EP1963470B1 - Préformulation d'additifs pour des lubrifiants synthétiques haute température - Google Patents

Préformulation d'additifs pour des lubrifiants synthétiques haute température Download PDF

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Publication number
EP1963470B1
EP1963470B1 EP06845688A EP06845688A EP1963470B1 EP 1963470 B1 EP1963470 B1 EP 1963470B1 EP 06845688 A EP06845688 A EP 06845688A EP 06845688 A EP06845688 A EP 06845688A EP 1963470 B1 EP1963470 B1 EP 1963470B1
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Prior art keywords
fluid
lubricant
weight percent
lubricant fluid
acid
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EP06845688A
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German (de)
English (en)
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EP1963470A2 (fr
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Dale D. Carr
Thomas G. Schaefer
Jeffrey A. Hutter
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Hatco Corp
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Hatco Corp
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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
    • 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
    • C10M169/04—Mixtures of base-materials and additives
    • C10M169/044—Mixtures of base-materials and additives the additives being a mixture of non-macromolecular and macromolecular compounds
    • 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
    • C10M141/00—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential
    • C10M141/12—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential at least one of them being an organic compound containing atoms of elements not provided for in groups C10M141/02 - C10M141/10
    • 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
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
    • C10M169/04—Mixtures of base-materials and additives
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
    • C10M169/06—Mixtures of thickeners and additives
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
    • C10M2201/087—Boron oxides, acids or salts
    • 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
    • C10M2207/28—Esters
    • C10M2207/283—Esters of polyhydroxy compounds
    • 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
    • C10M2207/28—Esters
    • C10M2207/283—Esters of polyhydroxy compounds
    • C10M2207/2835—Esters of polyhydroxy compounds used as base material
    • 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
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
    • C10M2215/064—Di- and triaryl amines
    • 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
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
    • C10M2215/064—Di- and triaryl amines
    • C10M2215/065—Phenyl-Naphthyl amines
    • 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
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/22—Heterocyclic nitrogen compounds
    • C10M2215/223—Five-membered rings containing nitrogen and carbon only
    • 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
    • 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
    • C10M2217/045—Polyureas; Polyurethanes
    • C10M2217/0456—Polyureas; Polyurethanes used as thickening agents
    • 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
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/06—Thio-acids; Thiocyanates; Derivatives thereof
    • C10M2219/062—Thio-acids; Thiocyanates; Derivatives thereof having carbon-to-sulfur double bonds
    • C10M2219/066—Thiocarbamic type compounds
    • 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
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/10—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring
    • C10M2219/104—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring containing sulfur and carbon with nitrogen or oxygen in the ring
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • 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
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/04—Groups 2 or 12
    • C—CHEMISTRY; METALLURGY
    • 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
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/14—Group 7
    • C—CHEMISTRY; METALLURGY
    • 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
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/02—Pour-point; Viscosity index
    • C—CHEMISTRY; METALLURGY
    • 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
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/08—Resistance to extreme temperature
    • C—CHEMISTRY; METALLURGY
    • 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
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/10—Inhibition of oxidation, e.g. anti-oxidants
    • C—CHEMISTRY; METALLURGY
    • 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
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/04—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives
    • C—CHEMISTRY; METALLURGY
    • 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
    • C10N2050/00—Form in which the lubricant is applied to the material being lubricated
    • C10N2050/10—Semi-solids; greasy
    • C—CHEMISTRY; METALLURGY
    • 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
    • C10N2060/00—Chemical after-treatment of the constituents of the lubricating composition
    • C10N2060/14—Chemical after-treatment of the constituents of the lubricating composition by boron or a compound containing boron

Definitions

  • This invention relates generally to high temperature lubricant fluids and, more particularly to an additive package including at least an oligomeric aromatic amine antioxidant and a borated compound for use with a polyol ester to provide a lubricant fluid suitable for use in applications operating at temperatures in excess of 250°C.
  • lubricant compositions suitable to operate at high temperature in excess of 250°C.
  • Such lubricants must provide lubrication and antiwear protection.
  • they must be stable in the high temperature environment, or decompose harmlessly without forming hard, varnish-like deposits or unacceptable amounts of smoke.
  • Many industrial processes involve operation of open chain and drive gear assemblies that are associated with ovens, furnaces, kilns and other hot equipment.
  • Such chain and drive gear assemblies are used in the manufacture of textiles, wallboard, corrugated metal, paper and plastic film.
  • the lubricants In addition to not forming deposits or varnish and possessing stability at high temperatures, the lubricants must perform under high load, be compatible with all materials in contact with the lubricant and be low in volatility.
  • Existing commercial lubricants for chain and drive gear operations which are based on vegetable oils or other glycerol-based esters and mineral oil, lack sufficient high-temperature stability.
  • Polyolefins or polyacid esters also lack the necessary high-temperature stability. All these lubricants are prone to varnish formation and are characterized by relatively high volatility, as well as severe compatibility problems with silicone elastomers.
  • Grease is a lubricating oil that contains a thickener to prevent the oil from leaking out of the area requiring lubrication.
  • Conventional greases use a mineral oil or PAO based lubricating oil and a fatty acid-metal salt, clay, PTFE, or polyurea thickening system.
  • the stability of the lubricating oil is a major factor in determining the suitability of a grease for a particular application. Difficult applications such as the constant velocity joints of front wheel drive automobiles can overstress conventional greases by exceeding their temperature limitations.
  • Additional high temperature lubricant compositions are set forth in U.S. Patent No. 6,436,881 that issued on August 20, 2002.
  • the lubricants described therein include a polyol ester base stock formed from a major proportion of dipentaerythritol and a mixture of C 5 to C 12 monocarboxylic acids.
  • the base stock is mixed with an additive package that includes a viscosity improver, antioxidants, extreme pressure/antiwear agents and a corrosion inhibitor. This lubricant is acceptable for many applications such as static chain oils, where pools of lubricants are subject to continual heating.
  • XP 13007534 "Fluid bearing spindle motor with special lubricant" discloses a system of additives comprising oligomers of dioctylphenylamine and phenylnaphtylamine, which improves oxidative stability of light duty FDB oils.
  • an improved additive package for a synthetic polyol ester lubricant fluid to be used as a high temperature oil or a component in a grease includes an effective amount of at least one oligomeric amine antioxidant and at least one borated extreme pressure/antiwear agent and may include a corrosion inhibitor.
  • the polyol ester fluid is formed by reacting pentaerythritol and a monocarboxylic acid having from 5 to 12 carbon atoms including at least 60 WT % iso C9 acid.
  • the resulting lubricant fluid does not require the addition of a viscosity index improver to be suitable for use in high temperature chain oil and grease applications.
  • the pentaerythritol is dipentaerythritol.
  • the additive package is added in an amount between 5 to 15 percent by weight of the lubricant fluid to provide an oil having a viscosity at 40°C of at least 120 cSt and preferably at 100°C of no less than about 15.0 cSt.
  • An object of the invention is to provide an improved synthetic polyol ester lubricant fluid including an additive package including at least one oligomeric amine antioxidant according to claims 4 and 8 and at least one borated extreme pressure agent suitable for use in high temperature chain oil and grease applications.
  • a further object of the invention is to provide an improved polyol ester lubricant additive package that includes at least an oligomeric amine antioxidant and a borated extreme pressure agent.
  • Yet another object of the invention is to provide an improved high temperature polyol ester synthetic lubricant including a dipentaerythritol ester and an additive package that has reduced weight loss when subject to heat for extended periods of time.
  • Still another object of the invention is to provide an improved polyol ester lubricant oil for high temperature application that does not form hard varnish and undesirable deposits when subject to high temperature.
  • the invention accordingly comprises a composition of matter possessing the characteristics, properties and the relation of components that will be exemplified in the compositions hereinafter described, and the scope of the invention will be indicated in the claims.
  • FIG. 1 is a photograph of panel coking tests for polyol ester based lubricant fluids in accordance with the invention and a lubricant of a polyol and an additive package formulated in accordance with U.S. Patent No. 6,436,881 .
  • the additive package in accordance with the invention suitable for use in 100% polyol ester high temperature lubricant fluids includes at least: (i) an oligomeric aromatic amine, and (ii) a borated extreme pressure agent.
  • the polyol esters suitable for high temperature application are the reaction product of pentaerythritol or dipentaerythritol, with a monocarboxylic acid or monocarboxylic acid mixture of C 5 to C 12 acids.
  • the polyol is a dipentaerythritol that is at least about 85 weight percent diPE and may include about 5 percent monopentaerythritol, and 10 percent tripentaerythritol plus higher pentaerythritols.
  • the acid mixture includes at least about 60 weight percent iso-C 9 acid.
  • the viscosity of the lubricating fluid base stock is at least about 120 cSt at 40°C.
  • lubricants such as oils and greases there is no need to add a viscosity index modifier.
  • the monocarboxylic acid found particularly suitable for use in preparing the high temperature fluid may be isononanoic (3, 5, 5-trimethylhexanoic) acid ("iso-C 9 acid”) for high viscosity lubricants and greases or mixtures of C 7 and C 8-10 normal monocarboxylic acids and iso-C 9 acid.. It is one of the preferred embodiment of the invention that the acid be only iso-C 9 acid. Mixtures including heptanoic (C 7 ) acid and caprylic/capric (C 8-10 ) acid with the iso-C 9 acid are within the scope of the invention. Preferred acid mixtures include between at least about 60 to 70 weight percent iso-C 9 acid with the balance being C 7 and C 8-10 straight chain acids.
  • the dipentaerythritol and acid composition it is possible to vary the dipentaerythritol and acid composition to provide an ester composition having a minimum viscosity at 40°C of at least about 140 cSt.
  • the viscosity of the polyol ester at 100°C should be between about 15 to 30 cSt and have a viscosity index in the range of about 60 to 120.
  • the polyol ester is dipentaerythritol isononanate having a viscosity at 40°C of about 360 to 400 cSt.
  • the acid mixture is varied to include C 7 and C 8-10 straight chain acids and iso-C 9 acid to yield polyols having a viscosity at 40°C of between 120 and 170 cSt, and most preferably about 150 cSt.
  • the additive package in accordance with the invention is added to the synthetic polyol ester base stock to form a lubricant fluid.
  • the additive package includes between about 3-8 weight percent antioxidant in combination with about 1-4 weight percent of a borated extreme pressure/antiwear agent, based on the total weight of the composition.
  • a minor effective amount of a corrosion inhibitor may also be added to the lubricant fluid. This yields a lubricant fluid having a density at 15.6°C of 960 to 990kg/m 3 (8.0 to 8.25 lbs./gal), a total acid number of about 0.30 to 0.40, a pour point of less than about -15°C and a flash point of at least about 285°C.
  • the lubricant fluids in accordance with the invention will include between about 5 to 10 parts by weight of the additive package and 100 parts by weight of the desired polyol ester base stock.
  • the lubricating fluid of the polyol ester and additive package is suitable for use directly as an oil lubricant.
  • the oil lubricant is particularly well suited for use in high temperature chain oil applications.
  • the lubricating fluid can also be utilized to form a grease.
  • a thickening agent to immobilize the fluid is included in the composition.
  • the concentration of thickener determines the consistency and general properties of the finished product and may be included in amounts ranging from 20 to 30 weight percent of the total composition.
  • thickener types are suitable. These include metallic soap thickeners, complex metallic soap thickeners, and non-soap thickeners.
  • the non-soap thickeners are organo-clay, polyurea; and PTFE.
  • Metallic soap thickeners are usually complex metallic soaps. These include aluminum, calcium, barium and lithium complexes.
  • the non-soap thickeners are the organo-clay greases, PTFE (Teflon) and silica gel greases.
  • PTFE Teflon
  • silica gel greases When polyurea greases are utilized, the oils are mixed with suitable amines and isocyanides or disocyanates making the polyurea greases particularly suitable for high temperature applications.
  • a grease in accordance with the invention includes between about 65 to 85 weight percent polyol ester, between about 15 to 35 percent polyurea or other suitable thickener and the additive package of between about 1 to 8 percent oligomeric aromatic amine antioxidant and about 0.10 to 4 percent borated extreme pressure agent. It has been found that such greases exceed 600 hours in the bearing life test at 1,000 rpm and 169 °C (325 °F) as described in ASTM D-3527.
  • Ester based grease is prepared by charging a standard grease manufacturing kettle having milling and recirculation capabilities with about 40 parts of ISO 400 grade polyol ester, 21 parts of the polyurea thickening agent components and 0.5 parts water and heated to 225° to 235°F. Heating is continued to 375° to 385°F then shut the heat off and agitated for 15 to 20 minutes. Three parts of a boron extreme pressure agent are added, and the oil is milled with the cooling oil on for at least 3 to 4 hours. After 1 to 1.2 hours of milling, the penetration of the grease is adjusted to a value of 240 to 260 by adding up to 22 parts of ISO 170 grade polyol ester while milling.
  • any polyol ester based lubricant must exhibit compatibility with materials it contacts.
  • the polyol ester lubricating fluid is prepared by placing the desired amount of polyol and carboxylic acid into a reaction vessel and conducting an esterification reaction to form the ester.
  • the carboxylic acid component is present in the reaction mixture in an excess of about 5 to 10 weight percent for the amount of polyol.
  • the excess carboxylic acid is used to force the reaction to completion.
  • the excess is not critical to carrying out the reaction, except that the smaller the excess, the longer the reaction time.
  • the esterification reaction is complete, the excess acid is removed by stripping and refining.
  • the esterification reaction is carried out in the presence of a conventional catalyst.
  • tin, titanium, zirconium or tungsten-based catalysts designed for high temperature systems are suitable. Uncatalyzed esterification may also be carried out.
  • High temperature lubricant fluids are prepared by mixing an additive package with the ester reaction product.
  • the additive package includes at least the oligomeric amine antioxidant and the borated extreme pressure and antiwear agent together with a corrosion inhibitor. Additional additives such as an antifoam agent, detergents, hydrolytic stabilizers and metal deactivators may also be included.
  • the antioxidant is an oligomeric aromatic amine, such as the reaction product of alkylated diphenylamine, an alkylated phenylnaphthylamine and an ester base stock, in amounts between about 3 to 8 parts by weight based on 100 parts of fluid.
  • the extreme pressure and antiwear agent is a borated compound selected from the group of borated amines, potassium tetraborate, borates of Group la alkali metals, borates of Group 2a alkaline earth metals, stable borates of transition metals, such as zinc, copper and tin, and boric acid.
  • the borated agents may be included in amounts between about 1 to 4 parts by weight.
  • a corrosion inhibitor, such as a benzotriazole may be added in minor amounts between about 0.01 to 0.10 parts by weight.
  • the lubricant fluid should have a viscosity at 40°C between about 120 to 400 cSt depending on the viscosity of the ester.
  • the viscosity at 100°C should be between about 15 to 30 cSt.
  • the viscosity index is between about 80 to 130 the pour point is below about -15°C and the flash point is in excess of about 285°C.
  • a polyol ester of desired viscosity can be prepared by blending a high viscosity polyol ester with a lower viscosity polyol ester.
  • a dipentaerythritol hexaisononanoate ester was prepared in a reaction vessel equipped with a mechanical stirrer, thermocouple, thermoregulator, Dean-Stark trap, condenser, nitrogen sparge and vacuum source. The following materials were charged to the reactor: INGREDIENT AMOUNT gms (moles) Dipentaerythritol 1225 g (4.8m) Isononanoic acid 5175 g (32.75m)
  • the reaction mixture was heated to 185°-190°C with agitation.
  • the water-of-reaction was collected in and removed from the Dean-Stark trap.
  • the temperature was gradually raised over 5-6 hours to about 230°C with application of vacuum to maintain reflux. This removed the reaction water and returned the acid collected in the trap to the reactor. These conditions were maintained to a point where the hydroxyl number of the reaction mixture was less than 3.0.
  • the bulk of the excess acid was then removed by vacuum distillation together with nitrogen sparge and then residual acidity was removed with alkali.
  • a dipentaerythritol ester having a viscosity of about 150 cSt at 40°C can be prepared in a vessel in the same manner as described for the ester in Example 1.
  • the following materials are charged to the reactor: INGREDIENT AMOUNT gms (moles) Dipentaerythritol 1225 g (4.8m) Heptanoic acid 597 g (4.59m) Caprylic/capric acid 1094 g (7.06m) Isononanoic acid 3283 g (20.78m)
  • the reaction mixture is heated to 185°-190°C with agitation.
  • the water-of-reaction is collected in and removed from the Dean-Stark trap.
  • the temperature is gradually raised over 5-6 hours to about 230°C with application of vacuum to maintain reflux. This removes the reaction water and returns the acid collected in the trap to the reactor. These conditions are maintained to a point where the hydroxyl number of the reaction mixture is less than 3.0.
  • the bulk of the excess acid is then removed by vacuum distillation together with nitrogen sparge and then residual acidity was removed with alkali.
  • the resulting product is dried and filtered to obtain 5000g of an ester product having a viscosity at 40°C of about 150.
  • the resulting lubricant fluids had the following physical properties: TABLE III Run 3 Run 4 Viscosity, cSt @ 100°C : 25.6 25.3 @ 40°C: 386 384 Viscosity Index : 86 87 Pour Point, °C : -20 (-5) -37 (-35) Flash Point, C.O.C., °C(°F): 310(590) 310 (590) Acid Valve, mgKOH/g: .36 .38
  • a lubricant fluid In order for a lubricant fluid to be acceptable in the high temperature applications, it must have low volatility and not form deposits or varnish when exposed to high temperatures for extended periods of time.
  • samples of the lubricant fluids of Example 2 were placed into an oven at high temperature for an extended period of time and the weight loss was measured.
  • Example 2 In order for a lubricant fluid to be acceptable in the high temperature applications, it must have superior oxidative and thermal stability.
  • the formulations of Example 2 were tested by the FED-STD-791 Method 5308, Oxidation and Corrosion Stability. In this test 100 ml of test oil is held at 425°F (218°C) for 72 hours in the presence of four different metals and a sparge of dry air. At the end of the test period, the test oil is evaluated for viscosity change, acidity change, and sediment/sludge formation. The test results are shown in Table V. TABLE V 425°F 72 hour OCS Test Run 3 Run 4 % Viscosity Change +12.5 +7.4 Acid Value change, mgKOH/g 1.29 0.12 Sediment/sludge, mg/100ml 1.9 3.2
  • a polyol ester high temperature lubricant prepared following the procedures of Example 2 in U.S. Patent No. 6,436,881 was prepared with the following components. TABLE VI Lubricant Parts by Weight Polyol ester of 100.00 Example 1-U.S. Patent 6,436,881 * Viscosity index improver 5.60 (2.8% polymer) Antioxidant 4.50 Extreme pressure and antiwear agents 2.25 Corrosion inhibitor 0.05 *Polyol Ester Base Stock: Dipentaerythritol 1225g (4.8m) Heptanoic acid 750g (5.77m) Caprylic/capric acid (acid no. 361.5) 750g (4.83m) Isononanoic acid 3500g (22.15m)
  • a lubricant fluid prepared in accordance with Example 3 was compared to the lubricant prepare in accordance with comparative Example 6 in a bench panel test.
  • a stainless steel panel is electrically heated by means of two heaters which are inserted into holes in the panel. The temperature is monitored by means of a thermocouple.
  • the panel is placed on a slight incline and heated to 540° F.
  • the lubricant to be tested is dropped onto the heated panel for 20 hours in the presence of 0.1-0.2 lpm humid air flow. The characteristics are observed and shown in FIG 1.
  • the lubricant contacts the panel near the top of the incline and is observed as a central dark band.
  • the lubricant then tends to thin out as it travels towards the pointed end of the heated panel. It is along the oil-air-metal interface that the degradation of the lubricant is best observed.
  • a grease using the polyol ester of Example 1 is prepared in accordance with the invention as follows.
  • a standard grease manufacturing kettle having milling and recirculation capabilities is charged with 40 parts of ISO 400 grade polyol ester, 8.95 parts of an aromatic diisocyanate, 9.1 parts of a tallowalkylamine, and 0.95 parts of ethylene diamine (an alkyldiamine).
  • ISO 400 grade polyol ester 8.95 parts of an aromatic diisocyanate
  • 9.1 parts of a tallowalkylamine 9.1 parts of a tallowalkylamine
  • 0.95 parts of ethylene diamine (an alkyldiamine) 0.95 parts of ethylene diamine (an alkyldiamine).

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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 (12)

  1. Fluide lubrifiant à base d'ester synthétique, comprenant :
    (A) une huile de base ester qui est le produit de réaction de :
    (i) pentaérythritol ; et
    (ii) un mélange d'acides monocarboxyliques comprenant au moins 60 pour cent en poids d'acide iso-C9 ; et
    (B) un ensemble d'additifs comprenant :
    - au moins un anti-oxydant amine aromatique oligomère qui est le produit de réaction d'une diphénylamine alkylée, d'une phénylnaphtylamine alkylée et d'une huile de base ester ; et
    - au moins un agent extrême pression/anti-usure boré ;
    l'ensemble d'additifs étant présent dans une quantité entre 5 à 15 pour cent en poids, sur la base du poids total du fluide ;
    le fluide lubrifiant ayant une viscosité à 40°C d'au moins 120 cSt.
  2. Ensemble d'additifs selon la revendication 1, dans lequel l'agent extrême pression/anti-usure boré est au moins l'un parmi une amine borée, le tétraborate de potassium, les borates de métaux alcalino-terreux du Groupe 2a, les borates stables de métaux de transition, comprenant le zinc, le cuivre et l'étain, et l'acide borique.
  3. Fluide lubrifiant synthétique selon l'une des revendications 1 et 2, dans lequel l'anti-oxydant est présent dans une quantité entre 1 à 10 pour cent en poids, sur la base du poids total du fluide.
  4. Fluide lubrifiant synthétique selon l'une des revendications 1 et 2, dans lequel l'agent anti-usure boré est présent dans une quantité entre 0,1 à 5 pour cent en poids sur la base du poids total du fluide.
  5. Fluide lubrifiant synthétique selon l'une des revendications 1 et 2, dans lequel le polyol est d'au moins 85 pour cent en poids le pentaérythritol, de préférence est d'environ 98 pour cent le pentaérythritol.
  6. Fluide lubrifiant synthétique selon l'une des revendications 1 et 2, comprenant en outre une quantité efficace d'un inhibiteur de corrosion, de préférence le benzotriazole.
  7. Fluide lubrifiant synthétique selon l'une des revendications 1 et 2, dans lequel le reste de l'acide monocarboxylique est les acides normaux en C7 à C10 et dans lequel le mélange d'acides est d'au moins 66 pour cent l'acide iso-C9.
  8. Fluide lubrifiant à base d'ester synthétique, comprenant :
    (A) une huile de base ester qui est le produit de réaction de :
    (i) dipentaérythritol ; et
    (ii) un mélange d'acides monocarboxyliques comprenant au moins environ 60 pour cent en poids d'acide iso-C9 et d'acides à chaîne droite en C7 et C8-10; et
    (B) un ensemble d'additifs comprenant :
    au moins un anti-oxydant amine aromatique oligomère qui est le produit de réaction d'une diphénylamine alkylée, d'une phénylnaphtylamine alkylée et d'une huile de base
    ester, et un agent extrême pression/anti-usure boré ;
    pour produire le fluide lubrifiant ayant une viscosité à 40°C d'au moins 120 cSt ;
    le fluide lubrifiant comprenant entre 5 à 10 parties en poids de l'ensemble d'additifs et 100 parties en poids de l'huile de base ester de polyol désirée.
  9. Fluide lubrifiant à base d'ester synthétique selon la revendication 8, dans lequel le dipentaérythritol est du dipentaérythritol à au moins 85 pour cent en poids.
  10. Fluide lubrifiant à base d'ester synthétique selon la revendication 8, dans lequel l'anti-oxydant est présent dans une quantité entre 3 à 8 pour cent en poids, sur la base du poids total du fluide.
  11. Fluide lubrifiant à base d'ester synthétique selon la revendication 8, dans lequel l'agent anti-usure boré est présent dans une quantité entre 0,5 à 4 pour cent en poids sur la base du poids total du fluide.
  12. Fluide lubrifiant à base d'ester synthétique selon l'une des revendications 1 ou 8, comprenant en outre un agent épaississant pour former une graisse, lequel agent épaississant est de préférence une polyurée.
EP06845688A 2005-12-16 2006-12-18 Préformulation d'additifs pour des lubrifiants synthétiques haute température Not-in-force EP1963470B1 (fr)

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US7413682B2 (en) * 2006-08-15 2008-08-19 Anderol, Inc. Antioxidants and methods of making antioxidants
US8209718B2 (en) * 2007-07-26 2012-06-26 The Directv Group, Inc. Method and system for positioning row advertising in a program guide
CN101368129B (zh) * 2008-08-06 2012-05-23 杭州得润宝油脂有限公司 一种脲基润滑脂组合物及制备方法
DE102009009124A1 (de) * 2008-10-24 2010-04-29 Paul Hettich Gmbh & Co. Kg Auszugsführung für Haushaltsgeräte
US20120329687A1 (en) * 2011-06-23 2012-12-27 Caterpillar Inc. Extreme pressure additives and lubricants containing them
CN102952607B (zh) * 2011-08-25 2014-10-01 中国石油化工股份有限公司 一种复合锆基六聚脲润滑脂及其制备方法
WO2017201333A1 (fr) * 2016-05-18 2017-11-23 Modernatx, Inc. Polynucléotides codant pour la lipoprotéine lipase destinés au traitement de l'hyperlipidémie
US20190093040A1 (en) * 2017-09-22 2019-03-28 Exxonmobil Research And Engineering Company Lubricating oil compositions with viscosity and deposit control
CN113817526B (zh) * 2021-10-29 2023-04-07 中国石油化工股份有限公司 一种高温链条油组合物及其制备方法

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JP4310286B2 (ja) * 2004-03-31 2009-08-05 三菱重工業株式会社 潤滑油組成物

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RU2008129100A (ru) 2010-01-27
WO2007075531A3 (fr) 2007-09-13
EP1963470A2 (fr) 2008-09-03
US20070184989A1 (en) 2007-08-09
CN101331216A (zh) 2008-12-24
JP2009520079A (ja) 2009-05-21
CN101331216B (zh) 2013-08-07
WO2007075531A2 (fr) 2007-07-05

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