EP0406894B1 - Diharnstoff-Schmierfettzusammensetzung - Google Patents

Diharnstoff-Schmierfettzusammensetzung Download PDF

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Publication number
EP0406894B1
EP0406894B1 EP90112952A EP90112952A EP0406894B1 EP 0406894 B1 EP0406894 B1 EP 0406894B1 EP 90112952 A EP90112952 A EP 90112952A EP 90112952 A EP90112952 A EP 90112952A EP 0406894 B1 EP0406894 B1 EP 0406894B1
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EP
European Patent Office
Prior art keywords
amine
diurea
formula
group
diisocyanate
Prior art date
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EP90112952A
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English (en)
French (fr)
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EP0406894A1 (de
Inventor
Hirotugu Kinoshita
Makoto Sekiya
Masaru Mishima
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Eneos Corp
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Nippon Oil 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
    • C10M115/00—Lubricating compositions characterised by the thickener being a non-macromolecular organic compound other than a carboxylic acid or salt thereof
    • C10M115/08—Lubricating compositions characterised by the thickener being a non-macromolecular organic compound other than a carboxylic acid or salt thereof containing nitrogen
    • 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
    • C10M2201/10—Compounds containing silicon
    • C10M2201/102—Silicates
    • C10M2201/103—Clays; Mica; Zeolites
    • 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
    • C10M2201/10—Compounds containing silicon
    • C10M2201/105—Silica
    • 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
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
    • C10M2205/026—Butene
    • 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
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/04—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing aromatic monomers, e.g. styrene
    • 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
    • C10M2207/40—Fatty vegetable or animal oils
    • 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
    • C10M2207/40—Fatty vegetable or animal oils
    • C10M2207/404—Fatty vegetable or animal oils obtained from genetically modified species
    • 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
    • C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/08—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type
    • C10M2209/084—Acrylate; Methacrylate
    • C—CHEMISTRY; METALLURGY
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    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions
    • C10M2215/10—Amides of carbonic or haloformic acids
    • C10M2215/102—Ureas; Semicarbazides; Allophanates
    • 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
    • C10M2215/24—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
    • C10M2215/30—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
    • 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
    • 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
    • C10M2219/102—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring containing sulfur and carbon only 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
    • 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
    • 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
    • C10M2219/106—Thiadiazoles
    • 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
    • C10M2223/045—Metal containing thio derivatives
    • 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

Definitions

  • This invention relates to a diurea grease composition. More particularly, it relates to a diurea grease composition which undergoes little changes in consistency after use at higher temperatures for a prolonged period of time and small oil separtion at higher temperatures and which is also superior in various other properties.
  • the lithium soap grease known as the "universal grease”
  • the universal grease has a dropping point of the order of 200°C or thereabouts and cannot be used at higher temperatures above 150°C.
  • urea greases such as diurea grease or tetraurea greases having modified terminal groups
  • the tetraurea grease tends to be hardened or increased in consistency when exposed to higher temperatures for prolonged time period, while it may be disadvantageously hardened or softened depending on different shearing speeds given to the grease.
  • the known diurea greases having only terminal alkyl groups have a low dropping point and undergoes considerable oil separation at higher temperatures so that they cannot be used for prolonged time at higher temperatures.
  • the diurea greases having only aromatic hydrocarbon terminal groups are at most equivalent or even inferior to the diurea greases having the terminal alkyl groups with respect to the properties as the thickener.
  • the present inventors have conducted researches towards overcoming the above mentioned drawbacks of the urea greases and have found that, while the diurea compound has highly desirable properties as the thickener, the terminal groups of the diurea compound plays an extremely important role.
  • This diurea compound has been applied for patent in our Japanese Patent Publication No. 11156/1980.
  • Ths diurea grease disclosed in the Japanese Patent Publication No. 11156/1980 has many excellent properties, such as
  • a diurea grease composition comprising a base oil and 2 to 25 wt.%, based on the total weight of the composition, of a diurea compound as an essential ingredient, said diurea grease compound being produced by reacting
  • any oils commonly used as the lube base oil may be employed.
  • mineral lube base oils mineral oils refined by a method consisting in a suitable combination of distillation under reduced pressure, solvent deasphalting, solvent extraction, hydrocracking, solvent dewaxing, hydrogenative dewaxing, washing by sulfuric acid, refining by terra abla or hydrofining.
  • ⁇ -olefin oligomers such as normal paraffins, isoparaffins, polybutene, polyisobutyrene or 1-decene oligomers
  • alkylbenzenes such as monoalkylbenzene, dialkylbenzene or polyalkylbenzene
  • alkyl naphthalenes such as monoalkyl naphthalene, dialkyl naphthalene or polyalkyl naphthalene
  • diesters such as di-2-ethylhexyl sebacate, dioctyl adipate, diisodecyl adipate, ditridecyl adipate or ditridecyl glutarate
  • polyol esters such as trimethylolpropane caprylate, trimethylolpropane pelargonate, pentaerithritol-2-ethyl hexanoate or pentaerithr
  • the diurea compound as the essential ingredient of the composition of the present invention may be obtained by reacting a diisocyanate mixture comprising diphenylmethane diisocyanate and tolylene diidocyanate with a amine compound selected from (a) a primary amine represented by the formula (I) R1-NH2 (I) wherein R1 stands for a hydrocarbon residue having 6 to 20 carbon atoms, (b) a secondary amine represented by the formula (II) wherein R2 and R3 may be the same or different and each stand for hydrocarbon residues having 6 to 20 carbon atoms, and (c) mixtures of (a) and (b)
  • the aforementioned mixture of diisocyanate includes mixtures of two or more compounds selected from diphenylmethane-4, 4'-diisocyanate and tolylene diisocyanate. More specifically, it may include a mixed system of diphenylmethane-4,4'-diisocyanate and a mixture of 2, 4-tolylene diisocyanate and 2, 6-tolylene diisocyanate.
  • the mixing ratios of the above mentioned diisocyanates may be suitably selected in dependence upon the structures of the diisocyanates and the consistency of the greases to be produced.
  • the mixing ratio may usually be 5 - 95 : 95 - 5, preferably 10 - 90 : 90 - 10, more preferably 20 - 80 : 80 - 20 and most preferably 30 - 70 : 70 - 30, in terms of a mol percent ratio.
  • a mixing ratio of less than the range of 5 - 95 : 95 - 5 is not desirable since problems are raised in changes in consistency after use or in oil separation so that the properties of the grese thickener are lowered.
  • the mixing ratio is preferably 10 to 95 mol percent, prferably 20 to 80 mol percent and most preferably 30 to 70 mol percent of diphenylmethane-4, 4'-diisocyanate and 5 to 90 mol percent, preferably 20 to 80 mol percent and most preferably 30 to 70 mol percent of tolylene diisocyanate.
  • the respective diisocyanates are preferably contained in amounts of not less than 5 mol percent and preferably not less than 10 mol percent.
  • the amine compound reacted with the mixed diisocyanate system is a primary amine, a mixture of two or more primary amines, a secondary amine, or a mixture of two or more different secondary amines, represented by the above formulas (I) and (II), or mixtures thereof.
  • R1, R2 and R3 may be the same or different groups and denote hydrocarbon residues with 6 to 20 carbon atoms.
  • hydrocarbon residues various groups such as alkyl, alkenyl, cycloalkyl or aromatic groups, may be employed.
  • the alkyl groups may include those with straight or branched chains, such as hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl or eicosyl groups.
  • the alkenyl groups may include those with straight or branched chains, such as hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl, nonadecenyl or eicosenyl groups.
  • cyclohexyl group and the groups derived from the cyclohexyl group may preferably be employed.
  • examples of the cyclohexyl group and its derivatives may include cyclohexyl, methyl cyclohexyl, dimethyl cyclohexyl, ethyl cyclohexyl, diethyl cyclohexyl, propyl cyclohexyl, isopropyl cyclohexyl, 1-methyl-3-propylcyclohexyl, butyl cyclohexyl, amyl cyclohexyl, amylmethyl cyclohexyl, hexyl cyclohexyl, heptyl cyclohexyl, octyl cyclohexyl, nonyl cyclohexyl, decyl cyclohexyl, undecyl cyclohexyl
  • cyclohexyl group and C7 to C8 groups derived from the cyclohexyl group such as, for example, methyl cyclohexyl, dimethyl cyclohexyl or ethyl cyclohexyl groups.
  • aromatic groups may include phenyl, toluyl, benzyl, ethyl phenyl, methyl benzyl, xylyl, propyl phenyl, cumenyl, ethyl benzyl, methyl phenetyl, butyl phenyl, propyl benzyl, ethyl phenetyl, pentyl phenetyl, butyl benzyl, propyl phenetyl, hexyl phenyl, pentyl benzyl, butyl phenetyl, heptyl phenyl, hexyl benzyl, pentyl phenetyl, octyl phenyl, heptyl benzyl, hexyl phenetyl, nonyl phenyl, octyl benzyl, heptyl phenety
  • the most preferred amine compound to be reacted with the above mentioned diisocyanate mixed system is a primary amine represented by the formula (I) in which R1 denotes a cyclohexyl group, a C7 to C12 alkylcyclohexyl group, a C 6 to C20 alkyl group or a C6 to C20 alkenyl group, or a secondary amine represented by the formula (II) in which R2 and R3 each denote a cyclohexyl group or a C7 to C12 alkylcyclohexyl group.
  • Most preferred is also an amine mixture in which the primary amine represented by the formula (I) is used and in which the ratio of the total number of cyclohexyl groups and/or the alkyl cyclohexyl groups to the number of the total amines given by the formula ⁇ (total number of the cyclohexyl groups and/or the alkylcyclohexyl groups)/(the total number of the groups selected from the group consisting of the cyclohexyl group, alkylcyclohexyl group, alkyl group and the alkenyl group bonded to the amine employed) ⁇ X 100 is 20 to 90 in terms of mol percent.
  • contents of the diurea compound containing both the cyclohexyl groups and/or alkylcyclohexyl groups and the alkyl groups and/or alkenyl groups in the produced diurea compound account for 10 mol percent or higher based on the total number of the produced diurea compounds.
  • an amine mixture consisting of a primary amine of the formula (I) in which R1 is a cyclohexyl group, a C7 to C12 alkyl cyclohexyl group or a C6 to C20 alkyl group,and a secondary amine of the formula (II) in which R2 and R3 each represent a cyclohexyl group or a C7 to C12 alkyl cyclohexyl group and in which the ratio of the contents of the secondary amine to the amount of total amine given by the formula ⁇ (number of amino groups in the secondary amine)/(number of the amino groups in the primary amine plus number of the amino groups in the secondary amine) ⁇ X 100 is 1 to 50 in terms of mol percent, or an amine mixture in which the total amount of the primary amine of the formula (I) in which R1 is a cyclohexyl group or an alkylcyclohexyl group bears a molar ratio of 1/4
  • the diurea compound acting as the thickener, is produced by reacting the above mentioned mixed system of the diisocyanates with the above mentioned primary amine and/or secondary amine. This point is most crucial in the present invention.
  • the effects of the present invention cannot be derived from the diurea grease obtained in any other methods, such as by separately reacting the above mentioned two or more diisocyanates with amines and subsequently mixing the produced two or more diurea compounds.
  • volatile solvents such as benzene, toluene, xylene, hexane, naphtha, diisobutyl ether, carbon tetrachloride or petroleum ether, may be employed.
  • Lube base oils may also be employed as suitable solvents.
  • the preferred reaction temperature is 100 to 200°C. The reaction system need be mixed and agitated thoroughly to produce a uniform diurea grease.
  • the thus produced diurea compound acting as the thickener, contains the diurea compounds in amounts corresponding to the mixing ratios of the diisocyanates. More specifically, if the mixed system consisting of 10 to 95 mol percent of diphenylmethane-4, 4'-diisocyanate and 5 to 95 mol percent of tolylene diisocyanate is employed, the thickener contains 10 to 95 mol percent of a diurea compound represented by the formula and 5 to 90 mol percent of a diurea compound represented by the formula wherein X1, X2, X3 and X4 each stand for one of the groups R1-NH- or where R1, R2 and R3 have the same meaning as R1, R2 and R3 in the above formulas (I) and (II).
  • the volatile solvent is used, the solvent is removed and a suitable amount of the lube base oil is added to give the grease.
  • the reaction product may be used directly as the grease.
  • the contents of the diurea compound acting as the thickener is 2 to 25 wt.% and preferably 3 to 20 wt.% based on the total weight of the composition.
  • the contents of the diurea compound less than 2 wt.% are not desirable because the effects as the thickener are nill, whereas the contents in excess of 25 wt.% are also not desirable because the grease becomes too hard and cannot exhibit the lubricating effects sufficiently.
  • the grease of the present invention may be admixed with suitable additives for further improving its properties.
  • suitable additives include other thickeners, such as metal soaps, bentone or silica gel, extreme pressure agents, such as chlorine, sulphur or phosphorus extreme pressure agents or zinc dithiophosphate, oiliness agents such as fatty oils, animal or vegetable oils, viscosity index improvers, such as polymethacrylate, polybutene or polystyrene, anti-oxidants such as amine, phenol or sulpher anti-oxidants or zinc dithiophosphate, or metal inactivators, such as benzotriazole or thiadiazole.
  • the dropping point was measured in accordance with the dropping point testing method in JIS K 2220 5.4.
  • the oil separation was measured at 150°C for 200 hours in accordance with the oil separation testing method in JIS K 2220 5.7.
  • the produced diurea compound was formed by 80 mol percent in total of diurea compounds represented by the formulas and and 20 mol percent in total of diurea compounds represented by the formulas and The contents in the composition of the thickener formed by the diurea compounds were 10 wt.%.
  • the produced diurea compound was formed by 30 mol percent in total of the diurea compounds reprsented by the formulas and and 70 mol percent in total of the diurea compounds represented by the formulas and The contents in the composition of the thickener formed by the diurea compounds were 10 wt.%.
  • the produced diurea compound was comprised of 50 mol percent in total of the diurea compounds represented by the formulas and and 50 mol percent in total of the diurea compounds represented by the formulas and with the sum of the amounts of the compounds represented by the formulas (2) and (5) being 50 mol percent.
  • the contents in the composition of the thickener formed by the diurea compounds were 10 wt.%.
  • the produced diurea compound was formed by 30 mol percent of a diurea compound represented by the formula and 70 mol percent of a diurea compound represented by the formula where Y1, Y2, Y3 and Y4 each stand for groups -NH-C18H37 or at a rate of 30 : 30 :40.
  • the contents in the composition of the thickener formed by the diurea compounds were 10 wt.%.
  • the performance appraisal tests similar to those of Example 1 were conducted on the produced diurea grease. The resulta are shown in Table 1.
  • the resulting mixture was agitated thoroughly and passed through a roll mill to produce a grease composition.
  • This diurea compounds were formed by 40 mol percent in total of diurea compounds represented by the formulas and and 60 mol percent in total of diurea compounds represented by the formulas and wherein the sum of the amounts of the compounds represented by the formulas (8) and (11) is 30 mol percent and the ratio of the contents of the methylcyclohexyl group and the octyl group is 70 : 30.
  • the contents in the composition of the thickener formed by the diurea compounds were 10 wt.%.
  • the produced diurea composition was formed by 60 mol percent of a diurea compound represented by the formula and 40 mol percent of a diurea compound represented by the formula wherein Y1, Y2, Y3 and Y4 each represent groups or at the ratio of 40 : 30 : 30.
  • the contents in the composition of the thickener formed by the diurea compounds were 10 wt.%.
  • the contents of the diurea compound of the formula acting as the thickener were 10 wt.%.
  • the contents of the diurea compound of the formula acting as the thickener were 10 wt.%.
  • the diurea composition was formed by 50 mol percent of a diurea compound represented by the formula and 50 mol percent of a diurea compound represented by the formula
  • the contents in the composition of the thickener formed by the diurea compounds were 10 wt.%.
  • the diurea grease composition of the present invention has an improved shearing stability and a high dropping point while being subject to small oil separation and exhibiting superior thickening properties.
  • the grease compositions of the Comparative Examples 1 to 5 are equivalent or inferior to the inventive grease composition in shearing stability and dropping point while being evidently inferior to the inventive grease in thickening properties and oil separation at higher temperatures.
  • the grease composition of the present invention is superior in its various properties to the compositions of the Comparative Exmples 1 to 5.

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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 (7)

  1. Diharnstoff-Schmierstoffzusammensetzung, welche ein Basisöl und 2 bis 25 Gew.-%, bezogen auf das Gesamtgewicht der Zusammensetzung, einer Diharnstoffverbindung als wesentlichen Bestandteil enthält, wobei die Diharnstoff-Schmierstoffverbindung durch Umsetzung von
    (A) einer Diisocyanatmischung mit
    (B) einer Aminverbindung, ausgewählt aus
    (a) einem durch die Formel (I)

            R₁ - NH₂   (I)

    wiedergegebenen primären Amin, worin R₁ für einen Kohlenwasserstoffrest mit 6 bis 20 Kohlenstoffatomen steht,
    (b) einem durch die Formel (II)
    Figure imgb0048
     wiedergegebenen sekundären Amin, worin R₂ und R₃ gleich oder verschieden sein können und jeweils für Kohlenwasserstoffreste mit 6 bis 20 Kohlenstoffatomen stehen, und
    (c) Mischungen aus (a) und (b) erzeugt ist,
    dadurch gekennzeichnet, daß die Diisocyanatmischung (A) Diphenylmethandiisocyanat und Tolylendiisocyanat enthält.
  2. Diharnstoff-Schmierstoffzusammensetzung nach Anspruch 1, worin das Mischungsverhältnis von Diphenylmethandiisocyanat und Tolylendiisocyanat in der Diisocyanatmischung 5 bis 95 : 95 bis 5, ausgedrückt als Mol-%, beträgt.
  3. Diharnstoff-Schmierstoffzusammensetzung nach Anspruch 1 oder 2, worin die Aminverbindung ein Amin der Formel (I) ist, worin R₁ eine Cyclohexylgruppe ist, ein Amin der Formel (I), worin R₁ eine Alkylcyclohexylgruppe mit 7 bis 12 Kohlenstoffatomen ist, ein Amin der Formel (I), worin R₁ eine Alkylgruppe mit 6 bis 20 Kohlenstoffatomen ist, ein Amin der Formel (I), worin R₁ eine Alkenylgruppe mit 6 bis 20 Kohlenstoffatomen ist, ein Amin der Formel (II), worin R₂ und R₃ jeweils eine Cyclohexylgruppe darstellen, ein Amin der Formel (II), worin R₂ und R₃ jeweils eine Alkylcyclohexylgruppe mit 7 bis 12 Kohlenstoffatomen darstellen, oder eine Mischung davon.
  4. Diharnstoff-Schmierstoffzusammensetzung nach Anspruch 1 oder 2, worin die Aminverbindung eine Mischung aus primären Aminen der Formel (I) von Cyclohexylamin, Alkylcyclohexylamin oder Mischungen davon ist, wobei die Gesamtmenge an Cyclohexylamin, Alkylcyclohexylamin und Mischungen davon 20 bis 90 Mol-% der Gesamtaminmenge ausmacht.
  5. Diharnstoff-Schmierstoffzusammensetzung nach Anspruch 1 oder 2, worin die Aminverbindung eine Aminmischung unter Einschluß eines primären Amins der Formel (I), worin R₁ ein Cyclohexylgruppe, eine C7- bis C12-Alkylcyclohexylgruppe oder eine C6- bis C20-Alkylgruppe, und eines sekundären Amins der Formel (II), worin jedes von R₂ und R₃ eine Cyclohexylgruppe oder eine C7- bis C12-Alkylcyclohexylgruppe ist, einschließt, worin der Gehalt des sekundären Amins 1 bis 50 Mol-% der Gesamtmenge der Aminverbindung ausmacht und worin die Gesamtmenge des primären Amins der Formel (I), worin R₁ eine Cyclohexylgruppe oder eine Alkylcyclohexylgruppe ist, ein Molverhältnis von 1/4 bis 4/1 in bezug auf die Menge des primären Amins der Formel (I), worin R₁ eine Alkylgruppe ist, ausmacht.
  6. Diharnstoff-Schmierstoffzusammensetzung nach Anspruch 1 oder 2, worin die Diharnstoff-Verbindung mit einer Cyclohexylgruppe, einer Alkylcyclohexylgruppe oder Mischungen davon und die Diharnstoff-Verbindung mit einer Alkylgruppe, einer Alkenylgruppe oder Mischungen davon in einer Menge vorhanden sind, die nicht weniger als 10 Mol-% der gesamten Diharnstoff-Verbindungen in der Zusammensetzung ausmacht.
  7. Diharnstoff-Schmierstoffzusammensetzung nach Anspruch 1, worin das Tolylendiisocyanat aus einer Mischung aus 2,4-Tolylendiisocyanat und 2,6-Tolylendiisocyanat besteht.
EP90112952A 1989-07-07 1990-07-06 Diharnstoff-Schmierfettzusammensetzung Expired - Lifetime EP0406894B1 (de)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP17408489 1989-07-07
JP174084/89 1989-07-07
JP155338/90 1990-06-15
JP2155338A JP2777928B2 (ja) 1989-07-07 1990-06-15 ジウレアグリース組成物

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EP0406894A1 EP0406894A1 (de) 1991-01-09
EP0406894B1 true EP0406894B1 (de) 1993-12-22

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JP2864473B2 (ja) * 1992-06-29 1999-03-03 昭和シェル石油株式会社 ウレア系グリース組成物
JP2002146377A (ja) * 2000-11-06 2002-05-22 Seiko Instruments Inc ハードディスク装置用グリース組成物及びその製造方法
JP2006249271A (ja) * 2005-03-11 2006-09-21 Ntn Corp グリース組成物およびグリース封入転がり軸受
JP5322393B2 (ja) * 2007-02-06 2013-10-23 協同油脂株式会社 グリース組成物及びその製造方法
JP5417621B2 (ja) * 2008-02-29 2014-02-19 協同油脂株式会社 グリース組成物及びその製造方法
US9012384B2 (en) * 2010-07-30 2015-04-21 Chevron U.S.A. Inc. Method of preparing greases
JP6838924B2 (ja) * 2016-10-13 2021-03-03 デュポン・東レ・スペシャルティ・マテリアル株式会社 グリース組成物およびその製造方法
CN111394150B (zh) * 2020-04-23 2022-01-28 沈阳理工大学 一种耐高温五聚脲润滑脂及其制备方法

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US3082170A (en) * 1960-09-23 1963-03-19 Gulf Research Development Co Polyorgano siloxane thickened to a grease consistency with a diazo compound and an arylurea
US3374170A (en) * 1966-04-04 1968-03-19 Gulf Research Development Co Grease composition
JPS52156274A (en) * 1976-06-21 1977-12-26 Nippon Oil Co Ltd Break grease composition
JPS61155496A (ja) * 1984-12-27 1986-07-15 Koyo Seiko Co Ltd ジウレア系グリ−ス組成物
JPH0660316B2 (ja) * 1986-04-22 1994-08-10 日本石油株式会社 ジウレアグリ−ス組成物
JPS63312397A (ja) * 1987-06-16 1988-12-20 Kyodo Yushi Kk 潤滑剤組成物
JPH0692592B2 (ja) * 1987-11-26 1994-11-16 昭和シェル石油株式会社 ウレアグリースの組成物

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DE69005380D1 (de) 1994-02-03
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JP2777928B2 (ja) 1998-07-23
JPH03128993A (ja) 1991-05-31

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