EP0903399B1 - Schmierstoffzusammensetzungen mit Thiophosphorsäureestern und Dithiophosphorsäureestern - Google Patents

Schmierstoffzusammensetzungen mit Thiophosphorsäureestern und Dithiophosphorsäureestern Download PDF

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Publication number
EP0903399B1
EP0903399B1 EP98810894A EP98810894A EP0903399B1 EP 0903399 B1 EP0903399 B1 EP 0903399B1 EP 98810894 A EP98810894 A EP 98810894A EP 98810894 A EP98810894 A EP 98810894A EP 0903399 B1 EP0903399 B1 EP 0903399B1
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Prior art keywords
acid ester
formula
alkyl
tert
butyl
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EP98810894A
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German (de)
English (en)
French (fr)
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EP0903399A1 (de
Inventor
Michael Fletschinger
Peter Rohrbach
Peter Collen Hamblin
Dudley Clark
Marc Ribeaud
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BASF Schweiz AG
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Ciba Spezialitaetenchemie Holding AG
Ciba SC Holding AG
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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
    • 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
    • C10M141/10—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 phosphorus-containing compound
    • 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
    • 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
    • C10M129/16—Ethers
    • C10M129/18—Epoxides
    • 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
    • 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
    • C10M129/68—Esters
    • C10M129/76—Esters containing free hydroxy or carboxyl groups
    • C—CHEMISTRY; METALLURGY
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    • 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
    • C—CHEMISTRY; METALLURGY
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    • 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
    • C10M133/08—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups
    • 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
    • C10M137/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus
    • C10M137/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus having no phosphorus-to-carbon bond
    • C10M137/04—Phosphate esters
    • C10M137/08—Ammonium or amine salts
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    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M137/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus
    • C10M137/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus having no phosphorus-to-carbon bond
    • C10M137/04—Phosphate esters
    • C10M137/10—Thio derivatives
    • C10M137/105—Thio derivatives not containing metal
    • C—CHEMISTRY; METALLURGY
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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
    • C10M2207/04—Ethers; Acetals; Ortho-esters; Ortho-carbonates
    • C10M2207/042—Epoxides
    • C—CHEMISTRY; METALLURGY
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    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/287—Partial esters
    • C—CHEMISTRY; METALLURGY
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    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/287—Partial esters
    • C10M2207/288—Partial esters containing free carboxyl groups
    • C—CHEMISTRY; METALLURGY
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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
    • C10M2207/28—Esters
    • C10M2207/287—Partial esters
    • C10M2207/289—Partial esters containing free hydroxy groups
    • 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
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
    • C10M2209/104—Polyethers, i.e. containing di- or higher polyoxyalkylene groups of alkylene oxides containing two carbon atoms 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
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions
    • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary 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
    • C10M2215/04—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms
    • 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
    • C10M2215/04—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2215/042—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Alkoxylated derivatives thereof
    • 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
    • C10M2215/24—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions having hydrocarbon substituents containing thirty or more carbon atoms, e.g. nitrogen derivatives of substituted succinic acid
    • C10M2215/26—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
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
    • C10M2219/044—Sulfonic acids, Derivatives thereof, e.g. neutral salts
    • C—CHEMISTRY; METALLURGY
    • 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
    • C10M2223/043—Ammonium or amine salts thereof
    • 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
    • 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
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/04—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives
    • C10N2040/042—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives for automatic transmissions
    • 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
    • C10N2040/044—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives for manual transmissions
    • 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
    • C10N2040/046—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives for 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
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/08—Hydraulic fluids, e.g. brake-fluids
    • 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
    • C10N2040/20—Metal working
    • C—CHEMISTRY; METALLURGY
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    • C10N2050/00—Form in which the lubricant is applied to the material being lubricated
    • C10N2050/10—Form in which the lubricant is applied to the material being lubricated semi-solid; greasy

Definitions

  • the invention relates to improved compositions with thiophosphoric acid esters and dithiophosphoric acid esters or phosphoric acid thioesters and the use of these lubricant compositions for improving the performance of lubricants, such as greases, metalworking, gear or hydraulic fluids.
  • Suitable lubricants additives are added, which must meet demanding tasks, such as high load bearing capacity, wear and corrosion protection and antioxidant effect.
  • Suitable for this purpose are zinc dialkyldithiophosphates which, however, the aim is to replace with metal-free compounds for reasons of environmental protection.
  • metal-free hydraulic fluids In particular, in agriculture or in general in mobile hydraulic systems in which there is a risk of soil or water contamination with zinc compounds by leaks, the use of metal-free hydraulic fluids is required. There is therefore a need for metal-free and ashless additives.
  • Suitable hydraulic fluids must also meet the specifications of the leading hydraulic machinery manufacturers, e.g. Denison HFO (Denison Hydraulics) or Vickers M-2980-S (Vickers) and be compatible with water. Furthermore, according to the specifications of DIN 51524 and Denison HFO, they should reach a fault load level (FLS) of at least 10 in the FZG test.
  • FLS fault load level
  • dithiophosphoric acid esters of the type: known under the trade name Irgalube 63 ® (trademark of Ciba Specialty Chemicals) are commercially available.
  • No. 5,531,911 discloses zinc-free hydraulic fluids containing phosphorus- and sulfur-containing additive components.
  • One component is a thiophosphoric acid ester of the triphenylthiophosphate type (IRGALUBE TPPT). This is combined with Dithiophosphorklareestern type IRGALUBE 63 and optional oil additive components, such as ammonium sulfonates.
  • Such formulations are disadvantageous because of their lack of compatibility with water.
  • the contamination of a hydraulic oil with water is common, especially in mobile hydraulic systems.
  • hydrolytic degradation occurs to form corrosive decomposition products. which can attack the metals used in the hydraulic systems, eg steel and copper alloys, and cause damage to the hydraulic pumps.
  • agglomerations of these decomposition products may block the filters of Bypase filtration equipment. Since the service life of hydraulic systems can be significantly extended by ultrafine filtering, the filter mesh sizes of modern bypass filtration systems have been reduced from previously 30 ⁇ m to currently 6 ⁇ m. Therefore, only those hydraulic oils are to be used, which form only very small amounts of hydrolytic decomposition products when contaminated with water.
  • the present invention has for its object to produce compositions with improved compatibility with water, which have a much lower tendency to form undesirable Hydrolperodukten.
  • compositions with thiophosphoric acid esters combined with dithiophosphoric acid esters or phosphoric acid esters have a significantly lower tendency to form corrosive hydrolysis products and very good filtration properties by addition of a further additive component from the group of polyol partial esters, amines and epoxides in the event of contamination with water.
  • additional oil additives eg. As ammonium phosphate esters, the load carrying capacity can be increased and reach FZG Fehierlastculturen ⁇ 10.
  • a particularly preferred embodiment relates to compositions wherein the phosphorus content of the thiophosphoric acid ester component b), combined with the dithiophosphoric acid ester or phosphoric acid thioester component c), based on the composition comprising components a), b) and c), is less than 400 ppm ,
  • a most preferred embodiment relates to compositions wherein the phosphorus content of the thiophosphoric acid ester component b) combined with the dithiophosphoric acid ester or phosphoric acid thioester component c) and the ammonium phosphate ester component e) is less than 400 ppm based on the total composition.
  • compositions are particularly suitable as multifunctional anti-wear additives - with additional antioxidant effect - for lubricants, such as greases, metalworking, gear or hydraulic fluids. They are largely metal and ash-free and meet the specifications mentioned.
  • lubricants such as greases, metalworking, gear or hydraulic fluids. They are largely metal and ash-free and meet the specifications mentioned.
  • mixtures of components b) and c) in the base oil a) give phosphorus concentrations of less than 400 ppm phosphorus very good anti-wear properties, ie very good VKA (test in Vierkugelapparat) and SRV (vibration friction wear) values.
  • These mixtures have on the addition of the additive component from the group of Polyolialialester, amines and epoxides (component d)) in contamination with water very good filtration properties.
  • Further oil additives can achieve FZG fault load levels ⁇ 10.
  • Such blends meet the hydraulic machinery specifications of leading manufacturers, especially Denison HFO.
  • a base oil of lubricating viscosity is useful for the production of greases, metalworking, gear and hydraulic fluids.
  • Suitable greases, metalworking, gear and hydraulic fluids are based, for example, on mineral or synthetic oils or mixtures thereof.
  • the lubricants are familiar to those skilled in the art and in the relevant literature, such as in Chemistry and Technology of Lubricants; Mortier, RM and Orszulik, ST (Editors); 1992 Blackie and Son Ltd. for GB, VCH Publishers NY for US, ISBN 0-216-92921-0, see pages 208 ff and 269 ff .; in Kirk-Othmer Encyclopedia of Chemical Technology, Fourth Edition 1969, J. Wiley & Sons, New York, Vol. 13, page 533 et seq. (Hydraulic Fluids); Performance Testing of Hydraulic Fluids; R.
  • the lubricants are in particular oils and fats, for example based on mineral oil or vegetable and animal oils, fats, tallow and wax or mixtures thereof.
  • Vegetable and animal oils, fats, tallow and wax are, for example, palm kernel oil, palm oil, olive oil, rapeseed oil, rapeseed oil, linseed oil, soybean oil, cottonseed oil, sunflower oil, coconut oil, corn oil, castor oil, walnut oil and mixtures thereof, fish oils and their chemically modified, e.g. epoxidized and sulfoxidated, or genetically engineered forms, for example, genetically engineered soybean oil.
  • Examples of synthetic lubricants include aliphatic or aromatic carboxylic ester based lubricants, polymeric esters, polyalkylene oxides, phosphoric acid esters, poly- ⁇ -olefins or silicones, the diacid diester with a monohydric alcohol such as dioctyl sebacate or dinonyl adipate, a triester of trimethylolpropane with a monovalent acid or with a mixture of such acids, such as trimethylolpropane tripelargonate, trimethylolpropane tricaprylate or mixtures thereof, a tetraester of pentaerythritol with a monohydric acid or with a mixture such acids as pentaerythritol tetracaprylate, or a complex ester of monohydric and diacid acids with polyhydric alcohols, eg, a complex ester of trimethylolpropane with caprylic and sebacic acid, or a
  • the said lubricants or mixtures thereof may also be treated with an organic. or inorganic. Thickener be added (base fat). Metalworking fluids and hydraulic fluids can be prepared based on the same substances as described above for the lubricants. Often these are also emulsions of such substances in water or other liquids.
  • R 1 , R 2 and R 3 with the meaning C 3 -C 20 -hydrocarbon radical are preferably C 3 -C 20 -alkyl, C 5 -C 12 -cycloalkyl, C 5 -C 12 -cycloalkyl-C 1 -C 4 - alkyl, phenyl, C 7 -C 20 alkylphenyl, C 7 -C 20 alkoxyphenyl, naphthyl and C 7 -C 9 phenylalkyl.
  • C 3 -C 20 -alkyl includes branched or unbranched alkyl radicals. Examples of these are n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, n-pentyl, isopentyl, n-hexyl, 2-ethylbutyl, 1-methylpentyl, 1,3-dimethylbutyl, n-heptyl, 3-heptyl , 1-methylhexyl, isoheptyl, n-octyl, 2-ethylhexyl, 1,1,3,3-tetramethylbutyl, 1-methylheptyl, n-nonyl, 1,1,3-trimethylhexyl, n-decyl, n-undecyl, n Dodecyl, 1-methylundecyl, n-tridecyl, n-tetradecyl, n-pent
  • a particularly preferred radical for R 1 , R 2 and R 3 is isopropyl.
  • the meanings of R 1 , R 2 and R 3 may be the same or different.
  • Thiophosphoric acid esters of the formula I are known, for example US Pat. No. 5,531,911.
  • C 5 -C 12 -cycloalkyl are, for example, cyclopentyl or -hexyl.
  • C 5 -C 12 -cycloalkyl-C 1 -C 4 -alkyl is, for example, cyclopentylmethyl, 2-cyclopentylethyl, cyclohexylmethyl or 2-cyclohexylethyl.
  • C 7 -C 20 -alkylphenyl is phenyl which is substituted, for example, by one to three of the above-described C 1 -C 4 -alkyl radicals or one to two C 1 -C 6 -alkyl radicals or a C 1 -C 12 -alkyl radical.
  • C 7 -C 20 -alkoxyphenyl is phenyl which is substituted, for example, by one to three C 1 -C 4 -alkoxy radicals, in particular methoxy or ethoxy, or one to two C 1 -C 6 -alkoxy radicals or a C 1 -C 12 -alkoxy radical is, which are analogous to the aforementioned alkyl radicals.
  • C 7 -C 9 phenylalkyl is, for example, benzyl, 1-phenyl-1-ethyl or 2-phenyl-1-ethyl.
  • component b) consists of a mixture of thiophosphoric acid esters of the formula: wherein x is 0 to 2.7, y is 3 - (x + z), z is 0 to 3 - (x + y) and x + y + z is 3, and Ar is phenyl, C 7 -C 18 alkylphenyl, C 7 -C 18 alkoxyphenyl, naphthyl and C 7 -C 9 phenylalkyl having the meanings given above.
  • thiophosphoric acid esters is described in EP-A-368 803 .
  • Triarylthiophosphatgemische type IRGALUBE 211 the formula Triarylthiophosphatgemische type IRGALUBE 211 with the ingredients such as n-decylphenyl-n-nonylphenyl-phenylthiophosphat, o-tert-butylphenyl-o-isopropylphenyl-phenylthiophosphat or n-hexylphenyl-phenylthiophosphat mixtures are preferred.
  • component b) consists of a thiophosphoric ester of the triphenylthiophosphate type (IRGALUBE TPPT).
  • X is preferably sulfur.
  • R 1 , R 2 and R 3 with the meaning of unsubstituted C 3 -C 20 -hydrocarbon radicals have the meanings given further below under component b) - thiophosphoric acid esters -, in particular C 3 -C 20 -alkyl.
  • R 1 and R 2 are unsubstituted C 3 -C 10 -hydrocarbon radicals and R 3 represents a substituted C 3 -C 10 -hydrocarbon radical.
  • a substituted C 3 -C 10 -hydrocarbon radical R 3 is preferably Carboxy or esterified carboxy-substituted C 2 -C 4 -alkyl, for example the partial formula: wherein R x and R y are hydrogen or C 1 -C 4 alkyl, or the corresponding carboxylate salt.
  • A is 2-carboxyeth-1-yl or 2-C 1 -C 4 -alkoxycarbonyleth-1-yl, for example methoxycarbonyleth-1-yl or ethoxycarbonylethl-yl, or carboxylate salts thereof.
  • the component b) used is a dithiophosphoric acid ester of the type IRGALUBE 63, which has the structural formula given further, optionally in admixture with a further dithiophosphoric acid ester of the formula II, wherein R 1 and R 2 are isopropyl, isobutyl or 2-ethylhexyl, and R 3 has the meaning of the partial formula A, wherein R x and R y are hydrogen, and 2-carboxy-1-ethyl.
  • Dithiophosphoric acid esters and phosphoric acid thioesters are known. Their preparation is described, for example, in US Pat. Nos. 4,333,841; 4,544,492 and 3,784,588 and British Patent 1,569,730.
  • the phosphorus content of components b) and c), based on the composition comprising components a), b) and c), is less than 400 ppm.
  • the phosphorus content of components b) and c) based on the composition comprising components a), b) and c) is 150-390 ppm, in particular 160-370 ppm.
  • the weight ratio of components b) and c) with each other may vary in the ranges of about 10:90 to 95: 5 weight percent.
  • Suitable oil additives are polyol partial esters, e.g. B. from the group of mono- and diglycerides, monoacetylated or diacetylated monoglycerides, polyglycerol fatty acid esters, sorbitan fatty acid esters and partial fatty acid esters of Polyoxyethylensorbitans. These oil additives are added in a concentration of about 0.01 to 2.0%.
  • Suitable mono- and diglycerides are derived from glycerol by esterification of one or two hydroxy groups with one or two acid residues of saturated or unsaturated carboxylic acids and even number of 8-20 carbon atoms.
  • the acid radical of a saturated 8-20 carbon atom saturated carboxylic acid which esterifies the polyglycerol backbone is preferably straight chained with 12, 14, 16 and 18 C atoms, e.g. n-dodecanoyl, n-tetradecanoyl, n-hexadecanoyl or n-octadecanoyl.
  • the acid radical of an even 8-20 carbon atom unsaturated carboxylic acid which esterifies the glycerol backbone is preferably straight chain with 12, 14, 16 and 18 carbon atoms and has 1 double bond, e.g. 9-cis-dodecenoyl, 9-cis-tetradecenoyl, 9-cis-hexadecenoyl or 9-cis-octadecenoyl.
  • 9-cis-dodecenoyl (lauroleoyl), 9-cis-tetradecenoyl (myristoleoyl), 9-cis-hexadecenoyl (palmitoleoyl), 6-cis-octadecenoyl (petroseloyl), 6-trans Octadecenoyl (petroselaidoyl), 9-cis-octadecenoyl (Oleoyl), 9-trans-octadecenoyl (elaidoyl), 11-cis-octadecenoyl (vaccenoyl), 9-cis-schenoyl (gadoleoyl), n-dodecanoyl (lauroyl), n-tetradecanoyl (myristoyl), n-hexadecanoyl (palmito
  • Particularly suitable mono- and diglycerides are available under the designations 16 Loxiol ® G 10 and G (Henkel), Nutrisoft ® 100 (Grunau), Kessco GMO (Akzo) or Edenor ® GMO, GDO (Henkel) is commercially available.
  • a suitable monoacetylated or diacetylated monoglyceride is a monoglyceride which, in addition to the acyl radical of a fatty acid, still preferably has one or even two acetyl radicals.
  • the acyl radical is preferably derived from one of said unsaturated fatty acids having more than ten and an even number of C atoms.
  • Preferred is a monoglyceride which is prepared from a mixture of monoacetylated or diacetylated monoglycerides using the usual separation methods, e.g. fractional distillation, available.
  • acetylated monoglycerides which are commercially available under the trademark MYVACET (Eastman). Acetylated monoglycerides of the MYVACET series are used industrially as lubricants, plasticizers, nonionic emulsifiers and solubilizers. Particularly preferred are the commercially available under the name MYVACET 5-07, 7-00, 7-07, 9-08, 9-40 and 9-45 K available products.
  • a suitable polyglycerol fatty acid ester consists of a substantially pure or a mixture of various polyglycerol fatty acid esters wherein the polyglycerol core preferably contains up to and including 10 glycerol units esterified with 1-10 acid residues of said saturated or unsaturated carboxylic acids and even 8-20 carbon atoms.
  • Suitable polyglycerol fatty acid esters having a uniformly defined structure are, for example, diglycerol monocaprate, diglycerol monolaurate, diglycerol diisostearate, diglycerol monoisostearate, diglycerol tetrastearate (polyglycerol 2-tetrastearate), triglycerol monooleate (polyglyceryl 3-monooleate), triglycerol monolaurate, triglycerol monostearate (US Pat.
  • polyglycerol 3-stearate triglycerol monoisosterate, hexaglycerol dioleate (polyglycerol 6-dioleate), hexaglycerol distearate (polyglycerol 6-distearate), decaglycerol dioleate (polyglycerol 10-dioleate), decaglycerol tetraoleate (polyglycerol 10-tetraoleate), decaglycerol decaoleate (polyglycerol 10 decaoleate), decaglycerol decastearate (10-decastearate polyglycerol). In brackets the CTFA nomenclature is given.
  • Mixtures of different polyglycerol fatty acid esters include names such as decaglycerol mono-, di-oleate, polyglycerol ester of mixed fatty acids, polyglycerol fatty acids, polyglycerol caprate, cocoate, laurate, lanolinate, isostearate or rizinolate and commercially (under the word mark Triodan ® and HOMODAN ® Trademark of the company Grindsted Products, Grindsted Denmark), exact product names: TRIODAN 20, 55, R90 and HOMODAN MO, Radiamuls ® (trademark of the company Petrofina (FINA), Brussels Belgium), exact product name RADIAMULS Poly 2253, the name CAPROL PGE860 or ET, or the word sign Plurol ® (trademark Gattefossé Etablmaschines, Saint-Priest, France), the exact product PLUROL Stearique WL1009 or WL1173 PLUROL Oleique available.
  • a suitable sorbitan fatty acid ester preferably consists of a substantially pure or a mixture of different sorbitan fatty acid esters in which the sorbitol starting material is esterified with 1-3 acid residues of one of said saturated or unsaturated straight-chain carboxylic acids and even 8-20 carbon atoms.
  • Suitable sorbitan fatty acid esters are, in particular, sorbitan monolaurate, monopalmitate, monostearate, tristearate, monooleate, sesquioleate and trioleate.
  • These products are commercially available under the mark clamping ® (trademark of Fa.Atlas, Wilmington USA), specific product names: SPAN 20, 40, 60, 65, 80 and 85, Arlacel ® (trademark of Fa.Atlas), specific product names: ARLACEL 20, 40, 60, 80, 83, 85 and C, Crill (trademark of Croda Chemicals Ltd, Cowick Hall, Snaith Goole GB.), specific product names: (CRILL 1, and 3 4, Dehymuls ® trademarks of.
  • the said partial fatty acid ester of the polyoxyethylene sorbitan is preferably composed of a substantially pure or mixture of different esters of sorbitan, wherein the structure of the fatty acid groups and the length of the polyoxyethylene chains vary.
  • the sorbitan is preferably etherified by three polyoxyethylene chains and esterified by a fatty acid group.
  • the sorbitan can also be etherified by only one or two polyoxyethylene chains and correspondingly esterified by two or three fatty acid groups.
  • the sorbitol basic body is substituted by at least two and at most four hydrophilic groups, wherein the term "hydrophilic group" summarizes the polyoxyethylene chains and fatty acid groups.
  • the polyoxyethylene chain is straight-chain and preferably has 4-10, especially 4-8, ethylene oxide units.
  • the ester groups on the sorbitol bulk are derived from a saturated or unsaturated straight chain carboxylic acid of even 8-20 carbon atoms.
  • the ester group derived from this carboxylic acid is preferably straight chained with 12, 14, 16 and 18 C atoms, e.g. n-dodecanoyl, n-tetradecanoyl, n-hexadecanoyl or n-octadecanoyl.
  • the ester group derived from an even 8-20 carbon atom unsaturated carboxylic acid is preferably straight chained with 12, 14, 16 and 18 C atoms, e.g. Oleoyl.
  • Suitable partial of polyoxyethylene sorbitan are available commercially under the trademark Tween ® from ICI company and the chemical names polyoxyethylene (20 or 4) -sorbitan monolaurate (TWEEN 20 and 21), polyoxyethylene (20) sorbitan monopalmitate or monostearate (TWEEN 40 and 60), polyoxyethylene (4 or 20) sorbitan monostearate or tristearate (TWEEN 61 and 65), polyoxyethylene (20 or 5) sorbitan monooleate (TWEEN 80 or 81) or polyoxyethylene (20) sorbitan trioleate (TWEEN 85) ,
  • Suitable amines are, for example, primary or secondary amines with the above-described C 1 -C 20 -alkyl radicals, in particular C 2 -C 20 -alkyl which may be substituted by hydroxy (alkanolamines) or interrupted by oxygen (etheramines), or polyoxyalkylenediamines, for example or polyoxyalkylenepolyamines, and also primary or secondary amines having C 5 -C 6 -cycloalkyl radicals, for example cyclopentyl or cyclohexyl radicals.
  • Suitable alkanolamines are e.g. Ethanolamine, isopropanolamine, 2-amino-2-methyl-1-propanol, 2- (2-aminoethoxy) ethanol, 3-amino-1-propanol, 2-amino-1-butanol, 2-amino-2-methyl 1,3-propanediol or 2-amino-2-ethyl-1,3-propanediol.
  • Suitable alkanolamines are commercially available, for example, under the word names Ethomeen and Propomeen (Armak Chemical Division of Akzona, Inc., Chicago USA), eg the products ETHOMEEN C / 15, C / 20, C / 25, O / 12, S / 15 , S / 20, T / 12, T / 15 or T / 25 or the corresponding products of the PROPOMEEN series.
  • Suitable etheramines are primary etheramines which are commercially available under the word sign Surfam (Mars Chemical Co., Atlanta USA), e.g. the products SURFAM P14B (decyloxypropylamine) or P16A or P17B (tridecyloxypropylamine).
  • Suitable polyoxyalkylene diamines are, for. B. alkoxylated diamines of the type Ethoduomeen ® (Armak), eg the products T / 13 and T / 20.
  • Suitable polyoxyalkylenepolyamines are commercially available, for example, under the name JEFFAMINE (Jefferson Chemical Co.), for example the products D-230, D-400, D-1000, D-2000 or T-403.
  • Suitable epoxides are, for example, C 4 -C 20 -epoxyalkanes, for example epoxybutane, or esters of C 10 -C 20 -fatty acids, namely esters of epoxidized fatty acids with monohydric alcohols or polyhydric alcohols, for example glycerides.
  • epoxidized esters of fatty acids with monohydric alcohols for example straight-chain and branched C 1 -C 10 -alkyl-C 1 -C 10 -alkoxy, aryl or C 5 -C 8 -cycloalkyl esters of C 10 -C 20 -fatty acids, for example Cyclopentyl or cyclohexyl, n-butyl, n-hexyl, benzyl, methoxyethyl, n-octyl, phenyl or tert-butylphenylepoxystearat or oleate and epoxidized soybean oil or linseed oil or epoxidized natural oils and fats, the are known for a high content of unsaturated fatty acids.
  • R 1 and R 2 represent C 1 -C 20 -hydrocarbon radicals and R a , R b , R c and R d independently of one another represent hydrogen or C 1 -C 20 -hydrocarbon radicals.
  • R 1 and R 2 and R a , R b , R c and R d with the meaning C 1 -C 20 -hydrocarbon radical are preferably C 1 -C 7 -alkyl, for example methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t- Butyl, n-pentyl, isopentyl, n-hexyl, 2-ethylbutyl, 1-methylpentyl, 1,3-dimethylbutyl or n-heptyl.
  • R and R 2 are C 1 -C 20 alkyl, one of R a , R b , R c and R d is hydrogen and the other radicals C 1 -C 20 alkyl.
  • the ammonium phosphate ester is added in a low concentration of about 200 to 500 ppm. This addition gives the hydraulic oil particularly good load bearing capacity (FZG fault load levels ⁇ 10).
  • the total phosphorus content of components b), c) and e), based on the total composition is less than 400 ppm.
  • lubricant compositions mentioned such as greases, transmission.
  • Metalworking and hydraulic fluids may additionally contain other additives which are added to further enhance their basic properties. These include: antioxidants, metal deactivators, rust inhibitors, viscosity index improvers, pour point depressants, Dispersants, detergents, high pressure additives and antiwear additives. Such additives are added in the amounts customary therefor in the range of from about 0.01 to 10.0% by weight.
  • additives are added in the amounts customary therefor in the range of from about 0.01 to 10.0% by weight.
  • additives are added in the amounts customary therefor in the range of from about 0.01 to 10.0% by weight.
  • additives are examples of other additives:
  • metal deactivators e.g. for copper:
  • viscosity index improvers polyacrylates, polymethacrylates, vinylpyrrolidone / methacrylate copolymers, polyvinylpyrrolidones, polybutenes, olefin copolymers, styrene / acrylate copolymers, polyethers.
  • pour point depressants poly (meth) acrylates, ethylene-vinyl acetate copolymer, alkyl polystyrenes, fumarate copolymers, alkylated naphthalene derivatives.
  • dispersants / surfactants polybutenylsuccinic amides or imides, polybutenylphosphonic acid derivatives, basic magnesium, calcium and barium sulphonates and phenolates.
  • Sulfur and halogen containing compounds such as e.g. chlorinated paraffins, sulfurized olefins or vegetable oils (soybean oil, rapeseed oil), alkyl or aryl di- or trisulfides, benzotriazoles or derivatives thereof such as bis (2-ethylhexyl) aminomethyl tolutriazole, dithiocarbamates such as methylene-bis-dibutyldithiocarbamate, derivatives of 2-Mercaptobenzothiazoles such as 1- [N, N-bis (2-ethylhexyl) aminomethyl] -2-mercapto-1H-1,3-benzothiazole, derivatives of 2,5-dimercapto-1,3,4-thiadiazole such as 2 , 5-bis (tert.nonyldithio) -1,3,4-thiadiazole.
  • chlorinated paraffins sulfurized olefins or vegetable oils (soybean
  • Reibwertverminderer for example, oil from lard, oleic acid, tallow, rapeseed oil, sulfurized fats, amines. Further examples are mentioned in EP 565487.
  • the components mentioned can be admixed to the lubricants in a manner known per se. It is also possible to produce a concentrate or a so-called additive package, which can be diluted in accordance with consumption to use concentrations for the corresponding lubricant.
  • the components are so assembled in the concentrate that it is liquid at room temperature without the addition of the base oil a) or a solvent.
  • the invention also relates to a process for improving the service properties of lubricants, characterized by adding components b), c) and d) preferably in a concentration such that the phosphorus content of these components, based on the total composition, is less than 400 ppm.
  • the various blends were prepared using ISO VG 46 mineral oil (kinematic viscosity at 40 ° C: 42-50 CSt) and a base-additive mixture typically used for hydraulic fluids.
  • This base additive blend is free of metal salts and is used at 0.29-0.47% (wt%).
  • an aromatic amine antioxidant such as Irganox ® L 57
  • a hindered phenol antioxidant such as Irganox ® L 135
  • other conventional additives such as pour point depressants (eg: Plexol ® 154), anti-foaming agents (eg, Mobilad C402 ®), Demulgieradditive (eg Synperonic ® PEL81), corrosion inhibitors (for example, Irgacor ® NPA) and metal (such as Irgamet ® 39).
  • pour point depressants eg: Plexol ® 154
  • anti-foaming agents eg, Mobilad C402 ®
  • Demulgieradditive eg Synperonic ® PEL81
  • corrosion inhibitors for example, Irgacor ® NPA
  • metal such as Irgamet ® 39

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  • General Chemical & Material Sciences (AREA)
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  • Organic Chemistry (AREA)
  • Lubricants (AREA)
EP98810894A 1997-09-18 1998-09-09 Schmierstoffzusammensetzungen mit Thiophosphorsäureestern und Dithiophosphorsäureestern Expired - Lifetime EP0903399B1 (de)

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DE59813902D1 (de) 2007-03-29
US20020016266A1 (en) 2002-02-07
JP4114180B2 (ja) 2008-07-09
JPH11217577A (ja) 1999-08-10
KR100538777B1 (ko) 2006-04-28

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