EP0420868B1 - Verfahren zur reduzierung des verschleisses auf oberflächen, die reibungskraeften ausgesetzt sind - Google Patents

Verfahren zur reduzierung des verschleisses auf oberflächen, die reibungskraeften ausgesetzt sind Download PDF

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Publication number
EP0420868B1
EP0420868B1 EP89906387A EP89906387A EP0420868B1 EP 0420868 B1 EP0420868 B1 EP 0420868B1 EP 89906387 A EP89906387 A EP 89906387A EP 89906387 A EP89906387 A EP 89906387A EP 0420868 B1 EP0420868 B1 EP 0420868B1
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carrier
heteropolar
compound
heteropolar compound
molecule
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French (fr)
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EP0420868A1 (de
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Josef Fodor
Jack Schofield
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BTG International Ltd
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BTG International Ltd
British Technology Group Ltd
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L10/00—Use of additives to fuels or fires for particular purposes
    • C10L10/08—Use of additives to fuels or fires for particular purposes for improving lubricity; for reducing wear
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/22—Organic compounds containing nitrogen
    • C10L1/232—Organic compounds containing nitrogen containing nitrogen in a heterocyclic 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
    • C10M107/00—Lubricating compositions characterised by the base-material being a macromolecular compound
    • C10M107/40—Lubricating compositions characterised by the base-material being a macromolecular compound containing nitrogen
    • C10M107/44—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • 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
    • 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
    • C10M133/38—Heterocyclic nitrogen 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
    • 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
    • C10M133/38—Heterocyclic nitrogen compounds
    • C10M133/40—Six-membered ring 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
    • 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
    • C10M173/00—Lubricating compositions containing more than 10% water
    • 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
    • C10M2201/02—Water
    • 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
    • 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
    • C10M2215/221—Six-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
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/22—Heterocyclic nitrogen compounds
    • C10M2215/225—Heterocyclic nitrogen compounds the rings containing both nitrogen and oxygen
    • 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
    • C10M2215/225—Heterocyclic nitrogen compounds the rings containing both nitrogen and oxygen
    • C10M2215/226—Morpholines
    • 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
    • C10M2215/30—Heterocyclic 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
    • 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
    • C10M2217/0403—Macromolecular compounds from nitrogen-containing monomers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds 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
    • 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
    • C10M2217/041—Macromolecular compounds from nitrogen-containing monomers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds involving a condensation reaction
    • C10M2217/0415—Macromolecular compounds from nitrogen-containing monomers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds involving a condensation reaction 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
    • 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
    • C10M2217/042—Macromolecular compounds from nitrogen-containing monomers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds between the nitrogen-containing monomer and an aldehyde or ketone
    • C10M2217/0425—Macromolecular compounds from nitrogen-containing monomers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds between the nitrogen-containing monomer and an aldehyde or ketone 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
    • 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
    • C10M2217/043—Mannich bases
    • C10M2217/0435—Mannich bases 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
    • 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
    • C10M2217/044—Polyamides
    • 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
    • C10M2217/044—Polyamides
    • C10M2217/0443—Polyamides 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
    • 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
    • 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
    • C10M2217/0453—Polyureas; Polyurethanes 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
    • 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
    • C10M2217/0465—Polyamines, i.e. macromoleculars obtained by condensation of more than eleven amine monomers used as base material
    • 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
    • C10N2050/01—Emulsions, colloids, or micelles

Definitions

  • the present invention relates to a method of reducing wear on surfaces subjected to frictional forces, particularly between moving surfaces.
  • extreme pressure lubricants To combat welding under such extreme conditions, extreme pressure lubricants were developed. Such lubricants contain additives which react at the high contact temperatures to form high-melting inorganic lubricant films on the metal surfaces which prevent massive welding and breakdown. Generally, these additives consist of sulphur, chlorine, phosphorus and lead compounds which act either by providing layers of low shear strength to minimise metal tearing or by serving as fluxing agents to contaminate the metal surface and prevent welding. Since all extreme-pressure additives are affected by chemical action, i.e. the formation of covalent bonds, their use is generally avoided to eliminate possible corrosion difficulties.
  • Dry sliding which involves solid-to-solid contact, not infrequently exists, even when adequate fluid film lubrication is provided. Dry sliding can occur for example, in starting up of a machine, with misalignment or inadequate clearance during run-in, during reversal of direction, and during any delays or interruptions in supply of the lubricating fluid. Where conventional oils and greases cannot be used because of extreme temperatures, high vacuum, radiation, or contamination, thin coatings of dry lubricants have been applied to reduce the higher friction and more extensive wear which otherwise obtain on rubbing the structural materials against each other.
  • a wide variety of compounds have been used for improving lubrication under boundary film conditions.
  • compounds containing oxygen such as fatty acids, esters and ketones, compounds containing sulphur or combinations of oxygen and sulphur, organic chlorine compounds such as chlorinated waxes, organic sulphur compounds such as sulphurised fats and sulphurised olefines compounds containing both chlorine and sulphur, organic phosphorous compounds such as tricresyl phosphate, thiophosphates and phosphites and also organic lead compounds have been used.
  • polar additives having a polar group at one end of the molecule and a solubilising group at the other - usually a long chain hydrocarbon to effect solubilisation in the lubricating oil, have been used to provide an adherent adsorped film over metallic surfaces.
  • a class of heterocyclic compounds useful as additives which provide friction modification and improved fuel economy are disclosed in WO 87/0596 and have the general formula: wherein Z is S, NR, PR or PRA, wherein A is 0 or S and R is H, alkyl, alkenyl, hydrocarbyl acyl, hydrocarbyl phenolate or -(CH 2 ) m Q, where m is 1 to about 12, and Q is O-alkyl or N-alkyl, X is independently H, COOH, NH 2 CONH 2 , NHNH 2 , OR, COR, NHR, OH, SH, or CN wherein R is the same as defined above; p is 0 to 2; e is 0 to 2 wherein e+p is 2 to about 4; T is NH 2 , NHR wherein R is the same as defined above, SH, OH or their tautomers, hydrocarbyl acyl or hydrocarbyl phenolate; and Y is CN, C0 2 H
  • Such adsorped films of additive have hitherto only been successful under relatively mild boundary lubrication conditions, primarily because the thickness of such films is very low and usually of the order of one nanometer.
  • substances like tricresyl phosphate or zinc dialkyl dithiophosphates have been found necessary and in extreme rubbing conditions where severe metal-to-metal contact would otherwise be encountered, active sulphur, chlorine and lead compounds have been found essential.
  • Such additives however react chemically to form low shear strength surface layers such as lead sulphide ion chloride or ion sulphide. This surface layer then prevents destructive welding, excessive metal transfer and severe surface breakdown.
  • Such chemical reactivity with the surfaces of the sliding parts however is not in general desirable and is only undertaken when no other alternative is available.
  • the polar type of compound which forms an adherent adsorped film over the moving surfaces is much to be preferred, but the thicknesses of such films which have been possible by the use of hitherto known additives in lubricating compositions have produced insufficient thicknesses of adsorped film to function under any conditions other than mild conditions.
  • US 3779920 discloses certain nitrogen-oxygen containing compounds in lubricating oil compositions comprising mineral oil of lubricating viscosity and at least one alkali metal and/or alkaline earth metal carbonate overbased sulphonate and/or phenate. These nitrogen-oxygen containing compounds are added to mop up the alkaline compound to prevent wear. In particular it discloses the use of 0.5% by weight hydroxyquinoline in one such composition.
  • SU 939527 discloses the use of 0.05 to 0.19% hydroxyquinoline in a composition also comprising a soapy plastics lubricant and copper. It is said that the alloying of the copper with the 8-hydroxyquinoline aids lubrication.
  • US 2030033 discloses the use of less than 1% dihydroxyquinoline as an inhibiter of gum formation in petroleum products.
  • US 3939084 discloses compositions for use as corrosion inhibitors. It is preferred that the compounds disclosed are used in amounts from 0.05 to 0.5% by weight. The most similar compounds to those of the invention include 4-6 dihydroxy pyrimidine each of which were used in amounts of 0.1 % by weight.
  • EP 69507 is concerned with additives which confer antioxidant and/or metal deactivating and/or electrical insulating properties.
  • the heteroaromatic nitrogen containing compound most similar to those of the invention is 6-aminopurine which is used in an amount of 0.054% by weight.
  • the present invention concerns a radical advance in lubrication by providing a regime in which multimolecular layers are adsorbed onto the surfaces to be protected thus enabling comparatively thick protective films to be built up on sufaces subject to frictional wear.
  • certain molecules have the property of forming such multimolecular layers when contacted with the surface as by incorporation in a carrier which is continuously or intermittently brought into contact with at least a portion of the surface to be protected.
  • the molecules which have been found to have this property are essentially single or condensed unsaturated ring systems which comprise at least one six-membered unsaturated heterocyclic ring comprising at least one heterocyclic moiety which acts as a hydrogen acceptor, the molecule also comprising at least one hydrogen donor moiety.
  • the molecules may comprise other five or six-membered unsaturated rings which together with the said six-membered unsaturated heterocyclic ring form a condensed ring system.
  • the multimolecular layers of the lubricating regime of the present invention are built up by initial adsorption of a layer of molecules onto the surface to be protected followed by adsorption of further molecules onto the initial layers to form a second layer and yet further adsorption to form more layers until films up to about 1 micrometer thick are formed.
  • adsorption of a layer of molecules onto the surface to be protected followed by adsorption of further molecules onto the initial layers to form a second layer and yet further adsorption to form more layers until films up to about 1 micrometer thick are formed.
  • substituents may be present on the heteropolar molecules provided they do not singly or collectively prevent interaction of the hydrogen donor and acceptor moieties as by steric hindrance.
  • hydrocarbon substituents such as alkyl groups should preferably not contain more than four carbon atoms, preferably not more than two carbon atoms.
  • the substituent is ortho to either the heteroatom or the hydroxyl group the steric hindrance effect is likely to be greater than when said substituent is in the meta or para position to either the heteroatom or a hydroxyl group.
  • Alkene and alkyne substituents, carboxyl containing and amine containing substituents will all effect the activity of the heteropolar molecules and should be avoided.
  • a method of reducing wear on a surface which is subject to frictional forces which comprises forming and maintaining on said surface a protective layer characterised in that said protective layer is a multi-molecular layer of a heteropolar compound comprising at least one unsaturated heterocyclic six-membered ring in which at least one wholly unsubstituted heteroatom moiety acts as a hydrogen acceptor and in which said compound also comprises at least one hydrogen donor moiety, and in which said heteropolar compound has no substituent which by itself or together with another substituent or substituents creates such steric hindrance and/or renders the molecule so basic or acidic or so alters the steric geometry of the molecule as to prevent interaction of the hydrogen donor and acceptor moieties of one molecule of the heteropolar compound with the hydrogen donor and acceptor moieties of another molecule of said heteropolar compound nor any substituent which by itself or together with another substituent or substituents has the effect of solubilizing said heteropolar compound in a selected carrier to the extent
  • Formation of the multimolecular layer of heteropolar molecules may be effected by incorporating the heteropolar compound in a carrier which is brought into contact with the surface to be lubricated. It has been found that the heteropolar molecules migrate through the carrier onto the surface to be lubricated and build up on that surface to form multimolecular layers.
  • the carrier may be a liquid such as an oil or grease or may even be aqueous. Solid carriers are also feasible such as polyamide plastics such as those used to build up worn machinery parts such as drive shafts and the like.
  • heteropolar molecules migrate laterally over the surface on which they are adsorbed beyond the boundaries of contact of that surface with the carrier material.
  • Contact of the carrier with the whole of the surface to be protected is not therefore necessary in order to form a lubricating layer of heteropolar molecules over all the surface to be protected.
  • the multimolecular layer is not of course formed instantaneously but builds up over a period of time. Relative movement of carrier and surface to be protected accelerate the formation and maintainance of the multimolecular layer of heteropolar molecules on the surface to be protected.
  • heteropolar molecules migrate through the carrier to the interfaces of the carrier with the surrounding environment.
  • Unsubstituted heteropolar heterocyclic unsaturated single or condensed ring systems having the aforementioned hydrogen donor and acceptor moieties have this property of migration.
  • Any substituents in such heteropolar molecules should not exert such a solubilizing effect on the heteropolar molecules that they lose their ability to migrate through the carrier to the interfaces of the carrier's environment. Since a major application of the compounds of the invention is in oils and greases it is essential that the molecules should not exert such a solubilizing effect that they fail to migrate. Consequently, where they are to be added to oils and greases any substituted groupings should not "over solubilize" the molecule. Therefore hydrocarbon substituents should preferably not contain more than 4 carbon atoms, preferably not more than 2 carbon atoms.
  • the carrier may be a liquid such as a lubricating oil or hydrocarbon fuel for an internal combustion engine or aqueous system, or the carrier may be a grease or semi-solid material (non-Newtonian fluid) such as a lubricating grease or grease-like lubricant.
  • the carrier may also be a solid such as a plastics composite, e.g. a polyamide used in repairing or rebuilding beading surfaces.
  • the content of heteropolar compound may be from 0.5% to 4% by weight based on the total weight of carrier and additive and in the case of greases or non-Newtonian fluids may be from 3% to 10% by weight based on the total weight of carrier plus additive.
  • the content of heteropolar compound is greater than 1%, e.g. from 1.1% to 4% by weight based on the total weight of carrier and additive.
  • concentration necessary in a solid carrier will depend on the type of solid carrier involved. In the case of polyamides somewhat more additive is in general necessary than that required in a semi-solid for equivalent results. This is the case of a 'Polyamid' bearing 10% by weight based on the total weight of 'Polyamid" and additive was found satisfactory. However amounts of greater than 10% e.g. 10.1% to 20% are preferred.
  • the preferred hydrogen donor moiety is a hydroxyl group. Both such moieties occur in the preferred heteropolar compound of the invention which is 8-hydroxyquinoline:-
  • Other unsubstituted heteropolar compounds useful in the method and compositions of the present invention include:
  • the number and size of the substituents which can be tolerated in the heteropolar molecule depends on the number and position of the hydrogen donor and acceptor moieties in the molecule. In general the substituents groups should not exceed four atoms in number (e.g. in the case of hydrocarbyl the butyl group), preferably no more than two atoms and more preferably still only one carbon atom.
  • a good indication of whether steric hindrance is likely to cause problems is given by measuring the adsorption-free energy of the compound in question. If the adsorption-free energy as measured on a copper surface is substantially in the range of 3 to 6 Kcal/mol then steric hindrance is unlikely to be a problem.
  • Shell Four Ball Machine Lubricating Medium Lithium grease, with 3% by weight of heteropolar compound. WITHOUT HETEROPOLAR welding at 2 7 - 2.27 N WITH HETEROPOLAR no welding at 3 7 N

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Lubricants (AREA)
  • Magnetic Record Carriers (AREA)
  • Moulds For Moulding Plastics Or The Like (AREA)
  • Polishing Bodies And Polishing Tools (AREA)

Claims (22)

1. Verfahren zur Verminderung des Verschleißes auf einer Oberfläche, die Reibungskräften ausgesetzt ist, das die Bildung einer Schutzschicht und deren Aufrechterhaltung auf der Oberfläche umfaßt, dadurch gekennzeichnet, daß die Schutzschicht eine Multimolekularschicht aus einer heteropolaren Verbindung ist, die wenigstens einen vollständig ungesättigten heterocyclischen sechsgliedrigen Ring umfaßt, bei dem wenigstens ein unsubstituiertes Heteroatomfragment als Wasserstoffakzeptor fungiert, die Verbindung auch noch zumindest ein Wasserstoffdonatorfragment umfaßt, und die heteropolare Verbindung keinen Substituenten aufweist, der als solcher oder zusammen mit einem anderen Substituenten oder anderen Substituenten eine solche sterische Behinderung bewirkt und/oder das Molekül so basisch oder sauer macht oder die sterische Geometrie des Moleküls so verändert, daß eine Wechselwirkung zwischen dem Wasserstoffdonator- und -akzeptorfragment eines Moleküls der heteropolaren Verbindung mit dem Wasserstoffdonator- und -akzeptorfragment eines anderen Moleküls der heteropolaren Verbindung verhindert wird, und auch keinen Substituenten, der als solcher oder zusammen mit einem anderen Substituenten oder anderen Substitutenten die heteropolare Verbindung in einem ausgewählten Träger soweit solubilisiert, daß die Wanderung der heteropolaren Verbindung zu den Grenzflächen zwischen dem Träger und seiner Umgebung verhindert wird und bei dem die Schutzschicht auf der zu schützenden Oberfläche durch Kontaktierung wenigstens eines Teils der Oberfläche mit einem Gemisch gebildet wird, das einen Träger und eine darin gelöste und/oder dispergierte wirksame Menge der heteropolaren Verbindung enthält.
2. Verfahren nach Anspruch 1, wobei wenigstens ein Teil der zu schützenden Oberfläche ständig mit dem Gemisch in Berührung gebracht wird.
3. Verfahren nach Anspruch 1, wobei wenigstens ein Teil der zu schützenden Oberfläche periodisch mit dem Gemisch in Berührung gebracht wird.
4. Verfahren nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß die heteropolare Verbindung bis zu drei kondensierte ungesättigte Ringe umfaßt, von denen einer der vollständig ungesättigte heterocyclische sechsgliedrige Ring ist.
5. Verfahren nach Anspruch 4, dadurch gekennzeichnet, daß einer der kondensierten Ringe ein fünfgliedriger ungesättiger heterocyclischer Ring ist.
6. Verfahren nach Anspruch 4, dadurch gekennzeichnet, daß alle kondensierten Ringe sechsgliedrige ungesättigte Ringe sind.
7. Verfahren nach einem der Ansprüche 1 bis 6, wobei der Träger eine Flüssigkeit ist.
8. Verfahren nach Anspruch 7, dadurch gekennzeichnet, daß die Flüssigkeit ein Schmieröl ist.
9. Verfahren nach Anspruch 8, dadurch gekennzeichnet, daß das Schmieröl wenigstens einen ungesättigten Kohlenwasserstoff umfaßt.
10. Verfahren nach Anspruch 9, dadurch gekennzeichnet, daß die heteropolare Verbindung in einer Menge von 1,1 bis 4 Gew.-%, bezogen auf das Gesamtgewicht von Träger und Zusatz, vorliegt.
11. Verfahren nach Anspruch 7, dadurch gekennzeichnet, daß der Träger eine wässerige Flüssigkeit ist.
12. Verfahren nach Anspruch 7, dadurch gekennzeichnet, daß der Träger ein flüssiger Kohlenwasserstoff-Kraftstoff für einen Verbrennungsmotor ist.
13. Verfahren nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, daß der Träger ein Schmierfett oder ein fettähnlicher Stoff ist.
14. Verfahren nach Anspruch 13, dadurch gekennzeichnet, daß die heteropolare Verbindung in einer Menge von 3 bis 10 Gew.-%, bezogen auf das Gesamtgewicht von Träger und Zusatz, vorliegt.
15. Verfahren nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, daß der Träger ein fester Kunststoff ist.
16. Verfahren nach Anspruch 15, dadurch gekennzeichnet, daß der feste Kunststoff ein Polyamid ist.
17. Verfahren nach Anspruch 16, dadurch gekennzeichnet, daß die heteropolare Verbindung in einer Menge von 10,1 bis 20 Gew.-%, bezogen auf das Gesamtgewicht von Träger und Zusatz, vorliegt.
18. Verfahren nach einem der vorangegangenen Ansprüche, dadurch gekennzeichnet, daß der als Wasserstoffakzeptor fungierende heterocyclische Anteil ein -N =-Fragment ist.
19. Verfahren nach Anspruch 18, dadurch gekennzeichnet, daß die heteropolare Verbindung bis zu vier -N =-Fragmente enthält.
20. Verfahren nach einem der vorangegangenen Ansprüche, dadurch gekennzeichnet, daß der Wasserstoffdonatoranteil eine -OH-Gruppe ist.
21. Verfahren nach einem der vorangegangenen Ansprüche, dadurch gekennzeichnet, daß die heteropolare Verbindung 8-Hydroxychinolin ist.
22. Verfahren nach einem der Ansprüche 1 bis 20, dadurch gekennzeichnet, daß die heteropolare Verbindung ausgewählt wird unter 2,3-Dihydroxypyridin, 4,6-Dihydroxypyrinidin, 2-Pteridinol, 2-Methyl-8-chinolinol, 2,4-Chinolindiol, 2,3-Dihydroxychinoxalin, 2,4-Pteridindiol, 6-Purinol, 3-Phenanthridinol, 2-Phenanthrolinol und 2-Phenazinol.
EP89906387A 1988-05-18 1989-05-17 Verfahren zur reduzierung des verschleisses auf oberflächen, die reibungskraeften ausgesetzt sind Expired - Lifetime EP0420868B1 (de)

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AT89906387T ATE94584T1 (de) 1988-05-18 1989-05-17 Verfahren zur reduzierung des verschleisses auf oberflaechen, die reibungskraeften ausgesetzt sind.

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GB8811696 1988-05-18
GB888811696A GB8811696D0 (en) 1988-05-18 1988-05-18 Method of reducing friction & wear between bodies in relative motion

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EP0420868B1 true EP0420868B1 (de) 1993-09-15

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DE (1) DE68909236T2 (de)
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GB2416172B (en) * 2004-07-13 2009-04-22 Alan Edwin Jemmett Rapeseed oil lubricant
HU228573B1 (hu) * 2010-04-12 2013-04-29 Jozsef Dr Fodor Növényi olajok kopást csökkentõ kenéstechnológiai alkalmazása

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US2030033A (en) * 1933-06-10 1936-02-04 Standard Oil Co Treatment of cracked petroleum distillates
US3078228A (en) * 1959-11-06 1963-02-19 Houghton & Co E F Imide compounds and lubricants containing the same
NL6704601A (de) * 1966-04-06 1967-10-09
GB1209919A (en) * 1967-07-21 1970-10-21 Geigy Uk Ltd Substituted benzotriazoles and the use thereof as metal deactivators
US3779920A (en) 1971-02-05 1973-12-18 Atlantic Richfield Co Lubricating oil composition
FR2249879A1 (en) * 1973-11-06 1975-05-30 Poudres & Explosifs Ste Nale 2,3-Dialkoxy-quinoxalines - for use as thermally stable lubricant base oils
US4075111A (en) * 1976-04-19 1978-02-21 Hughes Aircraft Company Heavy metal chalcogenide-polyimide lubricative composites
SU939527A1 (ru) 1980-05-22 1982-06-30 Особое Конструкторско-Технологическое Бюро Специального Материаловедения При Новочеркасском Политехническом Институте Металлоплакирующа смазка
US4392968A (en) * 1980-08-13 1983-07-12 Nippon Oil Company, Limited Metal deactivator and composition containing same
US4295861A (en) * 1980-10-24 1981-10-20 Phillips Petroleum Company Motor fuel
US4367152A (en) * 1981-07-02 1983-01-04 Exxon Research And Engineering Co. Selected heteroaromatic nitrogen compounds as antioxidant/metal deactivators/electrical insulators in lubricating oils and petroleum liquid fuels
JPS58225196A (ja) * 1982-06-24 1983-12-27 Nippon Mining Co Ltd デイ−ゼルエンジン用潤滑油
DE3232921A1 (de) * 1982-09-04 1984-03-08 Basf Ag, 6700 Ludwigshafen Inhibitoren gegen die korrosion von co(pfeil abwaerts)2(pfeil abwaerts) und h(pfeil abwaerts)2(pfeil abwaerts)s in wasser-in-oel-emulsionen
EP0168534A3 (de) * 1984-04-27 1986-10-22 Exxon Research And Engineering Company Dialkylaromate und hydrogenierte Dialkylaromate in synthetischen Schmierölen und speziellen Ölen
US4784782A (en) * 1986-03-27 1988-11-15 The Lubrizol Corporation Heterocyclic compounds useful as additives for lubricant and fuel compositions
EP0243026A3 (de) * 1986-04-14 1989-08-02 Exxon Research And Engineering Company Funktionelle Flüssigkeit oder Schmiermittel

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AU622912B2 (en) 1992-04-30
DK274090A (da) 1990-11-16
GB8811696D0 (en) 1988-06-22
NO302300B1 (no) 1998-02-16
CA1337292C (en) 1995-10-10
IE891588L (en) 1989-11-18
EP0420868A1 (de) 1991-04-10
DE68909236D1 (de) 1993-10-21
HU209491B (en) 1994-06-28
NO904941D0 (no) 1990-11-14
JPH03504252A (ja) 1991-09-19
FI905592A0 (fi) 1990-11-12
AU3697789A (en) 1989-12-12
NO904941L (no) 1990-11-14
DK274090D0 (da) 1990-11-16
WO1989011518A3 (en) 1990-02-08
WO1989011518A2 (en) 1989-11-30
NZ229188A (en) 1991-04-26
ES2017252A6 (es) 1991-01-16
HU893619D0 (en) 1991-05-28
ZA893729B (en) 1991-01-30
IE61949B1 (en) 1994-11-30
KR900701977A (ko) 1990-12-05
DE68909236T2 (de) 1994-03-17
HUT56389A (en) 1991-08-28

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