CN101981169B - 用于等速万向节的润滑脂组合物 - Google Patents
用于等速万向节的润滑脂组合物 Download PDFInfo
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- CN101981169B CN101981169B CN200880128562.7A CN200880128562A CN101981169B CN 101981169 B CN101981169 B CN 101981169B CN 200880128562 A CN200880128562 A CN 200880128562A CN 101981169 B CN101981169 B CN 101981169B
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- 239000004519 grease Substances 0.000 title claims abstract description 89
- 239000011575 calcium Substances 0.000 claims abstract description 32
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 32
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000002199 base oil Substances 0.000 claims abstract description 25
- 239000000344 soap Substances 0.000 claims abstract description 22
- JXLHNMVSKXFWAO-UHFFFAOYSA-N azane;7-fluoro-2,1,3-benzoxadiazole-4-sulfonic acid Chemical compound N.OS(=O)(=O)C1=CC=C(F)C2=NON=C12 JXLHNMVSKXFWAO-UHFFFAOYSA-N 0.000 claims abstract description 14
- KHYKFSXXGRUKRE-UHFFFAOYSA-J molybdenum(4+) tetracarbamodithioate Chemical compound C(N)([S-])=S.[Mo+4].C(N)([S-])=S.C(N)([S-])=S.C(N)([S-])=S KHYKFSXXGRUKRE-UHFFFAOYSA-J 0.000 claims description 26
- 239000005078 molybdenum compound Substances 0.000 claims description 19
- 150000002752 molybdenum compounds Chemical class 0.000 claims description 19
- 239000003921 oil Substances 0.000 claims description 19
- 239000000463 material Substances 0.000 claims description 17
- 239000003795 chemical substances by application Substances 0.000 claims description 14
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- XYRMLECORMNZEY-UHFFFAOYSA-B [Mo+4].[Mo+4].[Mo+4].[O-]P([O-])([S-])=S.[O-]P([O-])([S-])=S.[O-]P([O-])([S-])=S.[O-]P([O-])([S-])=S Chemical compound [Mo+4].[Mo+4].[Mo+4].[O-]P([O-])([S-])=S.[O-]P([O-])([S-])=S.[O-]P([O-])([S-])=S.[O-]P([O-])([S-])=S XYRMLECORMNZEY-UHFFFAOYSA-B 0.000 claims description 5
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- 229910052750 molybdenum Inorganic materials 0.000 abstract description 9
- 239000011733 molybdenum Substances 0.000 abstract description 9
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 abstract description 8
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- SNFRINMTRPQQLE-OFGNMXNXSA-N Montanin Natural products O=C1[C@@]2(O)[C@@H](O)[C@@]3(CO)O[C@H]3[C@@H]3[C@H]4[C@@]5(C(=C)C)O[C@](CCCCCCCCCCC)(O4)O[C@@]3([C@H](C)C5)[C@@H]2C=C1C SNFRINMTRPQQLE-OFGNMXNXSA-N 0.000 description 8
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- 229920002725 thermoplastic elastomer Polymers 0.000 description 8
- WMYJOZQKDZZHAC-UHFFFAOYSA-H trizinc;dioxido-sulfanylidene-sulfido-$l^{5}-phosphane Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([S-])=S.[O-]P([O-])([S-])=S WMYJOZQKDZZHAC-UHFFFAOYSA-H 0.000 description 8
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- 150000002632 lipids Chemical class 0.000 description 6
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 5
- 150000001721 carbon Chemical group 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
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- 238000005096 rolling process Methods 0.000 description 5
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- 150000003752 zinc compounds Chemical class 0.000 description 5
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- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 4
- 125000001931 aliphatic group Chemical group 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- VJHINFRRDQUWOJ-UHFFFAOYSA-N dioctyl sebacate Chemical group CCCCC(CC)COC(=O)CCCCCCCCC(=O)OCC(CC)CCCC VJHINFRRDQUWOJ-UHFFFAOYSA-N 0.000 description 4
- IRHTZOCLLONTOC-UHFFFAOYSA-N hexacosan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCO IRHTZOCLLONTOC-UHFFFAOYSA-N 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 229910052725 zinc Inorganic materials 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 239000004902 Softening Agent Substances 0.000 description 3
- 159000000007 calcium salts Chemical class 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 230000001965 increasing effect Effects 0.000 description 3
- 239000000314 lubricant Substances 0.000 description 3
- 238000005457 optimization Methods 0.000 description 3
- 125000000962 organic group Chemical group 0.000 description 3
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- MBBWTVUFIXOUBE-UHFFFAOYSA-L zinc;dicarbamodithioate Chemical compound [Zn+2].NC([S-])=S.NC([S-])=S MBBWTVUFIXOUBE-UHFFFAOYSA-L 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 241000158728 Meliaceae Species 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 150000004996 alkyl benzenes Chemical class 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 239000000806 elastomer Substances 0.000 description 2
- 150000002191 fatty alcohols Chemical class 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
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- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- XDVOLDOITVSJGL-UHFFFAOYSA-N 3,7-dihydroxy-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane Chemical compound O1B(O)OB2OB(O)OB1O2 XDVOLDOITVSJGL-UHFFFAOYSA-N 0.000 description 1
- IHLDEDLAZNFOJB-UHFFFAOYSA-N 6-octoxy-6-oxohexanoic acid Chemical compound CCCCCCCCOC(=O)CCCCC(O)=O IHLDEDLAZNFOJB-UHFFFAOYSA-N 0.000 description 1
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- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005069 Extreme pressure additive Substances 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- SDXQZTGJYPVZNI-UHFFFAOYSA-K P(=S)([S-])([O-])[O-].C(C)C(C[Mo+3])CCCC Chemical compound P(=S)([S-])([O-])[O-].C(C)C(C[Mo+3])CCCC SDXQZTGJYPVZNI-UHFFFAOYSA-K 0.000 description 1
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- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000012661 block copolymerization Methods 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
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- 229910052796 boron Inorganic materials 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical compound NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
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- 238000005336 cracking Methods 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
- QFKPJTUVZHVHRZ-UHFFFAOYSA-N decanedioic acid;sodium Chemical compound [Na].[Na].OC(=O)CCCCCCCCC(O)=O QFKPJTUVZHVHRZ-UHFFFAOYSA-N 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
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- XWVQUJDBOICHGH-UHFFFAOYSA-N dioctyl nonanedioate Chemical compound CCCCCCCCOC(=O)CCCCCCCC(=O)OCCCCCCCC XWVQUJDBOICHGH-UHFFFAOYSA-N 0.000 description 1
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- CJMZLCRLBNZJQR-UHFFFAOYSA-N ethyl 2-amino-4-(4-fluorophenyl)thiophene-3-carboxylate Chemical compound CCOC(=O)C1=C(N)SC=C1C1=CC=C(F)C=C1 CJMZLCRLBNZJQR-UHFFFAOYSA-N 0.000 description 1
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- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
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- 159000000003 magnesium salts Chemical class 0.000 description 1
- 238000005297 material degradation process Methods 0.000 description 1
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- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
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- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- VGTPKLINSHNZRD-UHFFFAOYSA-N oxoborinic acid Chemical compound OB=O VGTPKLINSHNZRD-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N pentanoic acid group Chemical group C(CCCC)(=O)O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
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- 239000001103 potassium chloride Substances 0.000 description 1
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- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
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- WBHHMMIMDMUBKC-QJWNTBNXSA-N ricinoleic acid Chemical compound CCCCCC[C@@H](O)C\C=C/CCCCCCCC(O)=O WBHHMMIMDMUBKC-QJWNTBNXSA-N 0.000 description 1
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- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
- C10M169/06—Mixtures of thickeners and additives
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
- C10M2201/06—Metal compounds
- C10M2201/065—Sulfides; Selenides; Tellurides
- C10M2201/066—Molybdenum sulfide
-
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Abstract
为了实现该目的，提供一种润滑脂组合物，该润滑脂组合物与橡胶或热塑弹性体制成的保护罩有良好兼容性，该润滑脂组合物应用于等速万向节时还产生增强的耐久性、低磨损及低摩擦，润滑脂组合物建议包含：a)至少一种基油；b)5％重量至40％重量的至少一种磺酸钙皂和/或磺酸钙络合物皂作为增稠剂；和c)至少一种含钼添加剂。
Description
本发明涉及旨在主要用于机动车辆的动力传动系统中所用等速万向节(尤其是球状节或三脚节(tripod-joint))的润滑脂。本发明还涉及包含本发明的润滑脂组合物的等速万向节。
等速万向节(CVJ)内元件的运动为组合了滚动、滑动和旋转的复合体。该万向节受到扭矩作用时，元件一起荷载，这不仅引起元件接触面的磨损，而且引起表面之间滚动接触疲劳和明显的摩擦力。磨损可导致万向节的故障且摩擦力可使动力传动系统产生噪声、振动并使其粗糙(NVH)。NVH通常通过测定倒转(plunging)型CVJ产生的轴向力来“测量”。理想的是用于等速万向节的润滑脂不仅能减少磨损，还应具有低摩擦系数以减少摩擦力并减少或阻止NVH。
等速万向节还具有弹性体材料的封闭保护罩(sealing boot)，该保护罩通常为风箱形，一端连接于CVJ外部且另一端连接于CVJ的互连轴或输出轴。该保护罩将润滑脂保留在万向节中并避免尘垢和水进入。
润滑脂不仅必须在CVJ中减少磨损和摩擦且阻止过早出现滚动接触疲劳，而且还必须与制成保护罩的弹性体材料兼容。否则，存在保护罩材料的降解，这会过早引起保护罩故障，使润滑脂可能流失并最终引起CVJ故障。用于CVJ保护罩的两种主要的材料为氯丁橡胶(CR)和热塑弹性体(TPE)，尤其是醚酯嵌段共聚热塑弹性体(TPC-ET)。
典型的CVJ润滑脂具有作为环烷(饱和环)和链烷(饱和直链和支链)矿物油的共混物的基油。也可以加入合成油。已知所述基油对CR和TPC-ET制成的两种保护罩的变劣(膨胀或收缩)均有大的影响。矿物基油和合成基油均从保护罩材料中提取增塑剂和其他油溶性保护剂。链烷矿物油和聚-α-烯烃(PAO)合成基油极少扩散进入尤其橡胶材料制成的保护罩引起收缩，但另一方面环烷矿物油及合成酯扩散进入保护罩材料并充当增塑剂，可引起膨胀。增塑剂或增塑剂组合物替换为环烷矿物油，可明显降低保护罩的性能，尤其低温时，并可能通过冷破裂引起保护罩故障，最终导致CVJ故障。如果发生明显的膨胀或软化，保护罩的最大高速性能由于高速运转时稳定性差和/或过度的径向膨胀而降低。
为了解决上述问题，US6,656,890B1提出一种特别的基油组合物，包含10至35％重量的一种或多种聚-α-烯烃，3至15％重量的一种或多种合成有机酯，20至30％重量的一种或多种环烷油，该组合物其余部分为一种或多种链烷油，还有锂皂增稠剂和无硫摩擦改性剂，可以为有机钼络合物，二硫代磷酸钼和二烷基二硫代磷酸锌，和其他添加剂例如腐蚀抑制剂、抗氧化剂、特压添加剂和粘合剂。然而，由SRV(德语词组Schwingungen、Reibung、Verschleiβ的缩写)测试所测量的US 6,656,890B1的润滑脂组合物的摩擦系数和磨损度有待改善。
因此本发明的目的是提供一种润滑脂组合物，主要应用于等速万向节，该润滑脂组合物与橡胶或热塑弹性体制成的防护罩具有良好的兼容性，且该润滑脂组合物应用于CVJ时还产生增强的耐久性、低磨损及低摩擦。
本发明的所述目标通过用于等速万向节的润滑脂组合物来实现，该润滑脂组合物包含：
a)至少一种基油；
b)作为增稠剂的5％重量至40％重量的至少一种磺酸钙皂和/或磺酸钙络合物皂；和
c)至少一种含钼添加剂。
关于要求保护的润滑脂组合物中包含的组分所使用的术语％重量，该术语％重量在本说明书中相对润滑脂组合物的总量，另有说明的除外。
优选地，本发明中用于润滑脂组合物的基油组合物包含聚-α-烯烃、环烷油、链烷油和/或合成有机酯。
作为本发明中的基油组合物，可以优选使用US 6,656,890B1公开的基油组合物，其公开内容通过引用并入本文。然而，任何其他种类的基油组合物，尤其是矿物油的共混物、合成油的共混物或矿物油和合成油混合物的共混物也可使用。基油组合物应该优选具有的运动粘度为40℃时约32至约250mm2/s且100℃时约5至约25mm2/s。矿物油优选选自至少一种环烷油和/或至少一种链烷油。可用于本发明中的合成油选自至少一种聚-α-烯烃(PAO)和/或至少一种合成有机酯。该合成有机酯优选为具有基于脂族醇的子基(subgroup)的二羧酸衍生物。优选地，该脂族醇具有2至20个碳原子的伯直碳链或支碳链。优选地，该合成有机酯选自癸二酸-双(2-乙基己酯)(“癸二酸二辛酯”(DOS))、己二酸-双-(2-乙基己酯)(“己二酸二辛酯”(DOA))和/或壬二酸-双(2-乙基己酯)(“壬二酸二辛酯”(DOZ))。
如果聚-α-烯烃存在于基油组合物中，选择的聚-α-烯烃优选具有粘度范围为100℃时约2至约40厘沲。选择用于基油组合物的环烷油优选具有的粘度范围为40℃时约3至约370mm2/s，更优选40℃时约20至约150mm2/s，然而如果基油组合物中存在链烷油，链烷油优选具有粘度范围为40℃时约9至约170mm2/s。
所述至少一种在本发明润滑脂组合物中用作增稠剂的磺酸钙皂和/或磺酸钙络合物皂主要为脂族酸或脂肪酸和/或羟基脂族酸和/或羟基脂肪酸的反应产物。脂肪酸或羟基脂肪酸优选选自含有12至30个碳原子，优选为12至24个，最优选为12至18个碳原子的脂肪酸或羟基脂肪酸。脂族酸和/或脂肪酸可选自十二烷酸、棕榈酸、硬脂酸、油酸、蓖麻油酸和/或12-羟基硬脂酸。优选羟基脂族酸和/或羟基脂肪酸是因为它们的增稠性更高。可用于制备磺酸钙润滑脂和/或磺酸钙络合物润滑脂的磺酸钙选自至少一种磺酸钙和/或至少一种高碱性磺酸钙。本发明中，优选高碱性磺酸钙，尤其为具有金属比为约6至35的高碱性磺酸钙。
可用作增稠剂的磺酸钙皂可通过前述磺酸钙组分和脂族酸和/或脂肪酸和/或羟基脂族酸和/或羟基脂肪酸进行反应来制备，反应时可存在其他试剂，尤其是转换(converting)试剂，包括例如水、醇(例如联苯酚、异丁醇、正戊醇或其混合物)或醇与水的混合物、烷撑二醇、烷撑二醇的单低级烷醚例如乙二醇的单甲基醚、低级脂族羧酸例如乙酸和丙酸、酮、醛、胺、含磷的酸(phosphorus acids)、烷基和芳香胺、咪唑啉(imidazoilines)、链烷醇胺、含硼的酸(boron acids)(包括硼酸、四硼酸、偏硼酸)和此类含硼的酸的酯，还有二氧化碳(本身，或者与水结合更好)。本发明中可用作增稠剂的磺酸钙络合物皂可通过至少一种脂族酸和/或脂肪酸或羟基脂族酸和/或羟基脂肪酸、至少一种上文提到的磺酸钙化合物与络合剂(例如一种或多种二羧酸或短和/或中链羧酸的混合物的硼酸盐)一起来制备使用。本发明中将磺酸钙络合物皂用作增稠剂使本发明的润滑脂组合物可在高至约180℃的温度下起作用，然而对于本发明中使用的可作为增稠剂的普通磺酸钙皂，润滑脂组合物仅可在高至约120℃的温度下起作用。然而，也可使用所有上述皂的混合物。
所述至少一种存在于本发明润滑脂组合物的含钼添加剂优选选自至少一种二硫代氨基甲酸钼、至少一种二硫代磷酸钼、MoS2、至少一种无S且无P的有机钼化合物和/或至少一种三核钼化合物。该至少一种三核钼化合物具有如下通式
Mo3SkLnQz (I)
其中L独立选自具有以下有机基团的配体：该有机基团有足够数量的碳原子以使该化合物可溶于或分散于油中，n为1至4，k为4至7，Q选自中性给电子化合物例如胺、醇、膦和醚，而z取值范围为0至5且包括非化学计量值。
存在于三核钼化合物的所有配体、有机基团中的碳原子数量至少为21个，优选至少25个，更优选至少30个，最优选至少35个。可用于本发明的三核钼化合物公开于US 6,172,013B1，其公开内容已通过引用结合至本发明。存在至少0.25％重量的三核钼化合物为优选且能在用于CVJ时显著降低摩擦系数和磨损度。
优选所述至少一种二硫代磷酸钼(MoDTP)和/或二硫代氨基甲酸钼(MoDTC)以约0.3％重量，更优选约0.5％重量，最优选约1.0％重量，至约3.5％重量，最优选约3％重量，存在于本发明的润滑脂组合物中，各种情况中均相对润滑脂组合物的总量。然而，任何其他的含钼化合物也可作为组分c)存在于本发明的润滑脂组合物中，其中优选有机钼化合物。本发明的润滑脂组合物可以包含一种或多种MoDTC和/或MoDTP，尤其是其混合物。本发明的MoDTP具有如下通式：
其中X或Y代表S或O而R1至R4包括R1和R4中每一个可以相同也可不同且每个代表具有6至30个碳原子的伯烷基(直链)或仲烷基(支链)。
本发明中MoDTC具有如下通式：
[(R5)(R6)N-CS-S]2-Mo2OmSn(III)
其中R5和R6各自独立代表具有1至24个碳原子，优选3至18个碳原子的烷基；m取值范围为0至3且n取值范围为4至1，条件是m+n＝4。
优选地，含钼添加剂选自至少一种二硫代氨基甲酸钼和至少一种三核钼化合物。本发明的更优选实施方案中润滑脂组合物包含0.2％重量至5.0％的至少一种三核钼化合物，优选0.25％重量至3％重量，最优选0.3％重量至2％重量，进一步更优选0.3％重量至1.25％重量。
本发明的进一步优选实施方案中，润滑脂组合物包含0.25至5％重量的至少一种固体或液体二硫代氨基甲酸钼，优选0.5％重量至3％重量，最优选0.8％重量至2％重量。本发明的进一步优选实施方案中，二硫代氨基甲酸钼选自至少一种固体二硫代氨基甲酸钼。
本发明的另一实施方案中，润滑脂组合物进一步包含至少一种抗氧化剂、至少一种缓蚀剂、至少一种抗磨剂、至少一种蜡、至少一种摩擦改性剂和/或至少一种特压剂。
作为摩擦改性剂，使用至少一种锌化合物添加剂，更优选锌化合物添加剂的量为约0.1％重量至约3.5％重量，优选至约2.5％重量，更优选约0.5％重量至约2.0％重量，相对润滑脂组合物的总量。最优选的锌化合物添加剂选自至少一种二硫代磷酸锌(ZnDTP)和/或二硫代氨基甲酸锌(ZnDTC)，且ZnDTP为最优选。二硫代磷酸锌优选选自具如下通式的二烷基二硫代磷酸锌：
(R7O)(R8O)SP-S-Zn-S-PS(OR9)(OR10)(IV)
其中R7至R10包括R7和R10中每一个可以相同也可不同且每个代表伯烷基或仲烷基，其中伯烷基最优选具有1至24个碳原子，优选3至20个，最优选3至5个碳原子。尤其，如果取代基R7、R8、R9和R10代表伯烷基和仲烷基的组合，且每个具有3至8个碳原子，可预期得到良好效果。
二硫代氨基甲酸锌可优选选自具有如下通式的二烷基二硫代氨基甲酸锌：
其中R11、R12、R13和R14可以相同也可不同且每个代表具有1至24个碳原子的烷基或具有6至30个碳原子的芳基。
向本发明润滑脂组合物中加入至少一种锌化合物添加剂，CVJ的摩擦系数和磨损度进一步显著减小。
EP剂优选为不含金属的聚硫化物或其混合物，例如硫化脂肪酸甲酯试剂，优选粘度为40℃时约25mm2/s，优选存在量为约0.1至约3％重量，优选0.3至约2％重量，相对润滑脂组合物总量。EP剂室温下无活性硫总量优选为约8至约50％重量，优选至约45％重量。按照ASTM D1662所测量活性硫的量可以最高约1％重量，优选100℃时最高约8％重量，且优选140℃时最高约20％重量，重量百分比相对EP剂本身的量。此种EP剂在阻止接触的CVJ内部元件的磨损方面表现出良好的效果。如果硫含量超过上文限定的上限，可能促使引发滚动接触疲劳和接触的金属元件磨损并可能导致CVJ保护罩材料降解。
作为抗氧化剂，本发明中的润滑脂组合物可以包含胺，优选芳香胺，更优选苯基-α-萘胺或二苯胺或其衍生物。抗氧化剂用于阻止润滑脂组合物与氧化作用有关的劣化。本发明的润滑脂组合物可包含含量范围为约0.1至约2％重量(相对润滑脂组合物总量)的抗氧化剂以抑制基油组合物氧化降解，以及延长润滑脂组合物的寿命，因此可延长CVJ的寿命。
通常，在CVJ组装之前的最后操作是清洗去除加工碎片，因此润滑脂必须吸收任何痕量残留水以阻止水引起的腐蚀及对CVJ运行的负面影响，所以需要添加缓蚀剂。作为缓蚀剂，本发明的润滑脂组合物可以包含选自以下的至少一种金属或二金属盐∶氧化蜡的金属盐、石油磺酸(petroleum sulphonate)的金属盐尤其是通过磺化存在于润滑油馏分的芳烃组份制备的石油磺酸的金属盐、和/或烷基芳族磺酸的金属盐例如二壬基萘磺酸、烷基苯磺酸或高碱性烷基苯磺酸的金属盐。金属盐的例子包括钠盐、钾盐、钙盐、镁盐、锌盐、季铵盐，最优选钙盐。氧化蜡的钙盐也确保具有良好效果。特别优选癸二酸二钠作为缓蚀剂。
本发明中抗磨剂通过加入成膜化合物来阻止金属-金属间接触以通过物理吸收或化学反应来保护表面。ZnDTP化合物也可用作抗磨剂。作为本发明的防腐剂优选使用钙磺酸盐，优选量为约0.5至约3％重量，相对润滑脂组合物总量。
作为蜡化合物，本发明的润滑脂组合物可以包含本领域已知的用于润滑脂组合物的任何种类的蜡(优选油性的蜡)或其混合物，其中最优选褐煤蜡，尤其酯褐煤蜡(为至少一种酸褐煤蜡和酯的反应产物)，及聚烯烃蜡(包括微粉化褐煤蜡和/或聚烯烃蜡)，或其混合物。出于本发明的目的褐煤蜡优选包含C22-C34-脂肪酸和可能的具有24至28个碳原子的蜡醇的酯。在本发明褐煤蜡中存在的酯可以在约35％重量至约70％重量范围。另外，游离脂肪酸和游离蜡醇和褐煤树脂可以存在。有用的褐煤蜡由例如Clariant GmbH公司，86005Augsburg，德国提供，尤其是以商品名“Licowax”提供和出售的褐煤蜡。出于本发明的目有用的聚烯烃蜡特别是聚丙烯蜡和/或聚乙烯蜡或其混合物，还包括改性的聚烯烃蜡，尤其通过乙烯与有用的共聚单体如乙烯基酯或丙烯酸进行共聚合来获得。按照DIN 53018来测量，蜡优选具有粘度为100℃时至少约50mPa*s，更优选100℃时至少约100mPa*s，且最优选100℃时至少约200mPa*s。润滑脂组合物中使用的蜡可以为粉末或薄片形式，并在加入润滑脂组合物时伴有长时间搅拌，优选在升高的温度下，尤其在约80℃至约100℃温度下。
也可用于本发明的例如脂肪酸酰胺和脂肪族胺磷酸盐的传统的摩擦改性剂已用于润滑脂和其他润滑剂很多年(见，如公开于Klamann，Dieter-“Lubricants”，Verlag Chemie GmbH 1983，第1版9.6章的改性剂)。它们的作用是使润滑剂在广泛操作条件下稳定但未必具有低摩擦性。
本发明的进一步实施方案中，要求保护的润滑脂组合物包含0.3％重量至2％重量，优选至1.25％重量的至少一种三核钼化合物和0.8％重量至3％重量，优选至2％重量的至少一种二硫代氨基甲酸钼。
本发明的进一步优选实施方案中，要求保护的润滑脂组合物包含65％重量至86.9％重量的基油组合物，16％重量至20％重量的至少一种磺酸钙皂和/或磺酸钙络合物皂，0.3％重量至2％重量的至少一种三核钼化合物和0.3％重量至3％重量的至少一种二硫代氨基甲酸钼。本发明中最优选润滑脂组合物包含16％重量至20％重量的至少一种磺酸钙皂和/或磺酸钙络合物皂，0.3％重量至0.7％重量的至少一种三核钼化合物，0.75％重量至1.8％重量的至少一种二硫代氨基甲酸钼，和66.45％重量至86.9％重量的基油组合物。要求保护的润滑脂组合物可以进一步包含上文所述其他试剂。
另外，本发明涉及本发明的润滑脂组合物在等速万向节中的用途，且进一步涉及包含要求保护的润滑脂组合物的等速万向节。该等速万向节特别包含保护罩，该保护罩至少部分地用本发明的润滑脂组合物填充，该保护罩包括分配到万向节的第一连接区域，及分配到轴的第二连接区域。保护罩可用普通夹持设备固定于节和/或轴上。
本发明将在以下实施例中进行更详细的解释。
实施例
为了测定通过本发明润滑脂组合物降低摩擦系数和磨损度的效果，使用Optimol Instruments SRV试验装置来进行SRV测试。由购自Munich，Westendstrasse 125的Optimol Instruments PrüftechnikGmbH的100Cr6标准轴承钢制成并用溶剂适当清洗的平圆盘下部样本(flat disc lower specimen)制备后与待检测的润滑脂组合物接触。SRV测试为工业标准测试且特别适合于测试用于CVJ的润滑脂。该测试包括具有直径为10mm由100Cr6轴承钢制成的上部球形样本，该上部球形样本在载荷时于上文所述的平圆盘下部样本上往复运动。在模拟三脚节(tripod joint)的测试中，使用40Hz的频率，500N外加负载，在80℃下进行60分钟(包括试运转)。行程(stroke)为3.0mm。得到的摩擦系数用计算机记录。对于每种润滑脂，报告的值为两次运行测试终点的两个数据的均值。磨损度通过轮廓曲线仪和数字面积仪来测量。通过使用轮廓曲线仪，可得到磨损表面中部横截面轮廓。横截面面积(S)可通过使用数字面积仪来测量。磨损量通过V＝SI来评定，其中V为磨损体积，I为行程。磨损率(Wr)通过Wr＝V/L[μm3/m]来获得，其中L为测试中总滑动距离。对于试运行，在上述特定条件下50N外加负载持续1分钟来开始。然后，外加负载在30秒内以50N的增加幅度增加到500N。
另外，对分别配有本发明的实施例C4的润滑脂组合物及与之比较的两种商业润滑脂组合物A和B的橡胶保护罩和TPE-保护罩性能进行测试，测试125℃下将保护罩材料浸入润滑脂达336小时的热老化前后硬度(肖氏硬度D)的变化和张力、伸长率及体积的变化百分比。所述值依照ISO868(肖氏硬度D)，ISO37(张力变化及伸长率变化)及ISO2781(体积变化)来测量。
在对比实施例A和B中使用的商业润滑脂为Axel CaSX 51646，购自荷兰Heijningen的Axel Christiernsson B.V.(比较实施例A)；以及Super Grease 2，购自中国天津的中国石油化工股份有限公司天津润滑油脂有限公司(津脂)(比较实施例B)。
以下物质用于本发明被检测的润滑脂组合物。
基油组合物(油共混物)
使用的基油组合物具有40℃时约165mm2/s的运动粘度和100℃时约16mm2/s的运动粘度。基油共混物可以为一种或多种链烷油、一种或多种环烷油和，如有必要，一种或多种聚-α-烯烃(PAO)的混合物，其中所述一种或多种链烷油的范围为约10至约60％重量，优选约20至40％重量，所述一种或多种环烷油的范围为约30至约80％重量，优选约55至约80％重量，所述一种或多种PAO的范围为约5至约40％重量，均相对油混合物总量。油共混物还可包含范围为约2至约10％重量的DOS，相对油混合物总量。该实施例中使用的具体油共混物由73％重量的环烷油SR130(由瑞典Stockholm的AB Petroleum生产)，25％重量的链烷油NS650(购自荷兰Europoort的Kuwait Petroleum Europoort B.V)及2％重量的DOS制成。
选择的环烷油在40℃时粘度范围在约20至约180mm2/s，链烷油粘度范围在40℃时在约25至约400mm2/s之间，而PAO粘度范围在100℃时在约6至约40mm2/s之间。
磺酸钙皂
本发明的实施例中使用的磺酸钙皂为高碱性磺酸钙皂，通过具有约6至35的金属比(metal ratio)的高碱性磺酸钙与12-羟基硬脂酸在溶剂中性油、碳酸钙、异丙醇和磷酸存在下进行反应获得。生产所使用的磺酸钙皂可能的方法描述于US 5,126,062。
三分子钼化合物(TNMoS)
本发明中用于润滑脂组合物的三分子钼化合物为含硫三核钼化合物，以商品名C9455B从英国Infineum International Ltd.购得。其结构于US 6,172,013B1详细阐明。
其他钼化合物
使用产自日本Asahi Denka Co.Ltd.的以商品名Sakuralube 300(S-300)销售的二硫代磷酸钼(MoDTP)，化学式为2-乙基己基二硫代磷酸钼，用矿物油稀释。另外，使用以商品名Sakuralube 600(S-600)销售，产自日本Asahi Denka Co.Limited，或者以商品名Molyvan A销售，产自美国R.T.Vanderbilt Company，Inc的固体二硫代氨基甲酸钼(MoDTC固体)。
另外，使用以商品名Sakuralube 200(MoDTC S-200)销售、产自日本Asahi Denka Co.Limited的液态二硫代氨基甲酸钼，及以商品名S-701销售、产自日本Asahi Denka Co.Limited的无S且无P有机钼添加剂(具有通式R2N-MoxOyH的钼胺络合物)以及普通MoS2。
其他添加剂
由英国Oxfordshire的Infineum International Ltd.销售的商品名为C9425的锌化合物添加剂即二硫代磷酸锌ZnDTP，用作摩擦改性剂，是具有伯烷基和/或仲烷基的二烷基二硫代磷酸锌，所述烷基特别是具有3至8个C原子，优选具有4至5个C原子，用矿物油稀释。
首先，本发明中润滑脂组合物的优势通过测量六种不同润滑脂的摩擦系数和焊接载荷(welding load)来衡量，如表1所示：
表1
实施例A1至A8摩擦系数以及焊接载荷测量的SRV-测量结果可从图1和图2获得。在加入简单MoS2时测量到最低摩擦系数，然而测量到最高的磨损度，而与实施例A1相比，实施例A3测量到非常低的磨损度以及增加的摩擦系数，实施例A1不属于本发明的润滑脂组合物，仅由基油和磺酸钙皂组成。另外，实施例A2和A5在磨损度方面也表现出好的测试结果。
另外的一系列测试中，TNMoS和MoDTC固体的量经过修改。十种润滑脂组合物依照表2制备。
表2
实施例B1至B3中TNMoS的量经过修改，其中实施例B4至B7中MoDTC固体的量经过修改。实施例B8至B10涉及0.5％重量的TNMoS与不同量MoDTC固体的混合物。关于摩擦系数及焊接载荷的SRV测量结果可从图3和图4获得。
实施例B3显示出最低摩擦系数，然而磨损度的结果在所得结果中仅处在中等。另外，对于实施例B9至B10测量到低的摩擦系数，其中实施例B9显示出测量到的最低磨损度之一。所述测试结果尤其表明不同含钼化合物的组合为优选，且含钼化合物的使用范围对于测量到的摩擦系数和磨损度非常敏感。
在第三测试系列中，研究了向1.5％重量MoDTC固体的量中加入用量为0.5％重量的不同含钼化合物和ZnDTP的效果。被检测的润滑脂组合物C1至C6如表3所示。
表3
摩擦系数及焊接载荷测量的SRV测量结果可以从图5和图6得到。容易看到作为1.5％重量的固态的MoDTC固体和含量为0.5％重量的三核钼化合物的组合物的组合物C4为最优选，因为摩擦系数和磨损度与其他组合物的结果比较均明显更低。
最后，三种钼化合物添加剂或两种钼化合物添加剂与ZnDTP的组合物按照表4检测。MoDTC固体的量没有变化。
表4
关于实施例D1至D5的图7和8表明，对于实施例D5测量到最低摩擦系数，而磨损度在实施例D2和D4中非常低。然而，由于最低摩擦系数，润滑脂组合物D5(与润滑脂组合物C4非常相似)显得是有利的。
最后，对配备不同润滑脂的保护罩的性能进行了测试。实施例C4的润滑脂组合物与作为可商业购得的润滑脂组合物的比较实施例A和B进行比较。结果如表5所示。
表5
| 实施例C4 | 比较实施例A | 比较实施例B | |
| 与橡胶的兼容性 | |||
| 硬度变化(肖氏硬度D) | -9 | +1 | 0 |
| 张力变化(％) | -4,5 | -5,4 | -2,3 |
| 伸长率变化(％) | -17,7 | -17,9 | -17,6 |
| 体积变化(％) | +8,9 | -3,0 | -2,8 |
| 与TPE的兼容性 | |||
| 硬度变化(肖氏硬度D) | -6 | -7 | -5 |
| 张力变化(％) | -40,4 | -63,9 | -11,7 |
| 伸长率变化(％) | -16,5 | -72,4 | +1,3 |
| 体积变化(％) | +12,9 | +10,0 | +9,2 |
从表5可看出，尤其是有关TPE材料制成的保护罩，测得了有关张力变化和伸长率变化方面的优选性能。对于实施例C4进行的耐久测试表明等速万向节的耐久性与配备了具有商业购得的诸如比较实施例A和B润滑脂的防护罩的万向节相比可增加至两倍寿命。
总之，本发明的润滑脂组合物对于摩擦系数和磨损度具有有利且显著的影响，产生好的特压表现。特别优选以总量至多3.5％重量加入到润滑脂组合物的两种或三种不同含钼化合物的组合物，其中加入三核钼化合物和二硫代氨基甲酸钼(优选为固态)组合为最优选。
Claims (6)
1.一种用于等速万向节的润滑脂组合物，所述润滑脂组合物包含：
a)基油组合物；
b)作为增稠剂的16％重量至20％重量的至少一种磺酸钙皂和/或磺酸钙络合物皂；和
c)0.3％重量至2.0％重量的至少一种三核钼化合物和0.25％重量至3％重量的至少一种二硫代氨基甲酸钼。
2.权利要求1的润滑脂组合物，其特征在于该二硫代氨基甲酸钼选自至少一种固体二硫代氨基甲酸钼。
3.权利要求1的润滑脂组合物，其特征在于该润滑脂组合物还包含至少一种二硫代磷酸钼。
4.权利要求1的润滑脂组合物，其特征在于该基油组合物包含聚-α-烯烃、环烷油、石蜡油和/或合成有机酯。
5.权利要求1的润滑脂组合物，其特征在于该润滑脂组合物还包含至少一种抗氧化剂、至少一种缓蚀剂、至少一种抗磨剂、至少一种蜡、至少一种摩擦改性剂和/或至少一种特压剂。
6.前述权利要求1至5的任一项的润滑脂组合物在等速万向节中的用途。
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| PCT/EP2008/002579 WO2009121378A1 (en) | 2008-04-01 | 2008-04-01 | Grease composition for use in constant velocity joints |
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| CN102455628B (zh) | 2010-10-29 | 2014-08-13 | 京瓷办公信息系统株式会社 | 图像形成装置 |
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| CN104769087B (zh) * | 2012-11-16 | 2018-07-03 | 出光兴产株式会社 | 润滑脂组合物 |
| JP6292569B2 (ja) * | 2013-12-04 | 2018-03-14 | 協同油脂株式会社 | 等速ジョイント用グリース組成物及びそのグリース組成物を封入した等速ジョイント |
| RU2581463C1 (ru) * | 2014-11-25 | 2016-04-20 | федеральное государственное бюджетное образовательное учреждение высшего профессионального образования "Российский государственный университет нефти и газа имени И.М. Губкина" | Пластичная смазка |
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| JP6605367B2 (ja) * | 2016-03-10 | 2019-11-13 | 協同油脂株式会社 | 等速ジョイント用グリース組成物及び等速ジョイント |
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| KR20220064397A (ko) * | 2019-09-18 | 2022-05-18 | 게케엔 드리펠린 인터나쇼날 게엠베하 | 이황화 몰리브덴 및/또는 이황화 텅스텐과 황화아연을 포함하는 등속 조인트용 그리스 조성물 |
| US11643613B2 (en) * | 2019-09-18 | 2023-05-09 | Gkn Driveline International Gmbh | Grease composition including copper sulfide for constant velocity joints |
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| CN114752429A (zh) * | 2022-05-31 | 2022-07-15 | 山东联博新材料科技有限公司 | 一种重负荷高温抗水轧辊轴承润滑脂及其制备方法 |
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| ES2436776T3 (es) | 2014-01-07 |
| US20110021391A1 (en) | 2011-01-27 |
| EP2260090B1 (en) | 2013-08-28 |
| CN101981169A (zh) | 2011-02-23 |
| JP5284372B2 (ja) | 2013-09-11 |
| BRPI0822394A2 (pt) | 2020-10-06 |
| WO2009121378A1 (en) | 2009-10-08 |
| JP2011512432A (ja) | 2011-04-21 |
| EP2260090A1 (en) | 2010-12-15 |
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