CN101018844A - 冷冻机油组合物 - Google Patents
冷冻机油组合物 Download PDFInfo
- Publication number
- CN101018844A CN101018844A CNA2004800439988A CN200480043998A CN101018844A CN 101018844 A CN101018844 A CN 101018844A CN A2004800439988 A CNA2004800439988 A CN A2004800439988A CN 200480043998 A CN200480043998 A CN 200480043998A CN 101018844 A CN101018844 A CN 101018844A
- Authority
- CN
- China
- Prior art keywords
- oil composition
- machine oil
- sulphur
- compound
- composition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000000203 mixture Substances 0.000 title claims abstract description 59
- 239000010721 machine oil Substances 0.000 title claims description 22
- -1 polyol ester Chemical class 0.000 claims abstract description 36
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000002199 base oil Substances 0.000 claims abstract description 18
- 150000002898 organic sulfur compounds Chemical class 0.000 claims abstract description 18
- 239000002480 mineral oil Substances 0.000 claims abstract description 14
- 235000010446 mineral oil Nutrition 0.000 claims abstract description 14
- 150000004996 alkyl benzenes Chemical class 0.000 claims abstract description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229920001515 polyalkylene glycol Polymers 0.000 claims abstract description 8
- 229920013639 polyalphaolefin Polymers 0.000 claims abstract description 8
- 229920005862 polyol Polymers 0.000 claims abstract description 8
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 7
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 5
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 5
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 4
- 239000005864 Sulphur Substances 0.000 claims description 43
- 239000003507 refrigerant Substances 0.000 claims description 30
- 125000004432 carbon atom Chemical group C* 0.000 claims description 24
- 238000007254 oxidation reaction Methods 0.000 claims description 7
- 239000003112 inhibitor Substances 0.000 claims description 5
- 230000003647 oxidation Effects 0.000 claims description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims description 4
- 239000011574 phosphorus Substances 0.000 claims description 4
- 239000005069 Extreme pressure additive Substances 0.000 claims description 3
- 235000011089 carbon dioxide Nutrition 0.000 claims description 3
- 239000013530 defoamer Substances 0.000 claims description 2
- 239000003921 oil Substances 0.000 abstract description 10
- 230000006378 damage Effects 0.000 abstract description 5
- 238000005057 refrigeration Methods 0.000 abstract description 5
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 abstract description 3
- 238000010792 warming Methods 0.000 abstract description 3
- 239000002826 coolant Substances 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 229910052717 sulfur Inorganic materials 0.000 abstract 2
- 239000011593 sulfur Substances 0.000 abstract 2
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract 1
- 239000001569 carbon dioxide Substances 0.000 abstract 1
- 238000005461 lubrication Methods 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 23
- 125000000217 alkyl group Chemical group 0.000 description 18
- 239000010687 lubricating oil Substances 0.000 description 12
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 9
- 235000019198 oils Nutrition 0.000 description 8
- 230000000903 blocking effect Effects 0.000 description 7
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 229910052802 copper Inorganic materials 0.000 description 6
- 239000010949 copper Substances 0.000 description 6
- 239000010802 sludge Substances 0.000 description 6
- 238000005299 abrasion Methods 0.000 description 5
- 125000002252 acyl group Chemical group 0.000 description 5
- 239000000654 additive Substances 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 5
- 239000001294 propane Substances 0.000 description 5
- 230000000996 additive effect Effects 0.000 description 4
- 150000001336 alkenes Chemical class 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- LTYMSROWYAPPGB-UHFFFAOYSA-N diphenyl sulfide Chemical compound C=1C=CC=CC=1SC1=CC=CC=C1 LTYMSROWYAPPGB-UHFFFAOYSA-N 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- GVIJJXMXTUZIOD-UHFFFAOYSA-N thianthrene Chemical compound C1=CC=C2SC3=CC=CC=C3SC2=C1 GVIJJXMXTUZIOD-UHFFFAOYSA-N 0.000 description 4
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 3
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical class C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical class CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000007710 freezing Methods 0.000 description 3
- 230000008014 freezing Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- OBETXYAYXDNJHR-SSDOTTSWSA-M (2r)-2-ethylhexanoate Chemical compound CCCC[C@@H](CC)C([O-])=O OBETXYAYXDNJHR-SSDOTTSWSA-M 0.000 description 2
- LVGUZGTVOIAKKC-UHFFFAOYSA-N 1,1,1,2-tetrafluoroethane Chemical compound FCC(F)(F)F LVGUZGTVOIAKKC-UHFFFAOYSA-N 0.000 description 2
- KVNYFPKFSJIPBJ-UHFFFAOYSA-N 1,2-diethylbenzene Chemical class CCC1=CC=CC=C1CC KVNYFPKFSJIPBJ-UHFFFAOYSA-N 0.000 description 2
- FCEHBMOGCRZNNI-UHFFFAOYSA-N 1-benzothiophene Chemical compound C1=CC=C2SC=CC2=C1 FCEHBMOGCRZNNI-UHFFFAOYSA-N 0.000 description 2
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 2
- NZQMQVJXSRMTCJ-UHFFFAOYSA-N 3-Methyl-hexanoic acid Chemical compound CCCC(C)CC(O)=O NZQMQVJXSRMTCJ-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- VOPWNXZWBYDODV-UHFFFAOYSA-N Chlorodifluoromethane Chemical compound FC(F)Cl VOPWNXZWBYDODV-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical class CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- FQYUMYWMJTYZTK-UHFFFAOYSA-N Phenyl glycidyl ether Chemical compound C1OC1COC1=CC=CC=C1 FQYUMYWMJTYZTK-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 238000004378 air conditioning Methods 0.000 description 2
- 239000002168 alkylating agent Substances 0.000 description 2
- 229940100198 alkylating agent Drugs 0.000 description 2
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 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 2
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 2
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 2
- PXBRQCKWGAHEHS-UHFFFAOYSA-N dichlorodifluoromethane Chemical compound FC(F)(Cl)Cl PXBRQCKWGAHEHS-UHFFFAOYSA-N 0.000 description 2
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- MNWFXJYAOYHMED-UHFFFAOYSA-N heptanoic acid Chemical compound CCCCCCC(O)=O MNWFXJYAOYHMED-UHFFFAOYSA-N 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 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 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- FBUKVWPVBMHYJY-UHFFFAOYSA-N nonanoic acid Chemical compound CCCCCCCCC(O)=O FBUKVWPVBMHYJY-UHFFFAOYSA-N 0.000 description 2
- 229940059574 pentaerithrityl Drugs 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- 239000005077 polysulfide Substances 0.000 description 2
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- 150000008117 polysulfides Polymers 0.000 description 2
- 238000004088 simulation Methods 0.000 description 2
- 238000001149 thermolysis Methods 0.000 description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 2
- 239000003981 vehicle Substances 0.000 description 2
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 1
- ZWAJLVLEBYIOTI-OLQVQODUSA-N (1s,6r)-7-oxabicyclo[4.1.0]heptane Chemical compound C1CCC[C@@H]2O[C@@H]21 ZWAJLVLEBYIOTI-OLQVQODUSA-N 0.000 description 1
- MEIRRNXMZYDVDW-MQQKCMAXSA-N (2E,4E)-2,4-hexadien-1-ol Chemical compound C\C=C\C=C\CO MEIRRNXMZYDVDW-MQQKCMAXSA-N 0.000 description 1
- UPYPTOCXMIWHSG-UHFFFAOYSA-N 1-dodecylsulfanyldodecane Chemical compound CCCCCCCCCCCCSCCCCCCCCCCCC UPYPTOCXMIWHSG-UHFFFAOYSA-N 0.000 description 1
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- 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
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- LLQHSBBZNDXTIV-UHFFFAOYSA-N 6-[5-[[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]methyl]-4,5-dihydro-1,2-oxazol-3-yl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC1CC(=NO1)C1=CC2=C(NC(O2)=O)C=C1 LLQHSBBZNDXTIV-UHFFFAOYSA-N 0.000 description 1
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- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 1
- 150000007979 thiazole derivatives Chemical class 0.000 description 1
- ZPHGMBGIFODUMF-UHFFFAOYSA-N thiophen-2-ylmethanol Chemical compound OCC1=CC=CS1 ZPHGMBGIFODUMF-UHFFFAOYSA-N 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- 229940005605 valeric acid Drugs 0.000 description 1
- 239000006200 vaporizer Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Chemical class 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
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Abstract
本发明提供一种冷冻机油组合物,其含有(A)包含选自聚亚烷基二醇、多元醇酯、聚α-烯烃、烷基苯和矿物油的至少1种的基油、(B)硫的含量为35质量%以下的有机硫化合物、和(C)包含选自二氧化碳、烃和氨的至少1种的冷却剂,全部硫的含量相对于(A)成分与(B)成分的总量为0.01~0.1质量%,本发明提供了一种新型的冷冻机油组合物,其没有破坏臭氧层或使地球变暖等的环境问题,可以长期维持润滑性能、且不堵塞制冷循环内的毛细管。
Description
技术领域
本发明涉及新型的冷冻机油组合物,特别地,涉及使用了自然系冷却剂、润滑性优良的冷冻机油组合物。
背景技术
一般地,冷冻机、例如包含压缩机、冷凝器、膨胀阀、蒸发器的压缩型冷冻机的压缩式制冷循环形成冷却剂与润滑油的混合液体在该密闭的体系内循环的结构。在这样的压缩型冷冻机中,冷却剂目前使用二氯二氟甲烷(R-12)或氯二氟甲烷(R-22)等含氯氟烃,另外,与其并用的多种润滑油被制造使用。当目前作为冷却剂使用的这些氟烃被排放到大气中时,有可能带来破坏在同温层存在的臭氧层等的环境污染,因此,作为新的冷却剂,使用了以1,1,1,2-四氟乙烷(R-134a)为代表的氢氟烃或氟烃等。该氢氟烃等不会破坏臭氧层,但由于其在大气中的寿命长,所以担心会对地球变暖有影响。近年来,人们开始考虑使用没有这些问题的自然系冷却剂。
另一方面,在冷冻机油组合物中,作为极压添加剂,使用了以磷酸三甲苯酯(TCP)为代表的磷系添加剂。但是,磷系的极压添加剂有由于热分解或水解、进而在摩擦面的摩擦化学反应等而导致变质、淤渣化的问题。另外,由于变质、淤渣化导致磷系添加剂消耗,因此有不能长时间维持润滑性能、以至引起烧熔、磨损的情况。
提出了一种含有硫的润滑油,其是在目前的使用了氟烃系冷却剂的冷冻机用润滑油组合物中,添加有机硫化合物而成的,其耐热性、耐磨损性优异、对于温度变化的粘度变化少、具有优异的氟烃溶解性的性能(专利文献1)。根据专利文献1,对于该氟烃系的冷冻机用润滑油组合物,有机硫化合物的含量是重要的,在例如使用矿物油作为基油时,即使有机硫化合物是在矿物油中天然存在的亦可。但是,对于使用了自然系冷却剂的冷冻机用润滑油组合物,仅控制硫含量不能赋予充分的耐磨损性、极压性。
专利文献1:特开昭58-103594号公报
发明内容
本发明是为了解决上述课题而作出的,其目的在于提供使用了自然系冷却剂的冷冻机用润滑油组合物,其可以长时间维持润滑性能,且不堵塞制冷循环内的毛细管。
本发明人为了开发具有上述特性的冷冻机用润滑油组合物,不断进行努力的研究,结果发现当在特定的基油中含有特定有机硫化合物的冷冻机油使用自然系冷却剂时,可以长时间维持润滑性能,且不堵塞制冷循环内的毛细管。本发明是基于上述认识而完成的。
即,本发明提供了一种冷冻机油组合物,其含有(A)包含选自聚亚烷基二醇、多元醇酯、聚α-烯烃、烷基苯和矿物油的至少1种的基油、(B)硫的含量为35质量%以下的有机硫化合物、和(C)包含选自二氧化碳、烃和氨的至少1种的冷却剂,全部硫的含量相对于(A)成分与(B)成分的总量为0.01~0.1质量%。
附图说明
[图1]表示毛细管堵塞试验机的图。
符号的说明
1.毛细管堵塞试验机
2.压缩机
2A.压缩机入口
2B.压缩机出口
3.毛细管
3A.毛细管入口
3B.毛细管出口
4.高温侧流路
5.低温侧流路
6.热交换器
7.排出侧压力计
8.吸入侧压力计
9.真空泵连接用阀
10.模拟循环体系
具体实施方式
对于本发明的润滑油组合物,使用(A)选自聚亚烷基二醇、多元醇酯、聚α-烯烃、烷基苯和矿物油的至少1种作为基油。
聚亚烷基二醇优选如下述通式(I)所示的化合物。
R1-[(OR2)m-OR3]n …(I)
这里,R1是氢、碳原子数为1~10的烷基、酰基或者具有2~6个结合部位的脂肪族烃基,R2是碳原子数为2~4的亚烷基,可以是均聚物、共聚物的任一种。R3是氢、碳原子数为1~10的烷基或者酰基,n是1~6的整数,m是使m×n的平均值为6~80的整数。
作为烷基,是直链状、支链状、环状的任意一者都可以。该烷基的具体例子可以列举甲基、乙基、正丙基、异丙基、各种丁基、各种戊基、各种己基、环戊基、环己基等。优选该烷基的碳原子数为10以下,当为10以下时,可以得到与冷却剂的充分的相溶性。
另外,酰基的烷基部分是直链状、支链状、环状的任意一者都可以。该酰基的烷基部分的具体例子可以列举甲基、乙基、正丙基、异丙基、各种丁基、各种戊基、各种己基、环戊基、环己基等。优选该酰基的碳原子数也与烷基同样为10以下,当为10以下时,可以得到与冷却剂的充分的相溶性。
上述R1和R3可以是同样的,也可以是相互不同的。对于本发明,在上述(I)式所示的聚亚烷基二醇中,优选R1或者R3的任意一者为氢、另一者为烷基的情况,优选该烷基是碳原子数为1~3的烷基,特别是甲基的情况。另外,优选R1和R3都是碳原子数为1~3的烷基的情况,特别地,优选R1和R3都是甲基的情况。本发明的基油可以将多种聚亚烷基二醇混合来使用。
多元醇酯可以列举含有至少2个羟基的多元羟基化合物的羧酸酯,例如优选下述通式(II)所示的化合物。
R4[OCOR5]f …(II)
这里,R4为烃基,R5为氢原子或者碳原于数为1~22的烃基,f表示2~6的整数,多个[OCOR5]可以是相同的,也可以是不同的。
在上述通式(II)中,用R4表示的烃基为直链状、支链状都可以,优选碳原子数为2~10的烷基。R5为氢原子或者碳原子数1~22的烃基,优选碳原子数2~16的烷基。上述通式(II)所示的多元醇酯可以通过使下述通式(III)
R4(OH)f …(III)
(式中,R4和f与上述相同。)所示的多元醇、与下述通式(IV)
R5COOH …(IV)
(式中,R5与上述相同。)所示的羧酸或者其酯或卤化物等反应性衍生物进行反应来得到。
上述通式(III)所示的多元醇可以使用各种化合物,可以列举例如乙二醇、丙二醇、丁二醇、新戊二醇、三羟甲基乙烷、三羟甲基丙烷、甘油、季戊四醇、二聚季戊四醇、山梨醇等。另一方面,如(IV)所示的羧酸没有特别地限定,可以列举例如丙酸、丁酸、新戊酸、戊酸、己酸、庚酸、3-甲基己酸、2-乙基己酸、辛酸、壬酸、癸酸、月桂酸、豆蔻酸、棕榈酸等。本发明的基油可以将多种多元醇酯混合来使用。
聚α-烯烃是碳原子数为3~12左右的α-烯烃的低聚物,优选分子量为200~5000,进而优选分子量为300-2000。本发明的基油可以将多种聚α-烯烃混合来使用。
烷基苯是用烷基化剂将苯、甲苯、二甲苯、乙基苯、甲基乙基苯、二乙基苯以及它们的混合物等的芳香族进行烷基化而成的,所述烷基化剂为乙烯、丙烯、丁烯、异丁烯等的低级单烯烃、由丙烯聚合得到的碳原子数为6~40的支链状烯烃、由蜡、石油馏分、聚乙烯、聚丙烯等的热分解得到的碳原子数为6~40的支链状烯烃等。烷基苯的苯具有的烷基数优选为1~3,特别地,优选大量含有具有2个烷基的烷基苯。并且,本发明的基油可以将多种烷基苯混合来使用。
本发明的作为基油使用的矿物油没有特别地限定,可以列举链烷烃系矿物油、环烷系矿物油等,优选硫含量为200质量ppm以下的矿物油。矿物油中的硫含量根据作为原料的原油中的硫含量的不同而不同,优选进行精制使其为200质量ppm以下。本发明的基油可以将多种矿物油混合来使用。
如上所述,本发明使用的(A)基油优选使用上述的化合物,其中,从稳定性、蒸发减量的观点考虑,聚亚烷基二醇、多元醇酯、聚α-烯烃、烷基苯是特别优选的。另外,这些化合物可以1种单独使用,或者2种以上混合使用。
本发明使用的(A)基油在40℃下的运动粘度优选为3~1000mm2/s。当为3mm2/s以上时,能够得到充分的润滑性能,当为1000mm2/s以下时,在不承担过度负载的情况下,能量效率变高。从以上的观点考虑,基油在40℃下的运动粘度优选为5~500mm2/s,进而优选5~150mm2/s的范围。
接着,在本发明中,(B)成分的特征在于含有硫含量为35质量%以下的有机硫化合物。当硫含量超过35质量%,有产生变质·淤渣化的情况。具体来说,在1分子中含有3个以上的硫的多硫化物有这样的危险。另外,从可以减少(B)成分的添加量的方面考虑,优选硫含量比5质量%多。
在本发明中优选使用的(B)有机硫化合物可以列举脂肪族硫化合物、杂环硫化合物、芳香族硫化合物等。
脂肪族硫化合物的碳原子数优选为12以上,进而优选14以上,特别优选18以上。具体来说,可以列举二辛基硫化物、双十二烷基硫化物、双十四烷基硫化物等。
杂环硫化合物的碳原子数优选为8以上,进而优选10以上,特别优选碳原子数为12以上。具体来说,可以列举苯并噻吩、硫芴、吩噻嗪、苯并噻喃、噻喃、噻蒽、二苯并噻喃、二硫杂蒽、和它们的烷基衍生物。
芳香族硫化合物的碳原子数优选为12以上,进而优选16以上。具体来说,可以列举4,4′-硫代双(3-甲基-6-叔丁基苯酚)、二苯硫、二辛基二苯硫、二烷基二苯硫等。
其他,也可以使用碳原子数为8以上的、除脂肪族硫化合物、杂环硫化合物、和芳香族硫化合物以外的有机硫化合物,可以列举例如,碳原子数为8以上、优选碳原子数为10以上,在分子内含有1个以上S原子的有机硫化合物,具体来说,可以列举砜、二苯亚砜、二苯砜、噻唑、噻唑衍生物、硫代金刚烷、2-噻吩基甲醇、噻吩乙酸等。
在以上的有机硫化合物中,优选使用二硫杂蒽、吩噻嗪、二烷基二苯硫。
本发明冷冻机油组合物中的硫含量,以(A)成分与(B)成分的总量作为基准,须为0.01~0.1质量%。如果该硫含量为0.01质量%以上,则可以实现充分的润滑性能,如果为0.1质量%以下,则可以充分抑制由变质等导致的淤渣的产生。从以上的观点考虑,硫含量优选为0.02~0.05质量%的范围,进而优选0.025~0.035质量%的范围。
另外,在本发明的润滑油组合物中可以配合在通常冷冻机油组合物中使用的添加剂,特别地,优选添加抗氧剂、酸捕捉剂和消泡剂。
抗氧剂没有特别地限定,可以使用例如酚系抗氧剂、胺系抗氧剂等。酸捕捉剂以水解稳定性作为目的被配合在冷冻机油组合物中,其可以列举例如,苯基缩水甘油基醚、烷基缩水甘油基醚、亚烷基二醇缩水甘油基醚、环己烷氧化物、α-氧化烯烃、环氧化大豆油等的环氧化合物。其中,从相溶性的方面考虑,优选苯基缩水甘油基醚、烷基缩水甘油基醚、亚烷基二醇缩水甘油基醚、环己烯氧化物、α-氧化烯烃。削泡剂可以列举出硅油或者氟化硅油等。
另外,在不妨害本发明目的的范围可以添加其他的添加剂、例如苯并三唑或其衍生物等的铜惰性化剂等。这些添加剂各自在通常为0.005~5质量%的范围添加。
在本发明的润滑油组合物中使用的冷却剂包含选自二氧化碳、烃和氨的至少1种。这里,烃是指通常作为冷却剂使用的化合物,可以列举例如丙烷、丁烷、它们的混合物等。
在冷冻机油组合物中,这些冷却剂的含量通常在10~99质量%的范围。如果为10质量%以上,则可以发挥充分的冷冻能力,如果为99质量%以下,则存在充足量的润滑油,没有烧熔或磨损的问题。从以上的观点考虑,进而优选30~95质量%的范围。
本发明的冷冻机油组合物可以用于各种的用途,例如可以作为空调用、冷库用、燃气加热泵、自动售货机、陈列柜冷冻用、车辆空调用、供热水用、房屋取暖用等来使用。
实施例
接着,通过实施例进而详细地说明本发明,但本发明不限定于这些例子。
(评价方法)
1.密封管试验(热稳定性)
在内容积为10ml的玻璃管中加入用各实施例和比较例记述的方法调制的冷冻机油组合物,并添加铜、铝、铁的金属催化剂。密闭玻璃管,在175℃下保持30天后,对于冷冻机油组合物的外观、铜的外观、淤渣的有无进行评价。
2.密闭法列克司试验(润滑性)
使用密闭式法列克司磨擦试验机,根据ASTM D2670求得磨损量(mg)。并且,试验条件是载重为1335N、旋转数为300rpm、温度为80℃、试验时间为1小时、使用的销子为AISIC1137、嵌决为SAE3135。
3.毛细管堵塞试验
使用图1所示的试验机,以1000小时后毛细管流量的降低率来评价。该试验装置1是在特开平11-183334中公开的装置,其具有压缩机2;作为热压减少装置的毛细管3;使压缩机2的排出口2A和毛细管3的入口3A连通的高温侧流路4;使毛细管3的出口3B和压缩机2的吸入口2B连通的低温侧流路5;在高温侧流路4以及低温侧流路5的中途设置的、在各流路4、5间进行冷却剂之间的热交换的热交换器6,在高温侧流路4上,在压缩机2与热交换器6之间设置排出侧压力计7,在低温侧流路5上,在热交换器6与压缩机2之间设置吸入侧压力计8,在其下流侧设置真空泵连接用的阀9。通过以上的构成部件构成使含有冷冻机油的冷却剂循环的模拟循环体系10。
试验条件是:吸入侧压力(Ps)为0.4MPa、排出侧压力(Pd)为3.3MPa、热交换机入口温度(Td)为110℃、热交换机出口温度(Ts)为30℃。冷却剂使用异丁烷(R600a),将各400g的样品油((A)成分和(B)成分的总量)和冷却剂进行混合来实施试验。
实施例1~8、比较例1~7
调制包含第1表所示的(A)基油和(B)特定有机化合物的冷冻机油,利用上述评价方法进行评价。结果示于第1表。
并且,这里使用的表示(A)成分和(B)成分的记号如下所述。
A-1:聚丙二醇二甲基醚(40℃粘度:46mm2/s)
A-2:聚乙二醇聚丙二醇共聚物二甲基醚(40℃粘度:100mm2/s)
A-3:季戊四醇与2-乙基己酸/3,5,5-三甲基己酸的1∶1混合物的酯(40℃粘度:65mm2/s)
A-4:聚α-烯烃(40℃粘度:63mm2/s)
A-5:烷基苯(40℃粘度:38mm2/s)
A-6:链烷烃系矿物油(40℃粘度:90mm2/s、硫含量为5质量ppm以下)
A-7:环烷系矿物油(40℃粘度:10mm2/s、硫含量为107质量ppm以下)
A-8:环烷系矿物油(40℃粘度:56mm2/s、硫含量为3000质量ppm以下)
B-1:苯并噻吩(硫含量为23.9质量%)
B-2:硫芴(硫含量为17.4质量%)
B-3:噻蒽(硫含量为29.6质量%)
B-4:吩噻嗪(硫含量为16.1质量%)
B-5:二苯硫(硫含量为17.2质量%)
B-6:二辛基二苯硫(硫含量为7.8质量%)
B-7:二辛基多硫化合物(硫含量为39质量%)
B-8:磷酸三甲苯酯
表1
第1表-1
实施例 | ||||||
1 | 2 | 3 | 4 | |||
(A)成分 | A·1 | 99.88 | - | - | - | |
A·2 | - | 99.83 | - | - | ||
A·3 | - | - | 99.9 | - | ||
A·4 | - | - | - | 99.82 | ||
A·5 | - | - | - | - | ||
A·6 | - | - | - | - | ||
A·7 | - | - | - | - | ||
A·8 | - | - | - | - | ||
(B)成分 | B·1 | 0.12 | - | - | - | |
B·2 | - | 0.17 | - | - | ||
B·3 | - | - | 0.1 | - | ||
B·4 | - | - | - | 0.18 | ||
B·5 | - | - | - | - | ||
B·6 | - | - | - | - | ||
B·7 | - | - | - | - | ||
B·8 | - | - | - | - | ||
B·9 | - | - | - | - | ||
硫含量(质量%) | 0.03 | 0.03 | 0.03 | 0.03 | ||
密封管试验 | 油外观 | 良好 | 良好 | 良好 | 良好 | |
铜外观 | 良好 | 良好 | 良好 | 良好 | ||
淤渣有无 | 无 | 无 | 无 | 无 | ||
法列克司试验(磨损量:mg) | 冷却剂:CO2 | 7 | 6 | 14 | 9 | |
冷却剂:丙烷 | 9 | 7 | 16 | 9 | ||
冷却剂:NH3 | 14 | - | - | - | ||
毛细管堵塞试验(流量降低率%) | 1 | 1 | 1 | 1 |
表2
第1表-2
实施例 | ||||||
5 | 6 | 7 | 8 | |||
(A)成分 | A·1 | - | - | - | 99.7 | |
A·2 | - | - | - | - | ||
A·3 | - | - | - | - | ||
A·4 | - | - | - | - | ||
A·5 | 99.83 | - | - | - | ||
A·6 | - | 99.6 | - | - | ||
A·7 | - | - | 99.6 | - | ||
A·8 | - | - | - | - | ||
(B)成分 | B·1 | - | - | - | - | |
B·2 | - | - | - | - | ||
B·3 | - | - | - | 0.3 | ||
B·4 | - | - | - | - | ||
B·5 | 0.17 | - | - | - | ||
B·6 | - | 0.4 | 0.4 | - | ||
B·7 | - | - | - | - | ||
B·8 | - | - | - | - | ||
B·9 | - | - | - | - | ||
硫含量(质量%) | 0.03 | 0.03 | 0.03 | 0.09 | ||
密封管试验 | 油外观 | 良好 | 良好 | 良好 | 良好 | |
铜外现 | 良好 | 良好 | 良好 | 良好 | ||
淤渣有无 | 无 | 无 | 无 | 无 | ||
法列克司试验(磨损量:mg) | 冷却剂:CO2 | 7 | 8 | 5 | 13 | |
冷却剂:丙烷 | 8 | 10 | 7 | 14 | ||
冷却剂:NH3 | - | - | - | - | ||
毛细管堵塞试验(流量降低率%) | 1 | 1 | 1 | 1 |
表3
第1表-3
比较例 | ||||||
1 | 2 | 3 | 4 | |||
(A)成分 | A·1 | 99.98 | 99.4 | 99.98 | 99.5 | |
A·2 | - | - | - | - | ||
A·3 | - | - | - | - | ||
A·4 | - | - | - | - | ||
A·5 | - | - | - | - | ||
A·6 | - | - | - | - | ||
A·7 | - | - | - | - | ||
A·8 | - | - | - | - | ||
(B)成分 | B·1 | 0.02 | 0.6 | - | - | |
B·2 | - | - | - | - | ||
B·3 | - | - | 0.02 | 1 | ||
B·4 | - | - | - | - | ||
B·5 | - | - | - | - | ||
B·6 | - | - | - | - | ||
B·7 | - | - | - | - | ||
B·8 | - | - | - | - | ||
B·9 | - | - | - | - | ||
硫含量(质量%) | 0.005 | 0.14 | 0.006 | 0.3 | ||
密封管试验 | 油外观 | 良好 | 淡黄色 | 良好 | 淡黄色 | |
铜外现 | 良好 | 变色 | 良好 | 变色 | ||
淤渣有无 | 无 | 无 | 无 | 无 | ||
法列克司试验(磨损量:mg) | 冷却荆:CO2 | 粘着 | 24 | 粘着 | 29 | |
冷却剂:丙烷 | 粘着 | 38 | 粘着 | 42 | ||
冷却剂:NH3 | 粘着 | 45 | - | - | ||
毛细管堵塞试验(流量降低率%) | - | 6 | - | 8 |
表4
第1表-4
比较例 | ||||||
5 | 6 | 7 | 8 | |||
(A)成分 | A·1 | - | 99.86 | 99.9 | 99 | |
A·2 | - | - | - | - | ||
A·3 | - | - | - | - | ||
A·4 | - | - | - | - | ||
A·5 | - | - | - | - | ||
A·6 | - | - | - | - | ||
A·7 | - | - | - | - | ||
A·8 | 99.88 | - | - | - | ||
(B)成分 | B·1 | 0.12 | - | - | - | |
B·2 | - | - | - | - | ||
B·3 | - | - | - | - | ||
B·4 | - | - | - | - | ||
B·5 | - | - | - | - | ||
B·6 | - | - | - | - | ||
B·7 | - | 0.14 | - | - | ||
B·8 | - | - | 0.1 | - | ||
B·9 | - | - | - | 1 | ||
硫含量(质量%) | 0.33 | 0.03 | 0.03 | - | ||
密封管试验 | 油外观 | 黄色 | 淡黄色 | 黄色 | 良好 | |
铜外观 | 变色 | 黑色 | 黑色 | 良好 | ||
淤渣有无 | 有 | 无 | 有 | 无 | ||
法列克司试验(磨损量:mg) | 冷却剂:CO2 | 17 | 18 | 81 | - | |
冷却剂:丙烷 | 21 | 28 | 36 | 17 | ||
冷却剂:NH3 | - | - | - | - | ||
毛细管堵塞试验(流量降低率%) | 5 | - | - | 7 |
产业实用性
本发明的新型冷冻机油组合物没有破坏臭氧层或使地球变暖等的环境问题,可以长期维持润滑性能、且不堵塞制冷循环内的毛细管。因此,可以优选作为空调用、冷库用、燃气加热泵、自动售货机、陈列柜冷冻用、车辆空调用、供热水用、房屋取暖用等来使用。
Claims (9)
1.一种冷冻机油组合物,其含有(A)包含选自聚亚烷基二醇、多元醇酯、聚α-烯烃、烷基苯和矿物油的至少1种的基油、(B)硫的含量为35质量%以下的有机硫化合物、和(C)包含选自二氧化碳、烃和氨的至少1种的冷却剂,全部硫的含量相对于(A)成分与(B)成分的总量为0.01~0.1质量%。
2.如权利要求1所述的冷冻机油组合物,(A)基油在40℃的粘度为3~1000mm2/s,且硫含量为200质量ppm以下。
3.如权利要求1或2所述的冷冻机油组合物,(B)有机硫化合物为选自脂肪族硫化合物、杂环硫化合物和芳香族硫化合物的至少1种。
4.如权利要求3所述的冷冻机油组合物,(B)有机硫化合物含有碳原子数至少为12以上的脂肪族硫化合物。
5.如权利要求3所述的冷冻机油组合物,(B)有机硫化合物含有碳原子数至少为8以上的杂环硫化合物。
6.如权利要求3所述的冷冻机油组合物,(B)有机硫化合物含有碳原子数至少为12以上的芳香族硫化合物。
7.如权利要求1或2所述的冷冻机油组合物,(B)有机硫化合物含有碳原子数至少为8以上的、除脂肪族硫化合物、杂环硫化合物、和芳香族硫化合物以外的有机硫化合物。
8.如权利要求1~7中任意一项所述的冷冻机油组合物,还含有抗氧剂、酸捕捉剂和消泡剂。
9.如权利要求1~8中任意一项所述的冷冻机油组合物,不含有磷系极压添加剂。
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PCT/JP2004/013367 WO2006030490A1 (ja) | 2004-09-14 | 2004-09-14 | 冷凍機油組成物 |
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US (1) | US7718083B2 (zh) |
EP (1) | EP1792970B1 (zh) |
JP (1) | JP4630283B2 (zh) |
KR (1) | KR101156388B1 (zh) |
CN (1) | CN101018844A (zh) |
WO (1) | WO2006030490A1 (zh) |
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- 2004-09-14 CN CNA2004800439988A patent/CN101018844A/zh active Pending
- 2004-09-14 JP JP2006534974A patent/JP4630283B2/ja not_active Expired - Fee Related
- 2004-09-14 WO PCT/JP2004/013367 patent/WO2006030490A1/ja active Application Filing
- 2004-09-14 EP EP04822285A patent/EP1792970B1/en not_active Expired - Fee Related
- 2004-09-14 KR KR1020077005368A patent/KR101156388B1/ko not_active IP Right Cessation
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JPWO2006030490A1 (ja) | 2008-05-08 |
US20070213239A1 (en) | 2007-09-13 |
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US7718083B2 (en) | 2010-05-18 |
EP1792970A1 (en) | 2007-06-06 |
KR20070052295A (ko) | 2007-05-21 |
KR101156388B1 (ko) | 2012-06-13 |
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