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WO1994011470A1 - Graisses - Google Patents

Graisses Download PDF

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Publication number
WO1994011470A1
WO1994011470A1 PCT/GB1993/002313 GB9302313W WO9411470A1 WO 1994011470 A1 WO1994011470 A1 WO 1994011470A1 GB 9302313 W GB9302313 W GB 9302313W WO 9411470 A1 WO9411470 A1 WO 9411470A1
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WO
WIPO (PCT)
Prior art keywords
grease
organo
grease according
alkyl
compound comprises
Prior art date
Application number
PCT/GB1993/002313
Other languages
English (en)
Inventor
Gareth Fish
Original Assignee
Gkn Technology Limited
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=10725130&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=WO1994011470(A1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Gkn Technology Limited filed Critical Gkn Technology Limited
Priority to GB9508436A priority Critical patent/GB2287715B/en
Priority to EP93924736A priority patent/EP0668900B2/fr
Priority to DE69321481T priority patent/DE69321481T3/de
Publication of WO1994011470A1 publication Critical patent/WO1994011470A1/fr

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    • C10N2040/50—Medical uses

Definitions

  • This invention relates to greases intended primarily but not exclusively for use in constant velocity joints.
  • Greases consist essentially of a base oil with a thickening agent and other additives may be included to promote specific properties, for example extreme pressure lubricants and anti-oxidants.
  • the thickening agent employed is traditionally a soap, but greases formulated in this way cannot achieve the high performance as required by modern technological demands and more recently greases have been made using organic polymers as a thickening agent, particularly polyureas. However, such greases offer little advantage since whilst achieving lower friction, they promote greater wear than traditional soap greases.
  • the object of the invention is to provide an improved grease offering low friction and low wear which is suitable for use in a constant velocity joint, but may also have other applications, and we have discovered that this can be achieved by utilising a lithium-based soap thickener in combination with other specific materials.
  • a grease comprising a base oil and a lithium-based soap thickener in combination with:-
  • organo-phosphorus compound extreme pressure additive (4) an organo-phosphorus compound extreme pressure additive.
  • greases according to such a formulation may be used as a base grease, together with other conventional additives, such as molybdenum disulphide, in the preparation of a grease composition which in testing and when used in a constant velocity joint provides both low friction and low wear in a manner not achievable by other known grease formulations or other trial formulations differing from the above formulation. It is thought that this combination of properties arises from a synergistic effect obtained by the use of the combination of the organo-sulphur and organo-phosphorus compounds in conjunction with the organo-molybdenum complex and the lithium-based soap.
  • the organo-molybdenum complex may comprise a molybdenum di- thiocarbamate in accordance with the formula
  • R primary or secondary alkyl or aryl or alkyl substituted aryl group or a mixture of such compounds.
  • the anti-wear/anti-oxidant compound may comprise an organo- metallic compound such as a metallic di-thiophosphate according to the formula
  • M Bi, Pb, Sb, Zn, Ni, W or Cd;
  • R primary or secondary alkyl or aryl or aryl with an alkyl substituent on the aromatic ring, or a mixture of such compounds.
  • R primary or secondary alkyl or aryl or aryl with an alkyl substituent on the aromatic ring, or a mixture of such compounds.
  • anti-wear/anti-oxidant compound could be employed.
  • the organo-sulphur compound may comprise one or more of the following
  • V (b) a synthetic sulphurised sperm oil typically comprising a mixture of unsaturated C 16 - C 24 fatty acids and their esters and glycerides which have been sulphurised;
  • the organo-phosphorus compound may comprise one or more of the following:-
  • R alkyl, aryl or alkyl substituted aryl group
  • the thickener may comprise a simple lithium soap formed from stearic acid or from 12-hydroxystearic acid or from other similar fatty acids, or a lithium complex soap formed from a mixture of such acids. More particularly, the lithium complex soap may comprise a mixture of hydroxy fatty acids and di-acid salts, such as lithium 12-hyroxystearate and lithium azelate.
  • Simple lithium soaps and complex lithium soaps when used in formulations in accordance with the invention appear to behave in substantially the same way, except that where the simple soap is employed the grease will operate only up to temperatures of about 120°C, whereas the complex soaps enable temperatures of up to about 180°C to be sustained.
  • the base oil may comprise a mineral oil or a synthetic oil or a mixture of such oils.
  • the invention also resides in a method of lubricating a constant velocity joint characterised by the use of such a grease, and further in a constant velocity joint packed with such a grease.
  • the base grease comprised a polyalphaolefin containing 10% lithium complex soap thickener consisting of a 60:40 mbcture of 12-hydroxystearate and azelate, with the addition of conventional additives such as tackiness agents, corrosion inhibiters and viscosity index improvers.
  • a polyalphaolefin containing 10% lithium complex soap thickener consisting of a 60:40 mbcture of 12-hydroxystearate and azelate
  • conventional additives such as tackiness agents, corrosion inhibiters and viscosity index improvers.
  • a lithium soap grease in accordance with the invention was made by using the above-mentioned base grease and adding thereto:-
  • organo-molybdenum complex comprising 2-ethylhexyl- molybdenum di-thiophosphate.
  • organometallic anti-wear/anti-oxidant comprising a zinc secondary alkyl di-thiophosphate.
  • a comparative lithium soap grease not in accordance with the invention was made by using the above-mentioned lithium complex base grease and adding thereto:-
  • organo-molybdenum complex comprising 2-ethylhexyl molybdenum di-thiophospjiate.
  • organo-metallic anti-wear/anti-oxidant comprising antimony di-amyldithiocarbamate.
  • a further comparison lithium soap grease not in accordance with the invention was made up using the same lithium complex base grease and adding thereto:-
  • Wear in the SRV test was determined by microscopic inspection to obtain a measurement of scar diameter, and a Rank Taylor Hobson Surtronic surface finish measuring machine was employed to determine the depth and cross- section of any scarring. These two measurements were used to calculate wear rate.
  • the term "low wear” as used herein generally indicates that no scar depth was measurable.
  • the grease of Example 3 performed only a little better in terms of co-efficient of friction than prior art grease (A) and not as well as prior art grease (B) and it also .did not exhibit the required low wear characteristic.
  • the grease of Example 2 performed somewhat better than prior grease (B) but again did not exhibit the required low wear characteristics.
  • the grease in accordance with Example 1 i.e. in accordance with the invention, not only had an improved co-efficient of friction relative to the other greases tested, but also exhibited low wear characteristics, as illustrated in Figure 2 which shows the surface profile of test samples from the SRV tests using the grease of Examples 1 and 2 at moderate load.
  • the grease of Example 1 in accordance with the invention shows no significant scarring, whereas that of Example 2 shows some scarring.
  • a further lithium soap grease in accordance with the invention was made up using the above-mentioned lithium complex base grease and adding thereto:-
  • organo-molybdenum complex comprising 2-ethyl hexyl molybdenum di-thiocarbamate.
  • organo-metallic anti-wear/anti-oxidant comprising a zinc secondary alkyl di-thiophosphate.
  • a further comparative lithium soap grease not in accordance with the invention was made up as in Example 4 but omitting the tritolylphosphate and substituting half of the stated organo-molybdenum complex by a primary alkyl molybdenum di-thiocarbamate.
  • a further comparative lithium soap grease not in accordance with the invention was made up as in Example 4 but omitting the tritolylphosphate.
  • a still further lithium soap grease in accordance with the invention was prepared as in Example 1 but using a sulphurised fatty acid ester instead of the sulphurised synthetic sperm oil.
  • Another blend also substituted tri- xylenylphosphate for the tritolylphosphate, giving similar results.
  • a still further comparative lithium soap grease not in accordance with the invention was prepared using the above-mentioned lithium complex base grease and adding thereto:-
  • organo-molybdenum complex comprising an equal mixture of 2-ethylhexyl molybdenum di-thiocarbamate and a primary alkyl molybdenum di-thiocarbamate.
  • a still further comparative lithium soap grease not in accordance with the invention was prepared using the above-mentioned lithium complex base grease and adding thereto:-
  • organo-sulphur compound comprising sulphurised synthetic sperm oil (but no organo-molybdenum complex and no organo-phosphorus compound)
  • the base grease comprises a mixture of polybutene and mineral oil containing the lithium-based complex soap thickener, also with the addition of conventional additives as previously mentioned.
  • a grease in accordance with the invention was made using the last- mentioned base grease and adding thereto.
  • organo-metallic anti-wear/anti-oxidant comprising a zinc secondary alkyl di-thiophosphate
  • a further grease, also in accordance with the invention was made in accordance with Example 11 but with the amounts of the specified additives reduced by 50% whilst retaining the same ratio to one another.
  • results for Example 11 showed slightly higher friction than for Examples 1 and 12 but less than those for Example 2, whereas the results for Example 12 are virtually indistinguishable from those for Examples 1 and 7.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Lubricants (AREA)

Abstract

Une graisse essentiellement destinée à être utilisée avec des joints à vitesse constante comprend une huile de base qui peut être une huile minérale, une huile de synthèse ou un mélange de telles huiles, et un épaississant à base de savon de lithium, lequel épaississant peut être un sel de lithium simple ou un sel de lithium complexe, en combinaison avec: (1) un complexe organomolybdique capable de fonctionner comme additif réduisant la friction; (2) un composé antiusure/antioxydant; (3) un additif organosoufré pour améliorer la résistance aux pressions extrêmes; et (4) un additif organophosphoré pour améliorer la résistance aux pressions extrêmes. Il a été trouvé qu'une graisse de cette formule présente une combinaison inattendue de caractéristiques de faible friction et d'usure réduite lorsqu'elle est utilisée dans des joints soumis à une vitesse constante.
PCT/GB1993/002313 1992-11-14 1993-11-10 Graisses WO1994011470A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
GB9508436A GB2287715B (en) 1992-11-14 1993-11-10 Greases
EP93924736A EP0668900B2 (fr) 1992-11-14 1993-11-10 Graisses
DE69321481T DE69321481T3 (de) 1992-11-14 1993-11-10 Schmierfetter

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB929223945A GB9223945D0 (en) 1992-11-14 1992-11-14 Greases
GB9223945.8 1992-11-14

Publications (1)

Publication Number Publication Date
WO1994011470A1 true WO1994011470A1 (fr) 1994-05-26

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PCT/GB1993/002313 WO1994011470A1 (fr) 1992-11-14 1993-11-10 Graisses

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EP (1) EP0668900B2 (fr)
DE (1) DE69321481T3 (fr)
GB (2) GB9223945D0 (fr)
WO (1) WO1994011470A1 (fr)

Cited By (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1995007966A1 (fr) * 1993-09-13 1995-03-23 Exxon Research And Engineering Company Composition lubrifiante contenant une combinaison d'additifs anti-usure et d'additifs anti-oxydants
WO1996002615A1 (fr) * 1994-07-15 1996-02-01 Kyodo Yushi Co., Ltd. Composition de graisse pour joints homocinetiques
EP0708172A2 (fr) * 1994-10-21 1996-04-24 Kyodo Yushi Co., Ltd. Composition de graisse pour joint homocinétique
WO1996037585A1 (fr) * 1995-05-26 1996-11-28 The Lubrizol Corporation Lubrifiants comprenant des compositions contenant du molybdene et leurs procedes d'utilisation
US5585335A (en) * 1996-03-12 1996-12-17 Exxon Research And Engineering Company Imide and pyrrolidone grease thickeners with terephthalate complexing agent
US5604187A (en) * 1996-03-22 1997-02-18 Kyodo Yushi Co., Ltd. Grease composition for constant velocity joints
US5607906A (en) * 1995-11-13 1997-03-04 Kyodo Yushi Co., Ltd. Grease composition for constant velocity joints
EP0767237A1 (fr) * 1995-10-05 1997-04-09 Nippon Oil Co. Ltd. Composition de graisse pour joint homocinétique
DE19547734C1 (de) * 1995-10-11 1997-07-03 Hyundai Motor Co Ltd Schmiermittel für unter konstanter Geschwindigkeit stehende Verbindungsstellen
FR2761372A1 (fr) * 1997-03-31 1998-10-02 Kyodo Yushi Composition de graisse pour joints a vitesse constante
EP0885949A1 (fr) * 1997-06-20 1998-12-23 FUCHS DEA Schmierstoff GmbH & Co. KG Composition de graisse pour arbre articulé de transmission ne nécessitant pas d'entretien
FR2765886A1 (fr) * 1997-07-08 1999-01-15 Gkn Automotive Ag Graisse pour joint homocinetique
WO1999014292A1 (fr) * 1997-09-12 1999-03-25 Shell Internationale Research Maatschappij B.V. Compositions lubrifiantes
EP0911382A1 (fr) * 1997-10-21 1999-04-28 Nippon Oil Co. Ltd. Composition de graisse pour palier à roulement
WO1999042544A1 (fr) * 1998-02-19 1999-08-26 Vedatech Ltd. Graisse a temperature moyenne pour ensembles a friction a forte charge
EP0958338A1 (fr) * 1996-09-11 1999-11-24 Exxon Research And Engineering Company Graisse a complexe lithium presentant une duree de lubrification prolongee
US6037314A (en) * 1996-06-07 2000-03-14 Kyodo Yushi Co., Ltd. Grease composition for constant velocity joints
WO2000055284A1 (fr) * 1999-03-15 2000-09-21 Shell Internationale Research Maatschappij B.V. Composition de graisse pour joints homocinetiques
WO2001064821A2 (fr) * 2000-02-29 2001-09-07 Shell Internationale Research Maatschappij B.V. Composition de graisse pour joints homocinetiques
US6319880B1 (en) 1999-06-29 2001-11-20 Kyodo Yushi Co., Ltd. Grease composition for constant velocity joint
US6355602B1 (en) 1999-06-29 2002-03-12 Kyodo Yushi Co., Ltd. Grease composition for constant velocity joint
EP1559771A1 (fr) * 2002-07-24 2005-08-03 Nippon Oil Corporation Composition de graisse
EP2154229A3 (fr) * 2008-07-25 2011-09-07 Fuchs Petrolub AG Graisses complexes de calcium/lithium, joints de transmission homocinétiques encapsulés comprenant de telles graisses de lubrification, leur utilisation et leur procédé de fabrication

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GB2346892B (en) * 1999-02-16 2002-10-09 Gkn Technology Ltd Grease for constant velocity joints

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EP0423724A1 (fr) * 1989-10-16 1991-04-24 Shin-Etsu Chemical Co., Ltd. Composition de graisse à base de silicone
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EP0508115A1 (fr) * 1991-03-07 1992-10-14 Nippon Oil Co. Ltd. Composition de graisse pour joint homocinétique
FR2674534A1 (fr) * 1991-04-01 1992-10-02 Ntn Toyo Bearing Co Ltd Composition de graisse pour joints homocinetiques.
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Cited By (37)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1995007966A1 (fr) * 1993-09-13 1995-03-23 Exxon Research And Engineering Company Composition lubrifiante contenant une combinaison d'additifs anti-usure et d'additifs anti-oxydants
WO1996002615A1 (fr) * 1994-07-15 1996-02-01 Kyodo Yushi Co., Ltd. Composition de graisse pour joints homocinetiques
US5516439A (en) * 1994-07-15 1996-05-14 Kyodo Yushi Co., Ltd. Grease composition for constant velocity joints
EP0708172A2 (fr) * 1994-10-21 1996-04-24 Kyodo Yushi Co., Ltd. Composition de graisse pour joint homocinétique
EP0708172A3 (fr) * 1994-10-21 1997-04-09 Kyodo Yushi Composition de graisse pour joint homocinétique
US5672571A (en) * 1994-10-21 1997-09-30 Kyodo Yushi Co., Ltd. Grease composition for constant velocity joints
WO1996037585A1 (fr) * 1995-05-26 1996-11-28 The Lubrizol Corporation Lubrifiants comprenant des compositions contenant du molybdene et leurs procedes d'utilisation
AU724613B2 (en) * 1995-05-26 2000-09-28 Elf Antar France Lubricants with molybdenum containing compositions and methods of using the same
EP0767237A1 (fr) * 1995-10-05 1997-04-09 Nippon Oil Co. Ltd. Composition de graisse pour joint homocinétique
DE19547734C1 (de) * 1995-10-11 1997-07-03 Hyundai Motor Co Ltd Schmiermittel für unter konstanter Geschwindigkeit stehende Verbindungsstellen
US5607906A (en) * 1995-11-13 1997-03-04 Kyodo Yushi Co., Ltd. Grease composition for constant velocity joints
US5585335A (en) * 1996-03-12 1996-12-17 Exxon Research And Engineering Company Imide and pyrrolidone grease thickeners with terephthalate complexing agent
US5604187A (en) * 1996-03-22 1997-02-18 Kyodo Yushi Co., Ltd. Grease composition for constant velocity joints
US6037314A (en) * 1996-06-07 2000-03-14 Kyodo Yushi Co., Ltd. Grease composition for constant velocity joints
EP0958338A1 (fr) * 1996-09-11 1999-11-24 Exxon Research And Engineering Company Graisse a complexe lithium presentant une duree de lubrification prolongee
EP0958338A4 (fr) * 1996-09-11 2000-09-27 Exxon Research Engineering Co Graisse a complexe lithium presentant une duree de lubrification prolongee
FR2761372A1 (fr) * 1997-03-31 1998-10-02 Kyodo Yushi Composition de graisse pour joints a vitesse constante
US5952273A (en) * 1997-03-31 1999-09-14 Kyodo Yushi Co., Ltd, Grease composition for constant velocity joints
EP0885949A1 (fr) * 1997-06-20 1998-12-23 FUCHS DEA Schmierstoff GmbH & Co. KG Composition de graisse pour arbre articulé de transmission ne nécessitant pas d'entretien
US6541427B1 (en) 1997-06-20 2003-04-01 Fuchs Europe Schmierstoffe Gmbh & Co. Kg Lubricant for maintenance-free cardan shafts
FR2765886A1 (fr) * 1997-07-08 1999-01-15 Gkn Automotive Ag Graisse pour joint homocinetique
WO1999002629A1 (fr) * 1997-07-08 1999-01-21 Gkn Automotive Ag Graisse pour joints homocinetiques
WO1999014292A1 (fr) * 1997-09-12 1999-03-25 Shell Internationale Research Maatschappij B.V. Compositions lubrifiantes
EP0911382A1 (fr) * 1997-10-21 1999-04-28 Nippon Oil Co. Ltd. Composition de graisse pour palier à roulement
WO1999042544A1 (fr) * 1998-02-19 1999-08-26 Vedatech Ltd. Graisse a temperature moyenne pour ensembles a friction a forte charge
US6403538B1 (en) 1999-03-15 2002-06-11 Shell Oil Company Grease composition for constant velocity joints
WO2000055284A1 (fr) * 1999-03-15 2000-09-21 Shell Internationale Research Maatschappij B.V. Composition de graisse pour joints homocinetiques
US6319880B1 (en) 1999-06-29 2001-11-20 Kyodo Yushi Co., Ltd. Grease composition for constant velocity joint
US6355602B1 (en) 1999-06-29 2002-03-12 Kyodo Yushi Co., Ltd. Grease composition for constant velocity joint
WO2001064821A2 (fr) * 2000-02-29 2001-09-07 Shell Internationale Research Maatschappij B.V. Composition de graisse pour joints homocinetiques
WO2001064821A3 (fr) * 2000-02-29 2002-04-18 Shell Int Research Composition de graisse pour joints homocinetiques
AU2001244178B2 (en) * 2000-02-29 2004-06-17 Shell Internationale Research Maatschappij B.V. Grease composition for constant velocity joints
US6894009B2 (en) 2000-02-29 2005-05-17 Shell Oil Company Grease composition for constant velocity joints
EP1559771A1 (fr) * 2002-07-24 2005-08-03 Nippon Oil Corporation Composition de graisse
EP1559771A4 (fr) * 2002-07-24 2007-02-14 Nippon Oil Corp Composition de graisse
EP2154229A3 (fr) * 2008-07-25 2011-09-07 Fuchs Petrolub AG Graisses complexes de calcium/lithium, joints de transmission homocinétiques encapsulés comprenant de telles graisses de lubrification, leur utilisation et leur procédé de fabrication
US8603958B2 (en) 2008-07-25 2013-12-10 Fuchs Petrolub Ag Calcium/lithium complex greases and encapsulated constant velocity joint containing the grease and method for their production

Also Published As

Publication number Publication date
DE69321481T3 (de) 2002-09-05
EP0668900A1 (fr) 1995-08-30
EP0668900B2 (fr) 2002-05-29
GB2287715A (en) 1995-09-27
DE69321481D1 (de) 1998-11-12
GB2287715B (en) 1996-08-21
GB9223945D0 (en) 1993-01-06
DE69321481T2 (de) 1999-05-27
EP0668900B1 (fr) 1998-10-07
GB9508436D0 (en) 1995-06-14

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