EP0450208B1 - Schmiermittelzusammensetzungen und Additive dafür - Google Patents
Schmiermittelzusammensetzungen und Additive dafür Download PDFInfo
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- EP0450208B1 EP0450208B1 EP90303536A EP90303536A EP0450208B1 EP 0450208 B1 EP0450208 B1 EP 0450208B1 EP 90303536 A EP90303536 A EP 90303536A EP 90303536 A EP90303536 A EP 90303536A EP 0450208 B1 EP0450208 B1 EP 0450208B1
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- European Patent Office
- Prior art keywords
- sulphur
- component
- acid
- iii
- lubricant
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- 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
- C10M159/00—Lubricating compositions characterised by the additive being of unknown or incompletely defined constitution
- C10M159/12—Reaction products
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- 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
- C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
- C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
- C10M129/26—Carboxylic acids; Salts thereof
- C10M129/28—Carboxylic acids; Salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
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- 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
- C10M133/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen
- C10M133/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of less than 30 atoms
- C10M133/04—Amines, e.g. polyalkylene polyamines; Quaternary amines
- C10M133/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms
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- 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
- C10M135/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
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- 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
- C10M135/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
- C10M135/02—Sulfurised compounds
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- 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
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/10—Carboxylix acids; Neutral salts thereof
- C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
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- 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
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/10—Carboxylix acids; Neutral salts thereof
- C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
- C10M2207/125—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/10—Carboxylix acids; Neutral salts thereof
- C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
- C10M2207/129—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of thirty or more carbon atoms
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- 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
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
- C10M2215/04—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
- C10M2215/04—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms
- C10M2215/044—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms having cycloaliphatic groups
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/26—Amines
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2217/04—Macromolecular compounds from nitrogen-containing monomers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2217/046—Polyamines, i.e. macromoleculars obtained by condensation of more than eleven amine monomers
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- 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
- C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2217/06—Macromolecular compounds obtained by functionalisation op polymers with a nitrogen containing compound
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- 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
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/02—Sulfur-containing compounds obtained by sulfurisation with sulfur or sulfur-containing compounds
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- 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
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/02—Sulfur-containing compounds obtained by sulfurisation with sulfur or sulfur-containing compounds
- C10M2219/022—Sulfur-containing compounds obtained by sulfurisation with sulfur or sulfur-containing compounds of hydrocarbons, e.g. olefines
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- 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
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/02—Sulfur-containing compounds obtained by sulfurisation with sulfur or sulfur-containing compounds
- C10M2219/024—Sulfur-containing compounds obtained by sulfurisation with sulfur or sulfur-containing compounds of esters, e.g. fats
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- 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
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
- C10M2219/082—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
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- 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
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
- C10M2219/082—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
- C10M2219/086—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing sulfur atoms bound to carbon atoms of six-membered aromatic rings
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- 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
- C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
- C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
- C10M2223/04—Phosphate esters
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- 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
- C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
- C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
- C10M2223/04—Phosphate esters
- C10M2223/042—Metal salts thereof
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- 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
- C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
- C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
- C10M2223/04—Phosphate esters
- C10M2223/043—Ammonium or amine salts thereof
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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- C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
- C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
- C10M2223/04—Phosphate esters
- C10M2223/047—Thioderivatives not containing metallic elements
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- C10M2227/00—Organic non-macromolecular compounds containing atoms of elements not provided for in groups C10M2203/00, C10M2207/00, C10M2211/00, C10M2215/00, C10M2219/00 or C10M2223/00 as ingredients in lubricant compositions
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- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/02—Bearings
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- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2070/00—Specific manufacturing methods for lubricant compositions
- C10N2070/02—Concentrating of additives
Definitions
- This invention relates to lubricating fluid compositions, and in particular to gear oils and to additives therefor.
- High performance gear oils usually consist of a major amount of mineral oil or synthetic base stock and a minor amount of suitable additives including in particular a sulphur-containing extreme pressure or antiwear agent.
- a sulphur-containing extreme pressure or antiwear agent such as sodium sulfate, sodium sulfate, sodium sulfate, sodium sulfate, sodium sulfate, sodium sulfate, sodium sulfate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium sulfate, sodium sulfate, sodium sulfate, sodium sulfate, sodium sulfate, sodium sulfate, sodium bicarbonate, sodium sulfate, sodium bicarbonate, sodium sulfate, sodium bicarbonate, sodium sulfate
- Gear oils for example the oils used in the gear boxes and differentials of motor vehicles, and other mechanisms involving metal on metal, for example steel on steel or steel on bronze, acting parts, are required to protect the metal surfaces and particularly the teeth of the gears. Typically, such oils remain in use for long periods without being changed. In addition to providing general lubrication, the fluid protects the loaded metal parts such as the gear teeth from damage. Gear oils are customarily tested for their ability to protect gear teeth from damage such as wear and pitting for long periods. In one system for testing such oils a gear train is run under conditions of variable and very heavy stress until the gears fail.
- this invention provides process for forming a lubricant additive comprising interacting as a temperature above 30°C prior to use as a lubricant (i) one or more highly-active sulphur-containing extreme pressure or antiwear agents, (ii) one or more amines, and (iii) one or more weak acids, such interactions occurring either concurrently or in any sequence.
- the proportions of components (i), (ii) and (iii) used in forming the product can be varied over reasonably wide limits provided there is a sufficiently high amount of amino nitrogen present to interact both with at least a portion of the sulfur-containing material(s) and at least a portion of the weak acid(s) used.
- the proportions of components (i) and (ii) are such that the mole percentages of sulphur in (i) to amino nitrogen in (ii) is in the range of 100:1 to 5:1 (preferably 40:1 to 5:1, and more preferably 25:1 to 5:1, and most preferably 20:1 to 25:1), and the proportion of component (iii) used in forming the product is usually such that there are from 0.2 to 2 chemical equivalents of acid per equivalent of amino nitrogen in component (ii).
- the proportions of component (iii) are such that there are from 0.2 to 0.9 (most preferably 0.4 to 0.8) chemical equivalents of acid per equivalent of amino nitrogen in component (ii).
- these preferred cases involve use of an amount of weak acid which theoretically is insufficient to neutralise all of the amine utilised in the combination.
- a mixture which includes or comprises components (i), (ii) and (iii) is heated to a performance-enhancing temperature, that is, to a temperature at which the resultant product is more effective in the standard planetary spur gear test than it would be in the absence of such heating. While such temperatures may vary from case to case, generally speaking heating to temperatures in the range of 30 to 70°C and preferably in the range of 40 to 70°C and most preferably in the range of 50 to 60°C for periods in the range of 0.5 to 3 hours and preferably in the range of 0.5 to 2 hours are suitable.
- Components (i), (ii) and (iii) may be subjected to such heating when in undiluted form, when dissolved in an oleaginous solvent (preferably at a concentration above 20% of the total weight of the solution), or when in admixture with other conventional components used in gear oil additive concentrates, such as antioxidants, antifoamants, demulsification agents, dispersants, detergents, viscosity index improvers or pour point depressants, and inert diluents.
- gear oil additive concentrates such as antioxidants, antifoamants, demulsification agents, dispersants, detergents, viscosity index improvers or pour point depressants, and inert diluents.
- the reactant mixture may be heated at any temperature above 30°C for any length of time which together yield a product that is more effective in the planetary spur gear test than the initial unheated mixture from which the product was made.
- the heating of the mixture of components (i), (ii) and (iii) is conducted in the presence of an ester of a pentavalent acid of phosphorus, such as the fully esterified or partially esterified phosphoric, phosphonic or pyrophosphoric acids or their sulphur-containing analogs.
- This heating process may be conducted in the presence of one or more compounds of the formula wherein each of R 1 , R 2 and R 3 is, independently, a hydrocarbyl group or a hydrogen atom, provided that at least one of R 1 , R 2 and R 3 is hydrocarbyl, and each X is, independently, an oxygen atom or a sulphur atom.
- R 1 , R 2 and R 3 are saturated or substantially saturated aliphatic, cycloaliphatic or polycycloaliphatic groups, such as alkyl, alkenyl, cycloalkyl, cycloalkenyl, cycloalkylalkyl, cycloalkylalkenyl, cycloalkenylalkyl, cycloalkenylalkenyl, and the like.
- hydrocarbyl groups are such that the compound is soluble in the base oil to at least the desired use concentration at ambient temperatures.
- the hydrocarbyl groups can contain functional substituents or non-hydrocarbon component groups which do not materially alter the predominantly hydro-carboneous character of the hydrocarbyl groups themselves.
- a sulphur-containing extreme pressure or antiwear agent is or is not "active"
- use can be made of a copper coupon corrosion test which is conducted as follows: A copper coupon approximately 70 x 15 mm and about 1.25 mm in thickness is cleaned by use of steel wool (0000 grade), washed with heptane, and then with acetone, dried, and weighed to the nearest 0.1 mg. The cleaned coupon is placed in a test tube and covered completely with the composition to be tested, and the system is heated to 125°C, by means of an oil bath maintained at this temperature. After holding the system at 125°C for three hours, the copper coupon is removed from the test tube, rinsed with heptane and then with acetone.
- the dried coupon is then rubbed with a paper towel moistened with acetone to remove any surface flakes formed by copper corrosion.
- the coupon is then air-dried and weighed to the nearest 0.1 mg.
- the difference in weight as between the initial copper coupon and the coupon after the test represents the extent to which the copper was corroded under the test conditions. Therefore the larger the weight difference, the greater the copper corrosion, and thus the more active the sulphur compound.
- the sulphur-containing agent is considered “active".
- a sulphur-containing extreme pressure or antiwear agent is deemed to be “highly-active” if the coupon weight loss in the above test is above 50 milligrams, and use of such "highly-active" sulphur-containing substances in forming the products of this invention is preferred.
- active as used in this specification and in the claims encompasses “highly active” as well.
- sulphur-containing compounds which possess a linkage of two sulphur atoms (i.e., -S-S-) or four or more sulphur atoms (e.g., -S-S-S-S-, -S-S-S-S-S-, etc.) tend to be "active” or even "highly active” in the sense used herein.
- a product from one manufacturer for example sulphurised isobutene -- may have a much higher activity than a similar product from another manufacturer.
- the amino nitrogen of any amine salt or amine complex with phosphorus acids such as dialkyl acid phosphates or phosphites is too tightly bound to be available for participation in the formation of the products of this invention, and thus although such amine salts or complexes may be present during the formation of the products of this invention, the amount of amino nitrogen in such amine salts or complexes should not be considered as amino nitrogen available for use in the formation of the products of this invention.
- such tightly-bound amine salts or complexes with phosphorus acids form no part of component (ii).
- an active sulphur-containing extreme pressure or antiwear agent that yields less than 700 ppm, more preferably less than 500 ppm, of vapour space H 2 S when heated by itself for one week at 65°C.
- the heating process involving at least components (i), (ii) and (iii)
- the performance of products made in a two-stage process tends to be even better than the performance exhibited by corresponding products made in a one stage operation.
- the product is produced by heating components (i) and (ii) in the first stage and then in the second stage heating component (iii) with the product formed from components (i) and (ii).
- the one-stage process of this invention involves heating components (i), (ii) and (iii) in the desired proportions all at the same time, or concurrently feeding all three components to the heated reaction in the desired proportions, either continuously or in incremental portions. Consequently, the reaction among components (i), (ii) and (iii) can be conducted in any sequence and in any number of reaction stages, although for the reasons already described, a two-stage process is preferred.
- the present invention accordingly further provides a lubricant composition containing a minor amount, for example 1 to 20% by weight, of a product resulting from interaction either concurrently or in any sequence at a suitably elevated temperature of (i) one or more active sulphur-containing extreme pressure or antiwear agents, (ii) one or more amines, and (iii) one or more weak acids, the proportions of components (i), (ii) and (iii) and the reaction conditions used in forming in the final product being as above-stated.
- additive concentrates containing from 10 to 90% by weight (preferably from 20 to 80% by weight) of a pre-heated combination or product of this invention formed as described above.
- Particularly preferred lubricants are those which contain a product formed from components (i), (ii) and (iii) in accordance with this invention and wherein the product and the concentration thereof enable the lubricant to give at least 60 and more preferably at least 75 hours of running time in the planetary spur gear test (in the form referred to hereinafter) before a substantial increase in iron content in the oil (an increase which usually occurs relatively rapidly) is observed or before gear tooth breakage occurs.
- the lubricant may be a mineral oil, a synthetic oil, a natural oil such as a vegetable oil, or a mixture thereof, e.g. a mixture of a mineral oil and a synthetic oil.
- Suitable mineral oils include those of appropriate viscosity refined from crude oil of any source including Gulf Coast, Midcontinent, Pennsylvania, California, Alaska, Middle East, North Sea and the like. Standard refinery operations may be used in processing the mineral oil.
- Synthetic oils include both hydrocarbon synthetic oils and synthetic esters.
- Useful synthetic hydrocarbon oils include liquid alpha-olefin polymers of appropriate viscosity.
- hydrogenated or unhydrogenated liquid oligomers of C 6 -C 16 alpha-olefins such as hydrogenated or unhydrogenated alpha-decene trimer.
- Alkyl benzenes of appropriate viscosity e.g. didodecylbenzene, can also be used.
- Useful synthetic esters include the esters of monocarboxylic and polycarboxylic acids with monohydroxy alcohols and polyols. Typical examples are didodecyl adipate, trimethylolpropane tripelargonate, pentaerythritol tetracaproate, di(2-ethylhexyl) adipate, and dilauryl sebacate.
- Complex esters made from mixtures of mono- and di-carboxylic acids and mono- and/or polyhydric alkanols can also be used.
- Typical natural oils that may be used include castor oil, olive oil, peanut oil, rape oil, corn oil, sesame oil, cottonseed oil, soybean oil, sunflower oil, safflower oil, hemp oil, linseed oil, tung oil, oiticica oil, jojoba oil, and the like. Such oils may be partially or fully hydrogenated, if desired. Viscosity index improvers may or may not be included in the natural oils in order to achieve the viscosity properties deemed necessary or desirable.
- the additives or additive concentrates of this invention can be blended into any such lubricant base stocks when forming the finished lubricants of this invention.
- the base oils for such use are generally mineral oil base stocks such as for example conventional and solvent-refined paraffinic neutrals and bright stocks, hydrotreated paraffinic neutrals and bright stocks, naphthenic oils, cylinder oils, etc., including straight run and blended oils.
- synthetic base stocks such as for example poly-alpha-olefins with synthetic diesters in weight proportions (PAO:ester) ranging from about 95:5 to about 50:50, typically about 75:25 can be treated.
- PAO:ester poly-alpha-olefins with synthetic diesters in weight proportions
- the product of this invention is also particularly suitable for use in PAO which contains little or no ester.
- the base stocks used in automotive gear oils range in viscosity grades from SAE 50 to 250 and preferably from 70 to 140. Suitable automotive gear oils also include cross-grades such as 75W-140, 80W-90, 85W-140, 85W-90, and the like. In general, the base stocks used in industrial gear oils will have a viscosity in the range of from about ISO grade 32 to ISO grade 680 and preferably from ISO grade 68 to ISO grade 460.
- the new lubricant compositions may be supplied either as finished lubricants ready for use or in the form of an additive package, i.e. a concentrate, which requires dilution with base lubricating fluid before use.
- the lubricant compositions of the invention may contain, in addition to the substances already mentioned, any usual additive for inclusion in such lubricants which is compatible with the product of this invention formed from a highly-active sulphur-containing agent, weak acid, and amine. Examples of such additives are given below.
- a very wide variety of active sulphur-containing oil-soluble extreme pressure or antiwear agents may be used in forming the compositions of the invention, and any known such agents may in principle be used. Examples of such agents are included within the categories of sulphurised olefins, sulphurised esters, sulphurised fatty acids, dialkylpolysulphides, diaryl polysulphides, diar-alkyl polysulphides, sulphur, and sulphurised oils.
- compositions of the invention the sulphur atoms in the active sulphur containing species are bound directly to carbon or to more sulphur.
- One preferred class of such agents is made by reacting an olefin such as isobutene with sulphur.
- the product e.g. sulphurised isobutene
- olefins or saturated hydrocarbons may be used in place of the isobutene.
- the candidate product should be subjected to the coupon corrosion test to ascertain that it qualifies as an "active" compound.
- sulphur-containing extreme pressure agents which, if "active", may be used in the compositions of the invention are sulphur and the sulphurised fatty esters and oils already mentioned, such as sulphurised sperm oil and sulphurised lard oil.
- the proportion of interacted product of this invention included in the lubricant compositions of the invention is typically 1 to 20% by weight, usually 1.7 to 10% by weight, and preferably 2-4%, based on the weight of the lubricant.
- the new compositions preferably contain a phosphorus-containing extreme pressure or anti-wear agent.
- phosphorus-containing agents include derivatives of phosphorus oxyacids, of phosphorus thioacids, of polyphosphorus oxyacids and of polyphosphorus thioacids, such as phosphites; mono-, di- and trithiophosphites; phosphates; mono-, di- and trithiophosphates and their corresponding phosphorothioates; and pyrophosphates and thiophosphates; and especially their oil-soluble esters, acid esters, and amine salts.
- a mono- or dihydrocarbyl phosphite, thiophosphite, phosphate, thiophosphate or thiophosphorothioate or a mixture thereof is used, where the hydrocarbyl groups may be alkyl, alkenyl, phenyl, alkylphenyl or dialkylphenyl.
- esters are monomethyl, dimethyl, mono-n-butyl, di-n-butyl, mono-isobutyl, di-isobutyl, monoamyl, diamyl, di-n-octyl, di-(2-ethyl-n-hexyl), monooleyl, dioleyl, monophenyl, diphenyl and di(dodecylphenyl) phosphite and phosphate, their sulphur analogs, and the amine salts of any of the foregoing.
- Such phosphorus-containing agents are usually included in the new compositions in a proportion of 0.01 to 3.5% based on the weight of the lubricant.
- compositions of the invention may also contain an alkali metal borate, e.g. sodium or potassium borate, e.g. in a proportion of 0.5 to 8% by weight of the lubricant.
- an alkali metal borate e.g. sodium or potassium borate
- the acid used in forming the new compositions is a weak acid, preferably one having a pKa of greater than about 2.0, and is usually a carboxylic acid in which one or more carboxyl groups are attached to a hydrocarbon radical of 1 to 100, preferably 2 to 50 carbon atoms, preferably an acyclic hydrocarbon radical, and most preferably 6 to 36 arbon atoms.
- Other weak acids e.g. a boric acid such as H 3 BO 3 or metaboric acid, may also be used.
- suitable acids are alkanoic and alkenoic mono-, di- or polycarboxylic acids of 1 to 100, preferably 2 to 54, carbon atoms, e.g.
- acetic acid n-octanoic acid, decanoic acid, myristic acid, oleic acid, linolenic acid, tetrapropenylsuccinic acid, azelaic acid or dimerised or trimerised linoleic acid.
- the acid used must be such as to form an oil-soluble salt with the amine used in forming the products of this invention.
- the most preferred acids are acyclic monocarboxylic acids in which the hydrocarbon group is a primary hydrocarbon group which is either saturated or mono- or polyethylenically unsaturated and contains from 12 to 36 carbon atoms.
- Such preferred acids include lauric acid, palmitic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, eleostearic acid, licanic acid, ricinoleic acid, palmitoleic acid, petroselenic acid, vaccenic acid, and erucic acid, among others.
- amines are aliphatic mono- and polyamines containing 2 to 40 carbon atoms per molecule.
- Primary, secondary and tertiary amines are suitable and these are preferably linear or branched aliphatic, cycloaliphatic or ethylenically unsaturated aliphatic amines of 6 to 22 carbon atoms, e.g. n-octylamine, oleylamine, cyclohexylamine, polyethylene polyamines such as triethylene tetramine, and the tertiary alkyl primary amines sold under the trade name Primene 81-R and Primene JM-T.
- the amine must be capable of forming an oil-soluble salt with the acid used.
- the most preferred amines are acyclic primary monoamines in which the hydrocarbon group is a primary hydrocarbon group which is either saturated or mono- or polyethylenically unsaturated and contains from 8 to 22 carbon atoms. Examples of such preferred amines include n-octylamine, n-nonylamine, n-decylamine, n-dodecylamine, n-tetradecylamine, n-pentadecylamine, n-octadecylamine and oleylamine, among others.
- an aminoacid may be used in an amount satisfying the proportions of amine and weak acid specified hereinabove. Suitable amino-acids include glycine, alanine, and phenylalanine. Similarly, one or more amino-acids may be used in combination with (i) one or more amino-free weak acids, (ii) one or more non-carboxylic amines, or (iii) one or more amino-free weak acids and one or more non-carboxylic amines.
- One measure for determining that the correct proportion of amine and acid have been used in forming the new products of this invention is a determination of the pH of the reaction product. Since the product compositions consist essentially of a solution of various organic compounds usually in an oil which is usually a hydrocarbon oil, the compositions have, in a strict sense, no pH. However, it has been found that if a sample of the product is diluted in a mixture of methanol and toluene and then assayed with a conventional pH probe as used in aqueous systems, a measurement is obtained with provides a useful measure of the relative proportions of basic and acidic materials present in the composition. Measured in this way, the pH of the compositions of the invention should be in the range of 3 to 10 or preferably of 7 to 9.
- compositions of the invention may contain other additives suitable for use in gear oils, for example:
- Zinc dihydrocarbyldithiophosphates such as zinc dialkyldithiophosphates, zinc dicycloalkyldithiophosphates and zinc diaryldithiophosphates; hindered phenols; amines and various organic compounds containing nitrogen, sulphur or phosphorus.
- Silicone-based fluids ethylene glycol-propylene glycol condensation products, alkylpolyacrylates.
- Polyalkenyl succinimides, succinate esters, N-vinylpyrrolidone-methacrylate ester copolymers, fatty acid esters and fatty acid amides, and carboxylic acid derivative compositions e.g., succinimides, succinic acid esters, succinic acid ester-amides, etc.
- carboxylic acid derivative compositions e.g., succinimides, succinic acid esters, succinic acid ester-amides, etc.
- one or more post-treating reagents such as boron oxide, boron oxide hydrate, boron halides, boron acids, esters of boron acids, carbon disulphide, hydrogen sulphide, sulphur, sulphur chloride, alkenyl cyanides, carboxylic acid acylating agents (e.g., maleic anhydride, maleic acid, fumaric acid, malic acid, azelaic acid, adipic acid, C1
- Alkylpolymethacrylates or olefin copolymers Alkylpolymethacrylates or olefin copolymers.
- Olefin polymers grafted with a nitrogen-containing moiety such as described in U.S. Pat. No. 4,519,929
- the invention includes within its scope lubricant additive concentrates comprising 5 to 95% of (a) one or more products formed by interacting (i) at least one highly-active sulphur-containing extreme pressure or anti-wear agent, (ii) at least one amine, and (iii) at least one weak acid, and 95 to 5% of (b) a diluent oil, the said percentages being by weight based on the total weight of the concentrate.
- Such concentrates may also contain 1 to 50% of one or more phosphorus-containing extreme pressure or anti-wear agents.
- this oil blend contains approximately 12.1 mole % sulphur per mole % of amino nitrogen, and approximately 0.77 chemical equivalents of weak acid per equivalent of amino nitrogen.
- a gear oil additive concentrate of this invention is formed by heating at 50°C for one hour a mixture of sulphurised isobutylene, trihydrocarbyl ester of dithiophosphoric acid, octyl amine, bis-2-ethylhexylphosphate, oleylamine, alkyl acid phosphite, a friction modifier and a succinimide type dispersant.
- oleic acid, antifoam agent, and process oil are added to the hot mixture produced in the first stage.
- the resultant concentrate is then allowed to cool to about 35° when metal deactivator is added.
- the resultant concentrate contains (apart from amine tied up with phosphorus acids) approximately 21 mole % of sulphur per mole of amino nitrogen and approximately 0.56 chemical equivalent of weak acid (oleic acid) per equivalent of amino nitrogen.
- a gear oil is formed by blending this additive concentrate to a level of 6.5% w/w in an SAE 90 base oil (equivalent to a concentration of 2.27 weight % of sulphurised isobutylene).
- An oil formulated in this manner gave trouble-free performance of over 100 hours in the planetary spur gear test.
- the lubricating fluid is circulated around the system by a pump and is maintained at between 95°C and 130°C. Samples of the lubricating fluid are removed periodically and analysed for iron content. The test is terminated when excessive wear is recorded either by high iron levels in the oil, or by gear tooth breakage.
- a mixture is formed from sulphurized isobutylene, oleylamine, octanoic acid, trihydrocarbyl dithiophosphate, a succinimide dispersant and a friction modifier in weight proportions of approximately 11.7:2.8:0.7:5.5:1:1 respectively.
- This mixture is heated at 60°C for one hour.
- octylamine, bis-2-ethylhexyl phosphate, an amine salt of a dihydrocarbyl thiophosphate and antifoam agent in weight proportions of approximately 0.2:0.4:3.3:0.2, respectively.
- the resultant concentrate contains approximately 35% of the initial sulphurized isobutylene and approximately 18.3% of the mineral oil diluent.
- the additive concentrate contains approximately 18 mole % of sulphur per mole of amino nitrogen and approximately 0.6 equivalent of weak acid per equivalent of amino nitrogen.
- An SAE 90 base oil containing 6.5% of this additive concentrate gives over 90 hours of trouble-free performance in the planetary spur gear test.
- Example 3 The procedure of Example 3 is repeated with the following modifications: the bis-2-ethylhexyl phosphate, the octylamine and the antifoam agent are included in the first stage, the oleyl amine, the dispersant and the friction modifier are introduced into the second stage reaction mixture, and the second stage reaction mixture is held at 50°C for 30 minutes.
- An SAE 90 mineral oil containing 6.5% w/w of this additive concentrate exhibited a period of over 60 hours of satisfactory performance in the planetary spur gear test.
- Example 4 The procedure of Example 4 is repeated except that the first stage reaction mixture is heated to 50°C for 20 minutes and the second stage reaction mixture is held at 50°C for one hour. Similar results are obtained in the planetary spur gear test.
- Example 3 The proceudre of Example 3 is repeated except that the octylamine is added in the first stage reaction, the octanoic acid is added in the second stage reaction mixture, the first stage reaction mixture is maintained at 50°C for one hour, and the amine salt of a dihydrocarbyl thiophosphate is added in a final stage along with the mineral oil and metal deactivator. Satisfactory planetary spur gear performance for 75 hours was achieved using a gear oil containing 6.5% w/w of this additive concentrate.
- Example 3 The procedure of Example 3 is repeated with the following modifications: the octylamine and the trihydrocarbyl dithiophosphate are introduced into the first stage reaction mixture, and the octanoic acid is introduced into the second stage reaction mixture. Performance in excess of 100 hours in the planetary spur gear test was achieved with a lubricating oil containing 6.5% w/w of such an additive concentrate.
- a commercially available gear oil additive formulation was found to be substantially insoluble in PAO (poly-alpha-olefin synthetic lubricating oil). Such a blend formed a very cloudy mixture which partially separated over a period of several days at ambient temperature. In contrast, a blend of the concentrate produced as in Example 2 at GL-5 dosage was found to be fully soluble in the PAO yielding a stable SAE 80W-90 GL-5 gear lubricating oil formulation.
- PAO poly-alpha-olefin synthetic lubricating oil
- the products of the invention may be used in a wide variety of automotive and industrial gear applications. Examples of such applications include use in hypoid axles and in mechanical steering drives in passenger cars and in cross-country vehicles. Further examples include use in hypoid axles, planetary hub reduction axles, mechanical steering and transfer gear boxes in utility vehicles such as trucks.
- Systems in which the products of the invention may additionally be used include pinion and planetary hub reduction gear boxes, synchromesh gear boxes, power take-off gears and limited slip rear axles; they are especially useful in synchroniser type gear boxes.
- the thermal stability and oxidative stability of the products of the invention make them particularly suitable for use in transmission systems which may be operating at high temperatures.
- the products of the invention may be used to formulate a single oil meeting the specifications of lubricants for use in both gear boxes and in rear axles, whereas hitherto two different oils were required to meet the specifications for these two uses.
- a product serving both such uses is referred to as a total drive line product.
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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)
Claims (18)
- Verfahren zur Herstellung eines Schmiermitteladditivs, bei dem man
bei einer Temperatur über 30°C vor der Verwendung als Schmiermittel entweder gleichzeitig oder in beliebiger Reihenfolge (i) ein oder mehrere aktiven Schwefel enthaltende Mittel zur Verwendung bei extremem Druck oder gegen Verschleiß, (ii) ein oder mehrere Amine und (iii) eine oder mehrere schwache Säuren miteinander agieren läßt, wobei die Verhältnisse der Komponenten (i) und (ii) derart sind, daß die Molprozentsätze von Schwefel in (i) zu Aminostickstoff in (ii) zur Verwendung bei der Herstellung des Schmiermitteladditivs im Bereich von 100 : 1 bis 5 : 1 liegen und der Anteil der zur Herstellung des Produkts verwendeten Komponente (iii) derart ist, daß 0,2 bis 2 chemische Säureäquivalente pro Aminostickstoffäquivalent in der Komponente (ii) vorliegen. - Verfahren nach Anspruch 1, bei dem die Interaktionstemperatur 30 bis 70°C beträgt.
- Verfahren nach Anspruch 2, bei dem die Interaktionstemperatur 40 bis 70°C beträgt.
- Verfahren nach Anspruch 3, bei dem die Interaktionstemperatur 50 bis 60°C beträgt.
- Verfahren nach einem der Ansprüche 1 bis 4, bei dem man die Komponenten bei der angegebenen Temperatur für einen Zeitraum im Bereich von 0,5 bis 3 Stunden miteinander agieren läßt.
- Verfahren nach Anspruch 5, bei dem man die Komponenten bei der angegebenen Temperatur für einen Zeitraum im Bereich von 0,5 bis 2 Stunden miteinander agieren läßt.
- Verfahren nach einem der Ansprüche 1 bis 6, das in mindestens zwei Stufen durchgeführt wird, wobei eine Stufe die Interaktion mindestens eines Teils der Komponenten (i) und (ii) in Abwesenheit der Komponente (iii) beinhaltet und eine folgende Stufe die Interaktion mindestens eines Teils der Komponente (iii) mit dem aus den Komponenten (i) und (ii) gebildeten Produkt beinhaltet.
- Verfahren nach einem der Ansprüche 1 bis 7, das in Gegenwart mindestens eines Teil- oder Vollesters einer Säure von fünfwertigem Phosphor durchgeführt wird.
- Verfahren nach einem der Ansprüche 1 bis 8, in dem die Verhältnisse der Komponenten (i) und (ii) derart sind, daß die Molprozentsätze von Schwefel in (i) zu Aminostickstoff in (ii) im Bereich von 40 : 1 bis 5 : 1 liegen.
- Verfahren nach einem der Ansprüche 1 bis 9, bei dem die Komponente (i) ein oder mehrere aktiven Schwefel enthaltende Mittel zur Verwendung bei extremem Druck oder gegen Verschleiß enthält, in dem die Schwefelatome direkt an Kohlenstoff oder weiteren Schwefel gebunden sind.
- Verfahren nach einem der Ansprüche 1 bis 10, bei dem die Komponente (i) ein oder mehrere geschwefelte Olefine umfaßt.
- Verfahren nach einem der Ansprüche 1 bis 11, bei dem die Komponente (ii) ein oder mehrere acyclische Monoamine umfaßt.
- Verfahren nach einem der Ansprüche 1 bis 12, bei dem die Komponente (iii) eine Carbonsäure mit einem pKa von mehr als 2,0 umfaßt.
- Verfahren nach einem der Ansprüche 1 bis 13, bei dem die Komponente (iii) eine oder mehrere aliphatische Carbonsäuren umfaßt.
- Verfahren nach einem der Ansprüche 1 bis 14, bei dem die Menge der Komponente (iii) theoretisch nicht ausreicht, um den Aminostickstoff der Komponente (ii) vollständig zu neutralisieren.
- Verfahren zur Herstellung einer Schmiermittelzusammensetzung, das das Verfahren nach einem der Ansprüche 1 bis 15 sowie den zusätzlichen Schritt, bei dem eine kleinere Menge des entstandenen Schmiermitteladditivs zu einer größeren Menge einer Schmiermittelgrundmischung gegeben wird, umfaßt.
- Verfahren nach Anspruch 17, bei dem die Schmiermittelgrundmischung flüssiges α-Olefinpolymeröl ist.
- Verwendung eines Schmiermitteladditivs, das durch das Verfahren nach einem der Ansprüche 1 bis 15 zur Herstellung eines Schmiermittels erhältlich ist.
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP90303536A EP0450208B1 (de) | 1990-04-02 | 1990-04-02 | Schmiermittelzusammensetzungen und Additive dafür |
AU52511/90A AU630176B2 (en) | 1990-04-02 | 1990-04-02 | Lubricant compositions and additives therefor |
DE69033375T DE69033375T2 (de) | 1990-04-02 | 1990-04-02 | Schmiermittelzusammensetzungen und Additive dafür |
JP8508290A JP2912415B2 (ja) | 1990-04-02 | 1990-04-02 | 潤滑油組成物及びその添加剤 |
CA002013698A CA2013698A1 (en) | 1990-04-02 | 1990-04-03 | Lubricant compositions and additives therefor |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP90303536A EP0450208B1 (de) | 1990-04-02 | 1990-04-02 | Schmiermittelzusammensetzungen und Additive dafür |
Publications (2)
Publication Number | Publication Date |
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EP0450208A1 EP0450208A1 (de) | 1991-10-09 |
EP0450208B1 true EP0450208B1 (de) | 1999-12-01 |
Family
ID=8205354
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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EP90303536A Expired - Lifetime EP0450208B1 (de) | 1990-04-02 | 1990-04-02 | Schmiermittelzusammensetzungen und Additive dafür |
Country Status (4)
Country | Link |
---|---|
EP (1) | EP0450208B1 (de) |
JP (1) | JP2912415B2 (de) |
AU (1) | AU630176B2 (de) |
DE (1) | DE69033375T2 (de) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8034754B2 (en) | 2005-03-31 | 2011-10-11 | The Lubrizol Corporation | Fluids for enhanced gear protection |
Families Citing this family (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP3510630B2 (ja) * | 1993-10-06 | 2004-03-29 | 出光興産株式会社 | 高速ギヤ用潤滑油組成物 |
EP0684298A3 (de) * | 1994-05-23 | 1996-04-03 | Lubrizol Corp | Zusammensetzungen zur Erhöhung der Lebensdauer von Dichtungen und diese enthaltende Schmiermittel und funktionelle Flüssigkeiten. |
GB9521352D0 (en) * | 1995-10-18 | 1995-12-20 | Exxon Chemical Patents Inc | Power transmitting fluids of improved antiwear performance |
GB9807843D0 (en) * | 1998-04-09 | 1998-06-10 | Ethyl Petroleum Additives Ltd | Lubricating compositions |
US6482777B2 (en) * | 1998-10-19 | 2002-11-19 | The Lubrizol Corporation | Lubricating compositions with improved thermal stability and limited slip performance |
US6179978B1 (en) | 1999-02-12 | 2001-01-30 | Eastman Kodak Company | Mandrel for forming a nozzle plate having a non-wetting surface of uniform thickness and an orifice wall of tapered contour, and method of making the mandrel |
US7648948B2 (en) | 2005-04-08 | 2010-01-19 | Exxonmobil Chemical Patents Inc. | Additive system for lubricants |
US7803332B2 (en) | 2005-05-31 | 2010-09-28 | Exxonmobil Chemical Patents Inc. | Reactor temperature control |
CN104073320A (zh) * | 2009-11-19 | 2014-10-01 | 株式会社捷太格特 | 润滑油、摩擦部件和齿轮式带限滑功能的差速器 |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2475410A (en) * | 1947-10-23 | 1949-07-05 | Gulf Oil Corp | Lubricants |
US3398095A (en) * | 1967-11-13 | 1968-08-20 | Shell Oil Co | Vapor-space inhibitors |
US4317739A (en) * | 1980-10-10 | 1982-03-02 | Standard Oil Company (Indiana) | Aminated sulfurized olefin funtionalized with a boron compound and formaldehyde |
JPH0826340B2 (ja) * | 1984-02-14 | 1996-03-13 | ザ▲ルーブリゾル コーポレイション | 窒素およびりんを含有する組成物類、および該組成物類を含有する水性系類 |
US4615818A (en) * | 1985-03-15 | 1986-10-07 | The Lubrizol Corporation | Hydrogen sulfide stabilized oil-soluble sulfurized organic compositions |
US4744912A (en) * | 1987-04-14 | 1988-05-17 | Mobil Oil Corporation | Sulfurized antiwear additives and compositions containing same |
US5251290A (en) * | 1991-03-25 | 1993-10-05 | Schlumberger Technology Corporation | Modeling method for sorting dependencies among geometric entities |
-
1990
- 1990-04-02 DE DE69033375T patent/DE69033375T2/de not_active Expired - Fee Related
- 1990-04-02 EP EP90303536A patent/EP0450208B1/de not_active Expired - Lifetime
- 1990-04-02 JP JP8508290A patent/JP2912415B2/ja not_active Expired - Fee Related
- 1990-04-02 AU AU52511/90A patent/AU630176B2/en not_active Ceased
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8034754B2 (en) | 2005-03-31 | 2011-10-11 | The Lubrizol Corporation | Fluids for enhanced gear protection |
Also Published As
Publication number | Publication date |
---|---|
AU630176B2 (en) | 1992-10-22 |
JPH03285990A (ja) | 1991-12-17 |
EP0450208A1 (de) | 1991-10-09 |
AU5251190A (en) | 1991-11-14 |
JP2912415B2 (ja) | 1999-06-28 |
DE69033375D1 (de) | 2000-01-05 |
DE69033375T2 (de) | 2000-05-11 |
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