的数使得m×n表示的数的平均值为6-80;
(4)如(1)-(3)任一项所述的用于二氧化碳致冷剂的致冷油组合物,其中聚乙烯基醚是通式(V)表示的化合物:
其中R16、R17和R18分别表示氢原子或有1-8个碳原子的烃基,R16、R17和R18表示的原子和基团可以彼此相同或不同;R19表示有1-10个碳原子的二价烃基;R20表示有1-20个碳原子的烃基;k表示的数平均值在0-10范围内;在构成的单元中R16至R20表示的原子和基团可以彼此相同或不同;并且,当存在多个R19O时,多个R19O可以表示相同或不同的基团;
(5)如(1)-(4)任一项所述的用于二氧化碳致冷剂的致冷油组合物,其含有一种酸清除剂;
(6)如(5)所述的用于二氧化碳致冷剂的致冷油组合物,其含有0.005-5.0重量%的酸清除剂;
(7)如(1)-(6)任一项所述的用于二氧化碳致冷剂的致冷油组合物,其含有一种耐特压添加剂;
(8)如(7)所述的用于二氧化碳致冷剂的致冷油组合物,其中耐特压添加剂是至少一种选自羧酸金属盐的试剂和含磷的耐特压添加剂。
(9)如(7)或(8)所述的用于二氧化碳致冷剂的致冷油组合物,其含有0.001-5.0重量%的耐特压添加剂;和
(10)如(1)-(9)任一项所述的用于二氧化碳致冷剂的致冷油组合物,其中二氧化碳致冷剂含有大于等于90%重量的二氧化碳。
附图说明
图1所示流程图表示压缩型制冷循环的一个例子,其中使用了本发明的致冷油组合物。
图2所示流程图表示压缩型制冷循环的另一个例子,其中使用了本发明的致冷油组合物。
图3所示的流程图仍然表示压缩型制冷循环的另一个例子,其中使用了本发明的致冷油组合物。
图4所示的流程图仍然表示压缩型制冷循环的另一个例子,其中使用了本发明的致冷油组合物。
在附图中,1表示压缩机,2表示冷凝器,3表示膨胀阀,4表示蒸发器,5表示油分离器,6表示热汽管线,7表示热汽管线的阀。
实施本发明的最佳方案
下面描述本发明优选的实施方案。
首先,本发明提供了一种用于二氧化碳致冷剂的致冷油组合物,其包括作为主要成分的一种混合物,包括(A)一种聚乙烯基醚,在100℃运动粘度为3-50mm2/s,优选5-30mm2/s,更优选7-20mm2/s,其量为大于40重量%且小于等于99.1重量%;和(B)一种聚氧化亚烷基二醇,在100℃运动粘度为3-50mm2/s,优选5-40mm2/s,更优选7-40mm2/s,最优选7-30mm2/s,其量为大于等于0.1重量%且小于40重量%。
基于下述原因将上述成分的运动粘度限定在上述范围内。限制下限使得包括成分混合物的用于二氧化碳致冷剂的致冷油组合物的运动粘度保持在适当的数值并且表现出润滑性。限制上限使得冷冻设备的实际操作不受到动力损失的不利影响。
本发明用于二氧化碳致冷剂的致冷油组合物包括含有成分(A)和成分(B)的混合物,其运动粘度选自范围3-50mm2/s,优选5-40mm2/s,更优选7-30mm2/s。粘度指数选自范围大于或等于90,更优选大于或等于95。当致冷油组合物的粘度指数小于90时,有时加入聚亚烷基二醇基本上表现为不起作用,不能达到获得适宜的粘度指数的目的。
在混合物中成分(A)聚乙烯基醚的量和成分(B)聚氧化亚烷基二醇的量如下。成分(A)的量选自范围大于40%重量且小于等于99.1%重量,成分(B)的量选自范围大于等于0.1重量%且小于40%重量。优选成分(A)的量选自范围大于60%重量且小于等于97%重量,成分(B)的量选自范围大于等于3重量%且小于40%重量。更优选成分(A)的量选自范围大于60%重量且小于等于95%重量,成分(B)的量选自范围大于等于5重量%且小于40%重量。当成分(B)的量小于上述范围,不能充分显示出致冷油组合物改进粘度指数的作用。当成分(B)的量超过上述范围,降低了两相分离的温度,即,不能混合的范围增加了。
在本发明中,用作成分(B)的聚氧化亚烷基二醇的例子包括通式(I)表示的化合物:
R1-[(OR2)m-OR3]n (I)
其中R1表示氢原子、有1-10个碳原子的烷基、有2-10个碳原子的酰基或有1-10个碳原子和2-6个结合部位的脂族烃基;R2表示有2-4个碳原子的亚烷基;R3表示氢原子、有1-10个碳原子的烷基或有2-10个碳原子的酰基;n表示1-6的整数;m表示的数使得m×n表示的数的平均值为6-80;
在上述通式(I)中,R1或R3表示的有1-10个碳原子的烷基可以是任何直链、支链和环状的烷基。烷基的例子包括甲基、乙基、正丙基、异丙基、各种类型的丁基、各种类型的戊基、各种类型的己基、各种类型的庚基、各种类型的辛基、各种类型的壬基、各种类型的癸基、环戊基和环己基。当烷基中碳原子数超过10时,与致冷剂的可混溶性降低,有时发生相分离。优选烷基中碳原子数为1-6。
在R1和R3表示的有2-10个碳原子的酰基中,烷基部分可以是任何直链、支链或环状的烷基。酰基中烷基部分的例子包括上述作为烷基的例子中有1-9个碳原子的烷基。当酰基中碳原子数超过10时,与致冷剂的可混溶性降低,有时发生相分离。优选烷基中碳原子数为2-6。
当R1和R3分别表示烷基或酰基时,R1和R3可以表示相同或不同的基团。
当n表示大于等于2的数时,在一个分子中多个R3表示的原子和基团可以彼此相同或不同。
当R1表示有1-10个碳原子和2-6个结合部位的脂族烃基时,脂族烃基可以是直链或环状的。有2个结合部位的脂族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。有3-6个结合部位的脂族烃基的例子包括从诸如三羟甲基丙烷、丙三醇、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的多元醇除去羟基得到的残基。
当脂族烃基中碳原子数超过10时,与致冷剂的可混溶性降低,有时发生相分离。优选碳原子数为2-6。
在本发明中,从粘度方面考虑,优选R1和R3至少一个表示烷基,更优选有1-3个碳原子的烷基,最优选甲基。从相同的立场出发,优选R1和R3均表示烷基,优选甲基。
在上述通式(I)中,R2表示有2-4个碳原子的亚烷基。作为重复单元的氧化亚烷基的例子包括氧化亚乙基、氧化亚丙基和氧化亚丁基。在一个分子中的氧化亚烷基可以彼此相同或可包括两种或多种氧化亚烷基。优选聚氧化亚烷基二醇是包括氧化亚乙基(EO)和氧化亚丙基(PO)的共聚物。从胶住载荷和粘度立场出发,优选EO/(PO+E0)的值在0.1-0.8范围内。从吸湿性立场出发,优选EO/(PO+EO)的值在0.3-0.6范围内。
在上述通式(I)中,n表示1-6的整数,其根据R1表示的基团的结合部位的数量确定。例如,当R1表示烷基或酰基时,n表示1;当R1分另表示有2、3、4、5或6个结合部位的脂族烃基时,n表示2、3、4、5或6。在通式(I)中,m表示的数使m×n表示的数的平均值在6-80范围内。当m×n的平均值超过上述范围时,有时本发明的目的不能充分实现。
上述通式(I)表示的聚亚烷基二醇包括在链端有羟基的聚亚烷基二醇。可有利地使用在链端有羟基的聚亚烷基二醇,只要基于链端基团的总数计链端羟基的含量小于等于50%摩尔。当上述含量超过50%摩尔时,吸湿性增加,粘度指数下降。因此,这样的含量不是优选的。
作为上述聚亚烷基二醇,从经济和效果的立场出发,优选下述通式表示的聚氧化亚丙基二醇二甲基醚:
其中x表示6-80的数,
以及下述通式表示的聚氧化亚乙基-聚氧化亚丙基二醇二甲基醚:
其中a和b分别表示大于或等于1的数,a和b表示的数的总和在6-80范围内;从经济立场出发,优选通式表示的聚氧化亚丙基二醇单丁基醚和聚氧化亚丙基二醇二乙酸酯:
其中x表示6-80的数。
通式(I)表示的聚氧化亚烷基二醇化合物的例子包括所有在日本专利申请公开No.平2(1990)-305893中详细描述的化合物。
在本发明中,可使用有至少一个下述通式(II)表示的组成单元的聚氧化亚烷基二醇衍生物:
在通式(II)中,R4至R7分别表示氢原子、有1-10个碳原子的一价烃基或通式(III)表示的基团:
并且R4至R7至少一个表示通式(III)所示的基团。在通式(III)中,R8和R9分别表示氢原子、有1-10个碳原子的一价烃基或有2-20个碳原子的烷氧基烷基,R10表示有2-5个碳原子的亚烷基、有烷基作为取代基且总共有2-5个碳原子的被取代的亚烷基或有烷氧基烷基作为取代基且总共有4-10个碳原子的被取代的亚烷基,n表示0-20的整数,R11表示有1-10个碳原子的一价烃基。在上述通式(II)中,R4至R7分别表示氢原子、有1-10个碳原子的一价烃基或通式(III)所示的基团。作为有1-10个碳原子的一价烃基,优选有6个或更少碳原子的一价烃基,更优选有3个或更少碳原子的烷基。
在通式(III)中,R8和R9分别表示氢原子、有1-10个碳原子的一价烃基或有2-20个碳原子的烷氧基烷基。这些基团中,优选有3个或更少碳原子的烷基和有6个或更少碳原子的烷氧基烷基。
R10表示有2-5个碳原子的亚烷基、有烷基作为取代基且总共有2-5个碳原子的被取代的亚烷基或有烷氧基烷基作为取代基且总共有4-10个碳原子的被取代的亚烷基。优选R10表示亚乙基或有6个或更少碳原子的被取代的亚乙基。
R11表示有1-10个碳原子的一价烃基,优选有6个或更少碳原子的烃基,更优选有3个或更少碳原子的烃基。
在上述通式(II)中,R4至R7至少一个表示通式(III)所示的基团。优选R4和R6之一表示通式(III)所示的基团,R4和R6中另一个基团、R5和R7分别表示氢原子或有1-10个碳原子的一价烃基。
聚氧化亚烷基二醇衍生物包括至少一个通式(II)所示的组成单元。聚亚烷基二醇衍生物可分成下述三种化合物:均聚物,含有单一类型的通式(II)所示的组成单元;共聚物,含有两种或多种类型的通式(II)所示的组成单元;共聚物,含有通式(II)所示的组成单元和其它组成单元,诸如通式(IV)所示的组成单元:
其中R12至R15分别表示氢原子或有1-3个碳原子的烷基。
上述均聚物的例子包括含有1-200个通式(II)所示组成单元且在每个链端有羟基、有1-10个碳原子的酰氧基、有1-10个碳原子的烷氧基或芳氧基的均聚物。
共聚物的例子包括含有各自数量为1-200、分别由通式(II)所示的两类组成单元(A)和(B)的共聚物和含有1-200个通式(II)所示的(A)组成单元和1-200个通式(III)所示的(C)组成单元的共聚物,每种共聚物在每个链端有羟基、有1-10个碳原子的酰氧基、有1-10个碳原子的烷氧基或芳氧基。上述共聚物包括含有组成单元A和组成单元B(或组成单元C)的交替共聚物、无规共聚物和嵌段共聚物,以及接枝共聚物,其包括含有组成单元A的主链和接枝在上面的组成单元B。
用作本发明成分(A)的聚乙烯基醚的例子包括含有通式(V)所示组成单元的聚乙烯基醚化合物:
其中R16、R17和R18分别表示氢原子或有1-8个碳原子的烃基,R16、R17和R18表示的原子和基团可以彼此相同或不同;R19表示有1-10个碳原子的二价烃基;R20表示有1-20个碳原子的烃基;k表示的数使得平均值在0-10范围内;在组成单元之间R16至R20表示的原子和基团可以彼此相同或不同;并且,当存在多个R19O时,多个R19O可以表示相同的基团或不同的基团。
还可以使用是含有通式(V)所示的组成单元和下述通式(VI)所示的组成单元的嵌段或无规共聚物的聚乙烯基醚化合物:
在通式(VI)中,R21至R24分别表示氢原子或有1-20个碳原子的烃基。R21至R24表示的原子和基团可以彼此相同或不同。在组成单元之间R21至R24表示的原子和基团可以彼此相同或不同。
在上述通式(V)中,R16、R17和R18分别表示氢原子或有1-8个碳原子、优选1-4个碳原子的烃基。R16、R17和R18表示的原子和基团可以彼此相同或不同。烃基的例子包括烷基,诸如甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基、叔丁基、各种类型的戊基、各种类型的己基、各种类型的庚基和各种类型的辛基;环烷基,诸如环戊基、环己基、各种类型的甲基环己基、各种类型的乙基环己基和各种类型的二甲基环己基;芳基,诸如苯基、各种类型的甲基苯基、各种类型的乙基苯基和各种类型的二甲基苯基;和芳烷基,诸如苄基、各种类型的苯乙基和各种类型的甲基苄基。优选R16、R17和R18分别表示氢原子。
在通式(V)中,R19表示有1-10个碳原子、优选2-10个碳原子的二价烃基。有1-10个碳原子的二价烃基的例子包括二价脂族基团,诸如亚甲基、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、各种类型的亚丁基、各种类型的亚戊基、各种类型的亚己基、各种类型的亚庚基、各种类型的亚辛基、各种类型的亚壬基和各种类型的亚癸基;在诸如环己烷、甲基环己烷、乙基环己烷、二甲基环己烷和丙基环己烷的脂环族烃上有两个结合部位的脂环基;二价芳烃基,诸如各种类型的亚苯基、各种类型的甲基亚苯基、各种类型的乙基亚苯基、各种类型的二甲基亚苯基和各种类型的亚萘基;在诸如甲苯、二甲苯和乙苯的烷基芳烃的每个烷基部分和芳基部分有一个一价结合部位的烷芳基;在诸如二甲苯和二乙苯的多烷基芳烃的烷基部分有结合部位的烷芳基。上述基团中,优选有2-4个碳原子的脂族基团。
在通式(V)中,k表示的数表示R19O所示基团的重复数,其平均值在0-10范围内,优选在0-5范围内。当存在多个R19O时,多个R19O可表示相同基团或不同基团。
在通式(V)中,R20表示有1-20个碳原子、优选1-10个碳原子的烃基。烃基的例子包括烷基,诸如甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基、叔丁基、各种类型的戊基、各种类型的己基、各种类型的庚基、各种类型的辛基、各种类型的壬基和各种类型的癸基;环烷基,诸如环戊基、环己基、各种类型的甲基环己基、各种类型的乙基环己基、各种类型的丙基环己基和各种类型的二甲基环己基;芳基,诸如苯基、各种类型的甲基苯基、各种类型的乙基苯基、各种类型的二甲基苯基、各种类型的丙基苯基、各种类型的三甲基苯基、各种类型的丁基苯基和各种类型的萘基;和芳烷基,诸如苄基、各种类型的苯乙基、各种类型的甲基苄基、各种类型的苯基丙基和各种类型的苯基丁基。
在组成单元中R16至R20所示的原子和基团可以彼此相同或不同。
优选在含有通式(V)所示组成单元的聚乙烯基醚化合物(1)中,碳与氧的摩尔量之比在4.2-7.0范围内。当比值小于4.2时,化合物是吸湿性的。当比值超过7.0时,与致冷剂的可混溶性有时降低。
在上述通式(VI)中,R21至R24分别表示氢原子或有1-20个碳原子的烃基。R21至R24所示的原子和基团可以彼此相同或不同。有1-20个碳原子的烃基的例子包括在上述通式(V)中描述的R20所示基团的例子。在不同组成单元中R21至R24所示原子和基团可以彼此相同或不同。
在本发明中,也可使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。
可分别通过将相应的乙烯基醚单体聚合和将有烯属双键的相应的烃单体和相应的乙烯基醚单体共聚制备在本发明中使用的聚乙烯基醚化合物(1)和(2)。
作为本发明中使用的聚乙烯基醚化合物,优选下述化合物:
聚乙烯基醚化合物,其一个链端具有通式(VII)或(VIII)所示的结构:
其中,R25、R26和R27分别表示氢原子或有1-8个碳原子的烃基,R25、R26和R27表示的原子和基团可以彼此相同或不同,R30、R31、R32和R33分别表示氢原子或有1-20个碳原子的烃基,R30、R31、R32和R33表示的原子和基团可以彼此相同或不同,R28表示有1-10个碳原子的二价烃基,R29表示有1-20个碳原子的烃基,p表示平均值为0-20的数,当存在多个R28O时,多个R28O可以表示相同的基团或不同的基团,其它链端具有通式(IX)或(X)表示的结构:
其中,R34、R35和R36分别表示氢原子或有1-8个碳原子的烃基,R34、R35和R36表示的原子和基团可以彼此相同或不同,R39、R40、R41和R42分别表示氢原子或有1-20个碳原子的烃基,R39、R40、R41和R42表示的原子和基团可以彼此相同或不同,R37表示有1-10个碳原子的二价烃基,R38表示有1-20个碳原子的烃基,q表示平均值为0-10的数,当存在多个R37O时,多个R37O可以表示相同的基团或不同的基团;和
聚乙烯基醚化合物,其一个链端具有上述通式(VII)或(VIII)所示的结构,其它链端具有通式(XI)所示的结构:
其中,R43、R44和R45分别表示氢原子或有1-8个碳原子的烃基,R43、R44和R45表示的原子和基团可以彼此相同或不同。
上述聚乙烯基醚化合物中,优选在本发明中使用下述化合物:
(1)化合物,其一个链端具有通式(VII)或(VIII)所示结构且其它链端具有通式(IX)或(X)所示结构,含有通式(V)所示结构单元,其中R16、R17和R18分别表示氢原子,k表示0-4的数,R19表示有2-4个碳原子的二价烃基,R20表示有1-20个碳原子的烃基;
(2)化合物,其只含有通式(V)所示结构单元,并且一个链端具有通式(VII)所示结构而其它链端具有通式(IX)所示结构,其中通式(V)中R16、R17和R18分别表示氢原子,k表示0-4的数,R19表示有2-4个碳原子的二价烃基,R20表示有1-20个碳原子的烃基;
(3)化合物,其一个链端具有通式(VII)或(VIII)所示结构且其它链端具有通式(XI)所示结构,含有通式(V)所示结构单元,其中R16、R17和R18分别表示氢原子,k表示0-4的数,R19表示有2-4个碳原子的二价烃基,R20表示有1-20个碳原子的烃基;和
(4)化合物,其只含有通式(V)所示结构单元,并且一个链端具有通式(VII)所示结构而其它链端具有通式(X)所示结构,其中通式(V)中R16、R17和R18分别表示氢原子,k表示0-4的数,R19表示有2-4个碳原子的二价烃基,R20表示有1-20个碳原子的烃基。
在本发明中,还可以使用的聚乙烯基醚化合物含有通式(V)所示结构单元,并且一个链端具有通式(VII)所示结构而其它链端具有下述通式(XII)所示结构:
在通式(XII)中,R46、R47和R48分别表示氢原子或有1-8个碳原子的烃基,R46、R47和R48表示的原子或基团可以彼此相同或不同;R49和R50分别表示有2-10个碳原子的二价烃基并且可以表示相同基团或不同基团;R51和R52分别表示有1-10个碳原子的烃基并且可以表示相同基团或不同基团;c和d分别表示平均值为0-10的数并且可以表示相同的数或不同的数;当存在多个R49O时,多个R49O可以表示相同的基团或不同的基团;当存在多个R51O时,多个R51O可以表示相同的基团或不同的基团。
可在本发明中使用的聚乙烯基醚化合物的其它例子包括含有通式(XIII)或(XIV)所示结构单元的烷基乙烯基醚均聚物或共聚物:
其中R53表示有1-8个碳原子的烃基,
其重均分子量为300-5000,一个链端具有通式(XV)或(XVI)所示的结构:
其中R54表示有1-3个碳原子的烷基,R55表示有1-8个碳原子的烃基。
上述聚乙烯基醚化合物的其它例子包括在日本专利申请公开No.平6(1994)-128578、平6(1994)-234814和平6(1994)-234815和日本专利申请No.平5(1993)-303736中详细描述的化合物。
作为本发明第一方面的致冷油组合物包括作为主要成分的特定量的成分(A)和成分(B)的混合物,并且可以进一步包括诸如多元醇酯的聚酯、碳酸酯、矿物油和诸如聚-α-烯烃的烃类。
作为本发明第二方面的致冷油组合物包括与上述作为本发明第一方面的致冷油组合物联合使用的酸清除剂或至少一种酸清除剂和一种耐特压添加剂。
在本发明的第二方面,由于存在酸清除剂,可提高暴露在超临界条件下的二氧化碳中的条件下时的稳定性,同时保持极好的与致冷剂的可混溶性。由于将耐特压添加剂与酸清除剂结合使用,稳定性和润滑性可进一步提高。
在本发明中使用的酸清除剂的例子包括环氧化合物,诸如缩水甘油基苯醚、缩水甘油基烷基醚、缩水甘油基亚烷基二醇醚、环己烯氧化物、α-烯烃氧化物和环氧化大豆油。上述酸清除剂中,从可混溶性立场出发,优选缩水甘油基苯醚、缩水甘油基烷基醚、缩水甘油基亚烷基二醇醚、环己烯氧化物、α-烯烃氧化物。
在缩水甘油基烷基醚中的烷基和在缩水甘油基亚烷基醚中的亚烷基可以是支链的并通常有3-30个碳原子,优选4-24个碳原子,更优选6-16个碳原子。作为α-烯烃氧化物,可使用通常总共有4-30个碳原子的化合物,优选总共有4-24个碳原子,更优选总共有6-16个碳原子。
在本发明中,酸清除剂可单独使用或两种或多种结合使用。优选用量选自0.005-5重量%,更优选0.05-3重量%。当用量小于0.005重量%时,加入酸清除剂的效果可能体现不出来。当用量超过5重量%时,可能形成沉淀物。
作为耐特压添加剂,可使用羧酸金属盐。羧酸金属盐的例子包括有3-60个碳原子的羧酸的金属盐,优选有3-30个碳原子的脂肪酸金属盐,更优选有12-30个碳原子的脂肪酸金属盐。羧酸金属盐的其它例子包括上述脂肪酸的二聚酸的金属盐和三聚酸的金属盐和有3-30个碳原子的二羧酸的金属盐。这些羧酸金属盐中优选有12-30个碳原子的脂肪酸金属盐和有3-30个碳原子的二羧酸金属盐。
作为构成羧酸金属盐的金属,优选碱金属和碱土金属,更优选碱金属。
构成羧酸金属盐的羧酸的例子包括各种羧酸,诸如饱和的脂族羧酸、不饱和的脂族羧酸、脂族二羧酸和芳族羧酸。饱和的脂族羧酸的例子包括直链饱和脂肪酸,诸如己酸、辛酸、癸酸、月桂酸、豆蔻酸、棕榈酸、硬脂酸、花生酸、蜡酸、虫胶酸(laccelic acid);支链脂肪酸,诸如异戊酸、2-甲基戊酸、2-甲基丁酸、2,2-二甲基丁酸、2-甲基己酸、5-甲基己酸、2,2-二甲基庚酸、2-乙基-2-甲基丁酸、2-乙基己酸、二甲基己酸、2-正丙基戊酸、3,5,5-三甲基己酸、二甲基辛酸、异十三烷酸、异豆蔻酸、异硬脂酸、异花生酸和异己酸。不饱和脂族羧酸的例子包括棕榈烯酸、油酸、反油酸、亚油酸、亚麻酸和不饱和羟基羧酸,诸如蓖麻油酸。脂族二羧酸的例子包括己二酸、壬二酸和癸二酸。芳族羧酸的例子包括苯甲酸、邻苯二甲酸、1,2,4-苯三酸和均苯四酸。羧酸其它的例子包括脂环脂族酸,诸如环烷酸。羧酸可单独使用或两种或多种结合使用。
对构成羧酸金属盐的金属没有特别的限制,可以使用不同的金属。金属的例子包括碱金属,诸如锂、钾和钠;碱土金属,诸如镁、钙和锶;以及其它金属,诸如锌、镍和铝。上述金属中优选碱金属和碱土金属,更优选碱金属。可使用单一的金属或两种或多种金属混合与上述一种羧酸结合。
在本发明的致冷油组合物中,上述羧酸金属盐的量优选为0.001-5重量%,更优选0.005-3重量%。当用量小于0.001重量%时,耐磨性不足。当用量超过5重量%时,稳定性有时降低。
作为生产含有羧酸金属盐的本发明组合物的方法,将羧酸金属盐混入上述含有成分(A)和(B)的致冷油组合物(基油)中即可,方法可选自生产组合物的各种方法。按照下述方法生产组合物是有效的,因为可以提高羧酸金属盐在基油中的溶解性。将羧酸和碱金属氢氧化物置于溶剂中,形成一种混合物,其中羧酸金属盐通过在室温或在加热下反应被溶解或分散,从而羧酸金属盐可预先溶于或分散于溶剂中。将溶解或分散在溶剂中的羧酸金属盐加入、混入和分散入基油中而无需进一步处理。通过预先将羧酸金属盐溶解或分散在溶剂中并将得到的羧酸金属盐的溶液或分散液加入基油中可有效地生产目标组合物。
作为上述使用的溶剂,可使用各种溶剂。溶剂的例子包括一元醇类,诸如正丁醇、异丁醇、仲丁醇、叔丁醇、正戊醇、异戊醇、仲戊醇、正己醇、甲基戊醇、乙基丁醇、庚醇、正辛醇、仲辛醇、2-乙基己醇、异辛醇、正壬醇、2,6-二甲基-4-庚醇、正癸醇和环己醇;二醇和多元醇,诸如乙二醇、二甘醇、三甘醇、四甘醇、丙二醇、一缩二丙二醇、1,4-丁二醇、2,3-丁二醇、己二醇、辛二醇和甘油;溶纤剂类,诸如乙二醇甲基醚、乙二醇乙基醚、乙二醇二乙基醚、乙二醇丁基醚、乙二醇二丁基醚、乙二醇苯基醚、乙二醇苄基醚、乙二醇乙基己基醚、二甘醇一乙醚、二甘醇二乙醚、二甘醇一丁醚、二甘醇二丁醚、丙二醇一甲醚、丙二醇一乙醚、丙二醇一丁醚、一缩二丙二醇一甲醚、一缩二丙二醇一乙醚、二缩三丙二醇一甲醚、四甘醇二甲醚和四甘醇二丁醚;冠醚类,诸如苯并15-冠-5,苯并12-冠-4、苯并18-冠-6和二苯并18-冠-6;酮类,诸如乙基丁基酮、二丙基酮、甲基戊基酮、甲基己基酮和二异丁基酮;脂肪酸类,诸如上述有3-30个碳原子的脂肪酸。
对溶解或分散在上述溶剂中的羧酸金属盐的浓度没有特别的限制,可以根据情况适当地选择。
在本发明中使用的耐特压添加剂的其它例子包括含磷的耐特压添加剂,诸如磷酸酯、酸式磷酸酯、亚磷酸酯、酸式亚磷酸酯和这些酯的胺盐。磷酸酯的例子包括磷酸三芳酯、磷酸三烷酯、磷酸三烷芳酯、磷酸三芳烷酯和磷酸三烯酯。特定的磷酸酯的例子包括磷酸三苯酯、磷酸三甲苯酯、磷酸苄基二苯基酯、磷酸乙基二苯基酯、磷酸三丁酯、磷酸乙基二丁基酯、磷酸甲苯基二苯基酯、磷酸二甲苯基苯基酯、磷酸乙苯基二苯基酯、磷酸二乙苯基苯基酯、磷酸丙苯基二苯基酯、磷酸二丙苯基苯基酯、磷酸三乙苯基酯、磷酸三丙苯基酯、磷酸丁苯基二苯基酯、磷酸二丁基苯基酯、磷酸三丁苯基酯、磷酸三己基酯、磷酸三(2-乙基己基)酯、磷酸三癸酯、磷酸三月桂酯、磷酸三肉豆蔻基酯、磷酸三(十六烷基)酯、磷酸三(十八烷基)酯和磷酸三油酯。
酸式磷酸酯的例子包括2-乙基己基酸式磷酸酯、乙基酸式磷酸酯、丁基酸式磷酸酯、油醇酸式磷酸酯、二十四烷基酸式磷酸酯、异癸基酸式磷酸酯、月桂基酸式磷酸酯、十三烷基酸式磷酸酯、硬脂基酸式磷酸酯和异硬脂基酸式磷酸酯。
亚磷酸酯的例子包括亚磷酸三乙酯、亚磷酸三丁酯、亚磷酸三苯酯、亚磷酸三甲苯酯、亚磷酸三(壬基苯基)酯、亚磷酸三(2-乙基己基)酯、亚磷酸三癸酯、亚磷酸三月桂酯、亚磷酸三异辛酯、亚磷酸二苯基异癸基酯、亚磷酸三(十八烷基)酯、亚磷酸三油酯和亚磷酸(2-乙基己基)二苯基酯。
酸式亚磷酸酯的例子包括亚磷酸氢二丁酯、亚磷酸氢二月桂酯、亚磷酸氢二油酯、亚磷酸氢二(十八烷基)酯和亚磷酸氢二苯基酯。
与上述酯形成胺盐的胺的例子包括通式(XVII)所示的单取代的胺,二取代的胺和三取代的胺:
RsNH3-s (XVII)
其中R表示有3-30个碳原子的烷基或烯基、有6-30个碳原子的芳基或芳烷基或有2-30个碳原子的羟烷基,s表示1、2或3,当存在多个R时,多个R可以表示相同基团或不同基团。在通式(XVII)中R表示的有3-30个碳原子的烷基或烯基可以是任何直链基团、支链基团和环状基团。
单取代的胺的例子包括丁胺、戊胺、己胺、环己胺、辛胺、月桂胺、硬脂胺、油胺和苄胺。二取代的胺的例子包括二丁胺、二戊胺、二己胺、二环己胺、二辛胺、二月桂胺、二硬脂胺、二油胺、二苄基胺、硬脂基一乙醇胺、癸基一乙醇胺、己基一丙醇胺、苄基一乙醇胺、苯基一乙醇胺和甲苯基一丙醇胺。三取代的胺的例子包括三丁胺、三戊胺、三己胺、三环己胺、三辛胺、三月桂胺、三硬脂胺、三油胺、三苄胺、二油基一乙醇胺、二月桂基一丙醇胺、二辛基一乙醇胺、二己基一丙醇胺、二丁基一丙醇胺、油基二乙醇胺、硬脂基二丙醇胺、月桂基二乙醇胺、辛基二丙醇胺、丁基二乙醇胺、苄基二乙醇胺、苯基二乙醇胺、甲苯基二丙醇胺、二甲苯基二乙醇胺、三乙醇胺和三丙醇胺。
在这些耐特压添加剂中,从耐特压性和摩擦性立场出发,优选磷酸三甲苯酯、亚磷酸三(壬基苯基)酯、亚磷酸氢二油基酯和亚磷酸(2-乙基己基)二苯基酯。
耐特压添加剂的其它例子包括含硫的耐特压添加剂,诸如被硫化的油和脂肪、被硫化的脂肪酸、被硫化的酯、烯烃硫化物、二烃基多硫化物、硫代氨基甲酸盐、硫代萜和硫代二丙酸二烷基酯。被硫化的油和脂肪可通过硫或含硫化合物与诸如猪油、鲸油、植物油和鱼油的油和脂肪反应得到。对硫的含量没有特别的限制。通常,优选使用含有5-30重量%的硫的被硫化的油和脂肪。被硫化的油和脂肪的例子包括被硫化的猪油、被硫化的菜籽油、被硫化的蓖麻油、被硫化的大豆油和被硫化的米糠油。被硫化的脂肪酸的例子包括被硫化的油酸。被硫化的酯的例子包括被硫化的油酸甲酯和被硫化的米糠脂肪酸的辛酯。
烯烃硫化物的例子包括下述通式(XVIII)所示的化合物:
R56-St-R57 (XVIII)
其中R56表示有2-15个碳原子的烯基,R57表示有2-15个碳原子的烷基或烯基,t表示1-8的整数。上述化合物可通过有2-15个碳原子的烯烃或其二聚物、三聚物或四聚物与诸如硫或氯化硫的硫化剂反应获得。作为烯烃,优选丙烯、异丁烯和二异丁烯。
二烃基多硫化物是下述通式(XIX)所示的化合物:
R58-Su-R59 (XIX)
其中R58和R59分别表示有1-20个碳原子的烷基或环烷基、有6-20个碳原子的芳基、有7-20个碳原子的烷芳基或有7-20个碳原子的芳烷基,并且可表示相同的基团或不同的基团,u表示2-8的整数。当R58和R59表示烷基时,通式(XIX)所示的化合物称为硫醚。
上述通式(XIX)中R58和R59表示的基团的例子包括甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基、叔丁基、各种类型的戊基、各种类型的己基、各种类型的庚基、各种类型的辛基、各种类型的壬基、各种类型的癸基、各种类型的十二烷基、环己基、环辛基、苯基、萘基、甲苯基、二甲苯基、苄基和乙氧苯基。
二烃基多硫化物的例子包括二苄基多硫化物、二叔壬基多硫化物、二(十二烷基)多硫化物、二叔丁基多硫化物、二辛基多硫化物、二苯基多硫化物和二环己基多硫化物。
硫代氨基甲酸盐的例子包括二硫代氨基甲酸锌。硫代萜的例子包括五硫化磷与萜反应的产物。硫代二丙酸二烷基酯的例子包括硫代二丙酸二月桂酯和硫代二丙酸二硬脂酯。
在本发明中,耐特压添加剂可单独使用或两种或多种结合使用。优选使用一种或多种选自羧酸金属盐和含磷耐特压添加剂的添加剂。更优羧酸金属盐和含磷耐特压添加剂结合使用。在后者情况下,使用一种或多种选自羧酸金属盐的盐和一种或多种选自含磷耐特压添加剂的添加剂。
基于组合物的量,诸如含磷耐特压添加剂和上述其它添加剂的耐特压添加剂的用量为0.001-5重量%,优选0.01-3重量%。当用量小于0.001重量%时,润滑性可能不足。当用量超过5重量%时,可能促进沉淀物的形成。
本发明用于二氧化碳致冷剂的致冷油组合物还可以含有抗氧化剂。
作为抗氧化剂,优选酚类抗氧化剂,诸如2,6-二叔丁基-4-甲基苯酚、2,6-二叔丁基-4-乙基苯酚、2,2’-亚甲基二(4-甲基-6-叔丁基苯酚);和胺抗氧化剂,诸如苯基-α-萘基胺、苯基-β-萘基胺和N,N’-二苯基-对苯二胺。基于组合物的量,抗氧化剂的用量为0.01-5重量%,优选0.05-3重量%。当用量小于0.01重量%时,有时效果不足。当用量超过5重量%时,也不能期望得到更好的效果。当上述抗氧化剂与上述酸清除剂和耐特压添加剂结合使用时,当致冷油暴露在超临界条件下的二氧化碳中时,致冷油的稳定性表现出进一步提高。
对于本发明的致冷油组合物,还可以适当加入各种常用的添加剂,只要不对本发明的目的产生损害。常用添加剂的例子包括铜失活剂,诸如苯并三唑和其衍生物,包括N-(N,N’-二烷基氨基甲基)甲苯并三唑,其中烷基有3-12个碳原子;和消泡剂,诸如硅油和氟化硅油。在致冷油组合物中所含添加剂的量为0.001-3重量%。
在本发明中,可使用任何二氧化碳致冷剂,只要致冷剂含有二氧化碳作为主要成分。致冷剂可进一步包括诸如丙烷和异丁烷的烃致冷剂、氨致冷剂和诸如氢氟烃和全氟烃的含氟致冷剂,其典型的例子是1,1,1,2-四氟烃(R-134a)。当致冷剂含有上述非二氧化碳的成分时,本发明也可以起作用,只要致冷剂含有二氧化碳作为主成分,优选含有大于等于90重量%的二氧化碳。
在用本发明的致冷油组合物润滑冷冻设备的过程中,二氧化碳致冷剂与致冷油组合物的重量比在99/1至10/90范围内,优选在95/5至30/70范围内。当上述比例小于上述范围时,制冷能力降低。当上述比例超过上述范围时,润滑性恶化。因此,不优选上述范围之外的比例。
本发明的致冷油组合物可用于多种冷冻设备。优选本发明的致冷油用于在压缩型冷冻设备中的压缩型制冷循环。例如当用于具有至少一个油分离器和热气管线的压缩型制冷循环,诸如附图1-4所示的制冷循环,本发明的致冷油可表现出有益的效果。通常,压缩型制冷循环由压缩机、冷凝器、膨胀阀和蒸发器组成。作为冷冻设备的润滑剂,使用表现出与使用的致冷剂有极好的可混溶性的润滑剂。但是,当含有二氧化碳作为主成分的致冷剂用于上述制冷循环中并且冷冻设备使用常规的致冷油润滑时,因为耐磨性差或稳定性不足而不能实现长期的稳定操作。尤其,当在制冷循环中使用毛细管作为膨胀阀,诸如在电冰箱和小型空调中采用的那些,这个缺点就很明显。即使当有至少一个油分离器和一个热气管线的压缩型制冷循环使用含有二氧化碳作为主成分的致冷剂进行操作时,本发明的致冷油组合物也可有效地使用。
正如上文详细描述的,本发明中,(1)致冷油组合物含有(A)一种聚乙烯基醚,在100℃运动粘度为3-50mm2/s,其量为大于40重量%且小于等于99.1重量%;和(B)一种聚氧化亚烷基二醇,在100℃运动粘度为3-50mm2/s,其量为大于等于0.1重量%且小于40重量%。该致冷油组合物表现出与含有二氧化碳作为主成分的致冷剂的极好的可混溶性。
(2)用于二氧化碳致冷剂的致冷油组合物,通过将酸清除剂加入(1)中所述的组合物中得到,其在超临界条件下的二氧化碳气氛中表现出极好的稳定性,同时保持上述极好的可混溶性。用于二氧化碳致冷剂的致冷油组合物,通过在上述(1)中所述的组合物中加入将酸清除剂和耐特压添加剂、优选通过加入羧酸金属盐和含磷耐特压添加剂得到,其在超临界条件下的二氧化碳气氛中表现出极好的稳定性和润滑性,并且可长期使用。
参考下述实施例更明确地说明本发明。
在实施例中使用的试验方法如下。
[稳定性试验]
在内体积为120ml的高压釜内加入40g润滑油样品、40g二氧化碳致冷剂气体和含有铜、铝和铁的金属催化剂,向体系中加入水,加入量使水的含量被调节到2000ppm。关闭高压釜,在175℃保持10天。然后分析润滑油样品。试验期间体系内部压力为16MPa。
[摩擦试验]
使用不锈钢(SUJ-2)制成的环和铝(A4032)制成的滑块,在封闭体系中根据LFW-1摩擦试验在二氧化碳致冷剂气体气氛中测量滑块磨损量(mg)。试验条件如下:润滑剂样品的量:100ml;油温:50℃;二氧化碳气体压力:2MPa;旋转速度:300rpm;负载:1372N;试验时间:60分钟。
[用作基油的化合物]
表1所示的化合物用作在实施例和比较实施例中的基油。基油含有1.5重量%的α-烯烃氧化物和0.5重量%的二叔丁基-4-甲基苯酚。
表1
样品号 | 样品类型 | 基油 | 在100℃的运动粘度(mm2/s) | 粘度指数 |
I | PVE-1 | 聚乙基乙烯基醚和聚异丁基乙烯基醚的共聚物(摩尔比9∶1) | 8.2 | 85 |
II | PVE-2 | 聚乙基乙烯基醚 | 10.2 | 86 |
III | PAG-1 | 聚氧化亚丙基二醇二甲基醚 | 10.9 | 208 |
IV | PAG-2 | 聚氧化亚乙基氧化亚丙基二醇二甲基醚(摩尔比PO∶EO=9∶1) | 9.9 | 218 |
[羧酸金属盐的制备]
使用一缩二丙二醇为溶剂,油酸作为羧酸,氢氧化钾作为碱金属氢氧化物,羧酸和碱金属氢氧化物进行反应,制备30重量%油酸钾的溶液。
实施例1-4和对比实施例1和2
用表2所示的组合物进行稳定性试验和摩擦试验。在表2中,耐特压添加剂的量基于组合物的量计。试验结果如表3所示。
在表2中,耐特压添加剂缩写如下:
TCP:磷酸三对甲苯酯
TNP:亚磷酸三壬基苯基酯
DOHP:亚磷酸氢二油基酯
表2
基油(重量%) | 油酸钾(重量%) | 耐特压添加剂 | 粘度指数 | 在100℃的运动粘度(mm2/s) | ||
类型 | 量(重量%) | |||||
实施例1实施例2实施例3实施例4比较实施例1比较实施例2 | PVE-1(95)+PAG-1(5)PVE-1(90)+PAG-1(10)PVE-2(70)+PAG-1(30)PVE-1(80)+PAG-2(20)PVE-1(100)PVE-2(100) | 1.00.50.51.00.50.5 | TCPTNPTCPDOHPTCPTCP | 1.01.01.01.01.01.0 | 951021301158586 | 7.98.08.38.1-- |
表3
高压釜试验 | 试验后的总酸值(mgKOH/g) | 磨损量(mg) | |||
油的外观 | 沉淀 | 金属催化剂 | |||
实施例1实施例2实施例3实施例4比较实施例1比较实施例2 | 好好好好好好 | 无无无无无无 | 无变化无变化无变化无变化无变化无变化 | 0.080.090.080.070.070.06 | 3.62.51.071.64.44.1 |
工业应用
本发明涉及致冷油组合物,其用于使用二氧化碳(CO2)致冷剂的冷冻设备。该致冷油组合物可用于使用二氧化碳致冷剂的压缩型冷冻设备,特别是用于冷冻和空调设备,诸如汽车空调、冰箱、冰库、空调和热泵。提高了与含有二氧化碳作为主成分的致冷剂的可混溶性,并且在超临界条件下的二氧化碳气氛中稳定性极好。因此,该致冷油组合物可长期使用。
Claims (8)
1.用于二氧化碳致冷剂的致冷油组合物,其含有作为主要成分的一种混合物,包括(A)一种聚乙烯基醚,在100℃运动粘度为3-50mm2/s,其量为大于40重量%且小于或等于99.1重量%,所述聚乙烯基醚是含有通式(V)所示组成单元的化合物:
其中R16、R17和R18分别表示氢原子或有1-8个碳原子的烃基,R16、R17和R18在组成单元中表示的原子和基团彼此相同或不同;R19表示有1-10个碳原子的二价烃基;R20表示有1-20个碳原子的烃基;k表示的数平均值在0-10范围内;在组成单元之间R16至R20表示的原子和基团彼此相同或不同;并且,当存在多个R19O时,多个R19O表示相同或不同的基团,碳与氧的摩尔量之比为4.2-7.0;和(B)一种聚氧化亚烷基二醇,在100℃运动粘度为3-50mm2/s,其量为大于或等于0.1重量%且小于40重量%,所述聚氧化亚烷基二醇是通式(I)表示的化合物:
R1-[(OR2)m-OR3]n (I)
其中R1表示氢原子、有1-10个碳原子的烷基、有2-10个碳原子的酰基或有1-10个碳原子和2-6个结合部位的脂族烃基;R2表示有2-4个碳原子的亚烷基;R3表示氢原子、有1-10个碳原子的烷基或有2-10个碳原子的酰基;n表示1-6的整数;m表示的数使得m×n表示的数的平均值为6-80。
2.根据权利要求1所述的用于二氧化碳致冷剂的致冷油组合物,其运动粘度在100℃为3-50mm2/s,并且粘度指数大于或等于90。
3.根据权利要求1的用于二氧化碳致冷剂的致冷油组合物,其含有一种酸清除剂。
4.根据权利要求3的用于二氧化碳致冷剂的致冷油组合物,其含有0.005-5.0重量%的酸清除剂。
5.根据权利要求1的用于二氧化碳致冷剂的致冷油组合物,其含有一种耐特压添加剂。
6.根据权利要求5的用于二氧化碳致冷剂的致冷油组合物,其中耐特压添加剂是至少一种选自羧酸金属盐和含磷的耐特压添加剂的试剂。
7.根据权利要求5的用于二氧化碳致冷剂的致冷油组合物,其含有0.001-5.0重量%的耐特压添加剂。
8.根据权利要求1的用于二氧化碳致冷剂的致冷油组合物,其中二氧化碳致冷剂含有大于或等于90%重量的二氧化碳。
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JP227340/99 | 1999-08-11 | ||
JP22734099A JP4242518B2 (ja) | 1999-08-11 | 1999-08-11 | 二酸化炭素冷媒用冷凍機油組成物 |
JP227340/11 | 1999-08-11 |
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CN1239687C true CN1239687C (zh) | 2006-02-01 |
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US (1) | US6613725B1 (zh) |
EP (1) | EP1234868B1 (zh) |
JP (1) | JP4242518B2 (zh) |
KR (1) | KR100714514B1 (zh) |
CN (1) | CN1239687C (zh) |
AT (1) | ATE547505T1 (zh) |
CA (1) | CA2381305A1 (zh) |
TW (1) | TW524850B (zh) |
WO (1) | WO2001012763A1 (zh) |
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1999
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- 2000-08-07 WO PCT/JP2000/005288 patent/WO2001012763A1/ja active Application Filing
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- 2000-08-07 US US10/048,475 patent/US6613725B1/en not_active Expired - Lifetime
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ATE547505T1 (de) | 2012-03-15 |
EP1234868B1 (en) | 2012-02-29 |
EP1234868A4 (en) | 2006-05-17 |
CA2381305A1 (en) | 2001-02-22 |
US6613725B1 (en) | 2003-09-02 |
KR20020052175A (ko) | 2002-07-02 |
CN1370218A (zh) | 2002-09-18 |
TW524850B (en) | 2003-03-21 |
WO2001012763A1 (fr) | 2001-02-22 |
JP4242518B2 (ja) | 2009-03-25 |
KR100714514B1 (ko) | 2007-05-07 |
JP2001049282A (ja) | 2001-02-20 |
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