EP0668900A1 - Greases - Google Patents
GreasesInfo
- Publication number
- EP0668900A1 EP0668900A1 EP93924736A EP93924736A EP0668900A1 EP 0668900 A1 EP0668900 A1 EP 0668900A1 EP 93924736 A EP93924736 A EP 93924736A EP 93924736 A EP93924736 A EP 93924736A EP 0668900 A1 EP0668900 A1 EP 0668900A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- grease
- organo
- grease according
- alkyl
- compound comprises
- 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.)
- Granted
Links
Classifications
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- C—CHEMISTRY; METALLURGY
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- 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
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- C10M117/00—Lubricating compositions characterised by the thickener being a non-macromolecular carboxylic acid or salt thereof
- C10M117/02—Lubricating compositions characterised by the thickener being a non-macromolecular carboxylic acid or salt thereof having only one carboxyl group bound to an acyclic carbon atom, cycloaliphatic carbon atom or hydrogen
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- C10M117/00—Lubricating compositions characterised by the thickener being a non-macromolecular carboxylic acid or salt thereof
- C10M117/02—Lubricating compositions characterised by the thickener being a non-macromolecular carboxylic acid or salt thereof having only one carboxyl group bound to an acyclic carbon atom, cycloaliphatic carbon atom or hydrogen
- C10M117/04—Lubricating compositions characterised by the thickener being a non-macromolecular carboxylic acid or salt thereof having only one carboxyl group bound to an acyclic carbon atom, cycloaliphatic carbon atom or hydrogen containing hydroxy groups
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- C10M135/06—Esters, e.g. fats
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- C10M2219/102—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring containing sulfur and carbon only in the ring
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- C10M2223/065—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having phosphorus-to-carbon bonds containing sulfur
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- C10M2223/10—Phosphatides, e.g. lecithin, cephalin
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- C10M2227/09—Complexes with metals
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- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
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- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
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- C10N2040/30—Refrigerators lubricants or compressors lubricants
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- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
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- C10N2040/32—Wires, ropes or cables lubricants
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
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- C10N2040/34—Lubricating-sealants
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- C10N2040/36—Release agents or mold release agents
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- C10N2040/38—Conveyors or chain belts
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- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/40—Generators or electric motors in oil or gas winning field
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- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/42—Flashing oils or marking oils
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- C10N2040/44—Super vacuum or supercritical use
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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.
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Lubricants (AREA)
Abstract
Description
Claims
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB9223945 | 1992-11-14 | ||
GB929223945A GB9223945D0 (en) | 1992-11-14 | 1992-11-14 | Greases |
PCT/GB1993/002313 WO1994011470A1 (en) | 1992-11-14 | 1993-11-10 | Greases |
Publications (3)
Publication Number | Publication Date |
---|---|
EP0668900A1 true EP0668900A1 (en) | 1995-08-30 |
EP0668900B1 EP0668900B1 (en) | 1998-10-07 |
EP0668900B2 EP0668900B2 (en) | 2002-05-29 |
Family
ID=10725130
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP93924736A Expired - Lifetime EP0668900B2 (en) | 1992-11-14 | 1993-11-10 | Greases |
Country Status (4)
Country | Link |
---|---|
EP (1) | EP0668900B2 (en) |
DE (1) | DE69321481T3 (en) |
GB (2) | GB9223945D0 (en) |
WO (1) | WO1994011470A1 (en) |
Families Citing this family (24)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB9318928D0 (en) * | 1993-09-13 | 1993-10-27 | Exxon Research Engineering Co | Lubricant composition containing combination of antiwear and antioxidant additives |
EP0719316B1 (en) * | 1994-07-15 | 1999-12-22 | Kyodo Yushi Co., Ltd. | Grease composition for constant velocity joints |
JP3320569B2 (en) * | 1994-10-21 | 2002-09-03 | 協同油脂株式会社 | Grease composition for constant velocity joints |
CA2222043A1 (en) * | 1995-05-26 | 1996-11-28 | Elf Antar France | Lubricants with molybdenum containing compositions and methods of using the same |
JP3670361B2 (en) * | 1995-10-05 | 2005-07-13 | 新日本石油株式会社 | Grease composition for constant velocity joints |
KR970021265A (en) * | 1995-10-11 | 1997-05-28 | 전성원 | Grease for Constant Velocity Joint |
EP0773280B1 (en) * | 1995-11-13 | 2002-10-09 | 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 |
JP3988895B2 (en) * | 1996-03-22 | 2007-10-10 | 協同油脂株式会社 | Grease composition for constant velocity joints |
JP3988897B2 (en) * | 1996-06-07 | 2007-10-10 | 協同油脂株式会社 | Grease composition for constant velocity joints |
US5731274A (en) * | 1996-09-11 | 1998-03-24 | Exxon Research And Engineering Company | Lithium complex grease with extended lubrication life |
TW374797B (en) * | 1997-03-31 | 1999-11-21 | Kyodo Yushi | Grease composition for constant velocity joints |
EP0885949B1 (en) * | 1997-06-20 | 2000-08-09 | FUCHS DEA Schmierstoff GmbH & Co. KG | Use of a grease composition for maintenance-free articulated transmission shaft |
GB9714292D0 (en) * | 1997-07-08 | 1997-09-10 | Gkn Technology Ltd | Grease for constant-velocity joints |
ZA988282B (en) * | 1997-09-12 | 1999-03-09 | Shell Int Research | Lubricating compositions |
JP3808609B2 (en) * | 1997-10-21 | 2006-08-16 | 新日本石油株式会社 | Grease composition for rolling bearings |
WO1999042544A1 (en) * | 1998-02-19 | 1999-08-26 | Vedatech Ltd. | Middle-temperature grease for high-loaded friction assemblies |
GB2346892B (en) * | 1999-02-16 | 2002-10-09 | Gkn Technology Ltd | Grease for constant velocity joints |
EP1169421B1 (en) * | 1999-03-15 | 2003-01-08 | Shell Internationale Researchmaatschappij B.V. | Grease composition for constant velocity joints |
JP4524007B2 (en) | 1999-06-29 | 2010-08-11 | 協同油脂株式会社 | Grease composition for constant velocity joints |
JP4248688B2 (en) | 1999-06-29 | 2009-04-02 | 協同油脂株式会社 | Grease composition for constant velocity joints |
AU4417801A (en) | 2000-02-29 | 2001-09-12 | Shell Int Research | Grease composition for constant velocity joints |
JP2004059604A (en) * | 2002-07-24 | 2004-02-26 | Nippon Oil Corp | Grease composition |
DE102008034959A1 (en) | 2008-07-25 | 2010-01-28 | Fuchs Petrolub Ag | Calcium / lithium complex fats and encapsulated constant velocity joint containing these and their application |
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US4536308A (en) * | 1984-10-01 | 1985-08-20 | Texaco Inc. | Lithium soap grease additive |
JPS6346299A (en) * | 1986-01-16 | 1988-02-27 | Ntn Toyo Bearing Co Ltd | Grease for constant speed joint |
JPS62207397A (en) * | 1986-03-06 | 1987-09-11 | Kyodo Yushi Kk | Extreme-pressure grease composition |
US4842752A (en) * | 1988-03-22 | 1989-06-27 | Conoco Inc. | Stable extreme pressure grease |
JPH0742472B2 (en) * | 1989-10-16 | 1995-05-10 | 信越化学工業株式会社 | Silicone grease composition |
GB2241707A (en) * | 1990-03-07 | 1991-09-11 | Exxon Research Engineering Co | Lubricating grease composition |
JP2799634B2 (en) * | 1991-03-07 | 1998-09-21 | 日本石油株式会社 | Grease composition for constant velocity joints |
JP2915611B2 (en) * | 1991-04-01 | 1999-07-05 | 協同油脂株式会社 | Grease composition for constant velocity joints |
JP2989311B2 (en) * | 1991-04-30 | 1999-12-13 | 協同油脂株式会社 | Grease composition for constant velocity joints |
-
1992
- 1992-11-14 GB GB929223945A patent/GB9223945D0/en active Pending
-
1993
- 1993-11-10 DE DE69321481T patent/DE69321481T3/en not_active Expired - Lifetime
- 1993-11-10 GB GB9508436A patent/GB2287715B/en not_active Expired - Lifetime
- 1993-11-10 WO PCT/GB1993/002313 patent/WO1994011470A1/en active IP Right Grant
- 1993-11-10 EP EP93924736A patent/EP0668900B2/en not_active Expired - Lifetime
Non-Patent Citations (1)
Title |
---|
See references of WO9411470A1 * |
Also Published As
Publication number | Publication date |
---|---|
DE69321481T2 (en) | 1999-05-27 |
GB2287715A (en) | 1995-09-27 |
EP0668900B2 (en) | 2002-05-29 |
WO1994011470A1 (en) | 1994-05-26 |
GB9223945D0 (en) | 1993-01-06 |
DE69321481D1 (en) | 1998-11-12 |
GB2287715B (en) | 1996-08-21 |
GB9508436D0 (en) | 1995-06-14 |
EP0668900B1 (en) | 1998-10-07 |
DE69321481T3 (en) | 2002-09-05 |
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