US3846315A - Grease thickened with polyurea metal salts and alkaline earth metal aliphatic monocarboxylate - Google Patents

Grease thickened with polyurea metal salts and alkaline earth metal aliphatic monocarboxylate Download PDF

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Publication number
US3846315A
US3846315A US00374212A US37421273A US3846315A US 3846315 A US3846315 A US 3846315A US 00374212 A US00374212 A US 00374212A US 37421273 A US37421273 A US 37421273A US 3846315 A US3846315 A US 3846315A
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Prior art keywords
polyurea
grease
metal
reaction
acid
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US00374212A
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English (en)
Inventor
G Stanton
J Dreher
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Chevron USA Inc
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Chevron Research and Technology Co
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Priority to US00374212A priority Critical patent/US3846315A/en
Priority to CA194,321A priority patent/CA1036147A/en
Priority to GB1465674A priority patent/GB1457316A/en
Priority to BE143703A priority patent/BE814283A/xx
Priority to JP5063474A priority patent/JPS5628960B2/ja
Priority to FR7421315A priority patent/FR2235189B1/fr
Priority to IT24329/74A priority patent/IT1019664B/it
Priority to DE2430505A priority patent/DE2430505A1/de
Priority to NL7408691A priority patent/NL7408691A/xx
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Publication of US3846315A publication Critical patent/US3846315A/en
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    • C10M123/00—Lubricating compositions characterised by the thickener being a mixture of two or more compounds covered by more than one of the main groups C10M113/00 - C10M121/00, each of these compounds being essential
    • C10M123/04—Lubricating compositions characterised by the thickener being a mixture of two or more compounds covered by more than one of the main groups C10M113/00 - C10M121/00, each of these compounds being essential at least one of them being a macromolecular compound
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    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04—Phosphate esters
    • C10M2223/042—Metal salts thereof
    • 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
    • C10M2227/00—Organic non-macromolecular compounds containing atoms of elements not provided for in groups C10M2203/00, C10M2207/00, C10M2211/00, C10M2215/00, C10M2219/00 or C10M2223/00 as ingredients in lubricant compositions
    • C10M2227/02—Esters of silicic acids
    • 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
    • C10M2229/00—Organic macromolecular compounds containing atoms of elements not provided for in groups C10M2205/00, C10M2209/00, C10M2213/00, C10M2217/00, C10M2221/00 or C10M2225/00 as ingredients in lubricant compositions
    • C10M2229/04—Siloxanes with specific structure
    • C10M2229/041—Siloxanes with specific structure containing aliphatic substituents
    • 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
    • C10M2229/00—Organic macromolecular compounds containing atoms of elements not provided for in groups C10M2205/00, C10M2209/00, C10M2213/00, C10M2217/00, C10M2221/00 or C10M2225/00 as ingredients in lubricant compositions
    • C10M2229/04—Siloxanes with specific structure
    • C10M2229/042—Siloxanes with specific structure containing aromatic substituents
    • 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
    • C10N2010/02—Groups 1 or 11
    • 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

  • An improved grease composition comprising a major portion of a lubricating oil containing (1) a polyurea metal salt wherein the polyurea portion of the molecule is prepared by reacting a diisocyanate, a polyamine with a monoisocyanate or monoamine and the metal salt portion is prepared by introducing into the above reaction product an acid group, such as a carboxylic or a sulfonic acid group, and neutralizing the terminal acid group with a basic metal compound, and (2) an alkaline earth metal aliphatic monocarboxylate having from 1 to 3 carbons.
  • a polyurea metal salt wherein the polyurea portion of the molecule is prepared by reacting a diisocyanate, a polyamine with a monoisocyanate or monoamine and the metal salt portion is prepared by introducing into the above reaction product an acid group, such as a carboxylic or a sulfonic acid group, and neutralizing the terminal acid group with a basic metal compound, and (2) an alkaline earth metal aliphatic
  • This invention relates to a novel grease composition. More particularly, this invention concerns grease composition containing a novel metal-containing polyurea thickening agent.
  • Another type of grease composition which has excellent lubricating properties at the higher temperatures is comprised of a lubricating oil (natural or synthetic) containing a polyurea thickener.
  • This type of lubricant is dis- 3,846,315 Patented Nov. 5, 1974 closed in US. Pat. Nos. 3,242,210; 3,243,372; 3,281,- 361; 3,284,357; 3,346,497; and 3,401,027, all assigned to the Chevron Research Company.
  • the polyurea thickener imparts a significant high temperature stability to the grease and, in fact, effects a mild anti-thixotropic property, i.e., increase in viscosity with increasing shear, to the lubricant. This property of the lubricant is advantageous to prevent the segregation or loss of grease from the moving parts of the machine.
  • Another type of grease which has excellent lubricating properties is comprised of a lubricating oil containing a polyurea metal salt thickener.
  • This type of grease is disclosed in US. application Ser. No. 259,053, filed June 2, 1972, now Pat. No. 3,769,212. While the above polyurea greases have solved most of the problems associated with the older lubricants, they are handicapped by the requirement of large amounts of polyurea or polyurea metal salt (between 8 and 20 weight percent) and its relatively high costs. In addition, the polyurea or polyurea metal salts do not impart extreme pressure properties to the lubricant and, accordingly, E.P. additives must be added in applications involving high contact pressures. A need therefore still exists for an improved grease thickener which, when incorporated into a grease composition, can be used for longer periods at elevated temperatures, that exhibits good stability over prolonged periods, that exhibits both extreme pressure and antiwear properties and that is relatively inexpensive to make.
  • a grease composition containing (1) an alkali or alkaline earth metal salt of a polyurea compound having a minimum of two ureido groups and having a molecular weight between about 250 and 2500 and preferably between about 300 and 2000 and (2) an alkaline earth metal aliphatic monocarboxylate having from 1 and 3 carbons.
  • the polyurea salts can be prepared by two different reaction schemes.
  • a diisocyanate, a polyamine (preferably a diarnine) and a monoisocyanate or monoamine are reacted with an amino acid metal salt or an amino carboxylic acid which is thereafter reacted with a basic metal compound capable of hydrolyzing the carboxylic acid group.
  • a diisocyanate and a polyamine are reacted with a monoamine or monoisocyanate to form an intermediate polyurea.
  • the terminal group is an isocyanate, it is then contacted with water in the presence of a caustic to form the corresponding polyurea amine and by-product carbon dioxide.
  • the polyurea amine is then reacted with an anhydrid'e, lactone or sultone and thereafter saponified with a basic metal compound to form the polyurea metal salt.
  • the polyurea content may be reduced by 50 percent of that required in the prior polyurea lubricants for the same dropping point and other physical properties. Moreover, the presence of the metal carboxylate imparts good extreme pressure properties to the lubricant and thus the addition of other E.P. additives in many cases is not necessary.
  • this combination effects a substantial increase in the extreme pressure properties as measured by its Timken test to values greater than that realized by the combination of polyurea and alkaline earth metal carboxylates.
  • this invention concerns a grease containing a thickening agent which is simply a carboxylate or sulfonate metal salt bonded to an organic polyurea radical having at least two ureido groups and preferably from 2 to 8 ureido groups.
  • a ureido group as referred to herein is defined as:
  • the preferred polyurea metal salts have structures defined by the following general formulae:
  • R 0 0 1 (P a M is a metal selected from Groups I and II of the Periodic Table;
  • n is an integer from to 3 and preferably 1;
  • n is an integer from 1 to 3 and preferably 1;
  • n is an integer from 0 to 1;
  • w is an integer from 1 to 2 and sufficient to make the compound electroneutral;
  • z is an integer from 0 to 2;
  • v is an integer from 0 to 1;
  • t is an integer equal to 1 when v is 0 and 0 when v is 1;
  • R is the same or different hydrocarbylene having from 2 to 30 carbons and more preferably an arylene having from 6 to 20 carbons;
  • R is the same or different trivalent hydrocarbon radical having from 1 to 30 carbons and preferably from 1 to 12 carbon atoms.
  • hydrocarbyl is a monovalent organic radical composed essentially of hydrogen and carbon and may be aliphatic, aromatic or alicyclic or combinations thereof, e.g., aralkyl, alkyl, aryl, cycloalkyl, alkylcycloalkyl, etc., and may be saturated or ethylenieally unsaturated (one or more double bonded carbons, conjugated or nonconjugated).
  • the hydrocarbylene is a divalent hydrocarbon radical which may be aliphatic, alicyclic, aromatic or combinations thereof, e.g., alkyl, aryl, alkylaryl, aralkyl, alkylcycloalkyl, cycloalkylaryl, etc., having its two free valences on different carbon atoms.
  • a small amount of inert substituents may be included within the hydrocarbyl chain without affecting the properties of the grease.
  • the above formulas represent only a general description of the poly'urea metal salts of this invention. It should be recognized, for example, that in the preparation of the above polyurea salts some of the molecules may have less than all of the carboxylic groups bonded to a metal atom (M). Some of the metal atoms may be bonded to carboxylate or sulfonic acid groups in two or more polyurea compounds, such as metals bonded to two molecules of any one structure or molecules of different structures, etc. Moreover, some of the metal atoms may be partially or fully ionized and exist as cations within the product mixture.
  • M metal atom
  • the polyurea metal salts can be conveniently prepared by two different reaction schemes.
  • a polyurea compound is prepared by reacting n molar parts of polyamine with n+1 molar parts of diisocyanate and one molar part of a monoamine.
  • This reaction product will have a free terminal isocyanate group which can be bydrolyzed to a free terminal amine group by reaction with an aqueous base.
  • n+1 molar parts of polyamine and n molar parts of diisocyanate are employed and a monoisocyanate is used in place of the monoamine above, the resulting polyurea compound has a terminal amine group and, hence, the hydrolysis step is not necessary.
  • the polyurea reaction products having a free terminal amine group is then further reacted with an anhydride, lactone or sultone having from 2-24 carbons to form a polyurea having one or more free carboxylic acid or sulfonic acid groups.
  • the polyurea metal salt is formed by reacting the polyurea carboxylic or sulfonic acid with a metal base.
  • Polyurea metal salts having structures set forth by Formula 2 are prepared when a monoamine is employed. When a monoisocyanate is used, the polyurea metal salts will have structures as set forth in Formula 3.
  • the carboxylic or sulfonic acid group is attached in situ during the reaction of the polyurea precursors.
  • the compounds prepared have structures as shown in Formulae 1 and 4. These compounds are prepared by reacting n or n molar parts of a polyamine with n+1 or In molar parts of a diisocyanate, one molar part of a monoamine or monoisocyanate and one molar part of an amino carboxylic acid, amino sulfonic acid or a metal salt thereof. The reaction product having a free carboxylic or sulfonic acid group is then reacted with a metal base to form polyurea metal salt.
  • the desired reactants diisocyanate, polyamine, carboxyl group source and monoamine or monoisocyanate are admixed within a suitable reaction vessel in the proper proportions and preferably within an inert liquid reaction medium.
  • the reaction may proceed without the presence of a catalyst and is initiated by merely contacting the reactants under conditions conducive for the reaction.
  • Typical reaction temperatures range from 200 to 300 F. and preferably between about 150 and 260 F. Elevated pressures as well as reduced pressures may be employed. In many cases, the reaction will be exothermic and the temeprature will rise during the course of the reaction. External heating or cooling, however, may be employed as required.
  • reaction conditions are maintained for a period sufiicient to produce the intermediate polyurea with a free terminal carboxyl or sulfonic acid group.
  • the reaction time is dependent upon the process conditions, reactants, presence of a catalyst, etc., but generally varies between about 0.5 and 4 hours.
  • the reaction vessel After formation of the intermediate polyurea compound, i.e., formation of a polyurea compound having a terminal sulfonic acid, or carboxylic acid, or ester thereof, the reaction vessel is charged with a basic metal compound, preferably within an aqueous or alcoholic solution.
  • the metal base reacts to form the terminal carboxyl or sulfonic acid groups to produce the polyurea metal salt and by-product water, or alcohol.
  • the reaction may also proceed without the presence of a catalyst and is initiated by merely contacting the intermediate polyurea with the basic metal compound under conditions conducive for the reaction.
  • Typical reaction temperatures range from 200 to 350 F. and preferably between about 250 and 320 F.
  • the reaction is preferably conducted at atmospheric pressure; however, it may be advantageous to conduct the reaction at subatmospheric pressures so that the by-product water, or alcohol may be continuously removed from the system as soon as it is formed. It the by-products are not stripped during the reaction, they may be removed from the system on completion of the reaction by heating the products to about 200 F. to 340 F. for approximately 30 to 120 minutes.
  • oil to be thickened typically a hydrocarbon oil and preferably the oil to be thickened.
  • the entire volume of oil to be thickened may be present, or, alternatively, a concentrate of thickened material containing up to 60 weight percent of the polyurea metal salt composition may be formed and this may subsequently be diluted to the desired concentration of the thickener.
  • the reaction of the basic metal compound and the intermediate polyurea may be avoided by replacing the carboxyl or sulfonic-acid group source reactant with a metal salt of an amino acid in the initial reaction.
  • the polyurea metal salt is formed directly by reacting the polyurea precursors (diisocyanate, polyamine, and monoisocyanate or monoamine) with an amino acid etal salt.
  • the reaction conditions are the same as described above, i.e., temperatures of to 300 F., etc.
  • the molar ratio of diisocyanate and polyamine present within the reaction medium during the initial reaction will control the size of the polyurea component.
  • the ratio of monoamine, monoisocyanate and carboxylic group source or amine carboxylate salt present to the diisocyanate will control the point at which the polyurea polymer chain is terminated.
  • an excess of the latter reactants will terminate the polyurea chain early and result in low molecular weight products, whereas, an excess of the former reactants will result in long chain or high molecular weight products.
  • the amounts of the various reactants within the reaction medium are set forth in the following Table II and expressed in terms of mol percent based on the mols of reactants present.
  • the monoamine or monoisocyanate used in the formulation of the polyurea salt will form one of the terminal end groups.
  • these terminal end groups will have from 1 to 30 carbon atoms, but are preferably from 5 to 28 carbons, and more desirably from l2l8 carbon atoms.
  • Illustrative of various monoamies are phenylamine, hexylamine, heptylamine, octylamine, decylamine, dodecylamine, tetradecylamine, hexadecylamine, octadecylamine, eicosylamine, dodecenylamine, hexadecenylamine, octadecenylamine, octadecadienylamine, abietylamine, aniline, toluidine, naphthylamine, cumylamine, bornylamine, fenchylamine, tertiary butyl aniline, benzylamine, betaphenethylamine, etc.
  • Particularly preferred amines are those made from natural oils or fats or from the straight chain acids derived therefrom. These starting materials may be converted to amides by reactions with ammonia and the amides can then be dehydrated to give nitriles. The nitriles are then reduced, preferably catalytically, to give the desired amines.
  • Exemplary amines prepared by the method include stearylamine, laurylamine, palmitylamine, oleylamine, petroselinylamine, linoleylamine, linolenylamine, eleostearylamine, etc. The unsaturated amines are particularly preferred.
  • monoisocyanates are hexylisocyanate, decylisocyanate, dodecylisocyanate, tetradecylisocyanate, hexadecylisocyanate, phenylisocyanate, cyclohexylisocyanate, xylylisocyanate, cumenylisocyanate, abietylisocyanate, cyelooctylisocyanate, etc.
  • the polyamines which form one of the internal hydrocarbon bridges between the ureido groups preferably contain from 2 to 30 carbon atoms, more preferably from 2 to 20 carbon atoms, and more desirably from 2 to carbon atoms.
  • Exemplary polyamines include ethylenediamine, propylenediamine, butylenediamine, hexylenediamine, dodecylenediamine, octylenediamine, hexadecylenediamine, cyclohexylenediamine, cyclooctylenediamine, phenylenediamine, tolylenediamine, xylylenediamine, dianiline methane ditoluidinemethane, bis(aniline), bis(toluidine), piperazine, diethylene triamine, tert-N-methyl diethylene triamine, triethylene tetramine, dipropylene triamine, N- methyl-imino-bis(propyl amino
  • diisocyanates include hexylenediisocyanate, decylenediisocyanate, octadecylenediisocyanate, phenylenediisocyanate, tolylenediisocyanate, diphenyldiisocyanate, methylene bis(phenylisocyanate), etc.
  • aromatic diisocyanates such as tolylenediisocyanate are preferred.
  • the carboxyl or sulfonic acid group source as referred to herein must be capable of reacting with an isocyanate to form a ureido group and must have a terminal carboxyl or sulfonic acid group (acid or ester) capable of being reacted with a basic metal compound to form the corresponding metal salt.
  • Carboxyl and sulfonic acid group sources which may be employed in the practice of this invention include amino acids, amino esters, lactams, and amino sulfonic acids and esters.
  • the preferred carboxyl or sulfonic acid group source is selected from an amino carboxylic acids, an amino ester, a lactam or mixtures thereof.
  • the most preferred carboxylic acid group source is a lactam.
  • the amino monocarboxylic acid or amino dicarboxylic acid and the C -C esters thereof will contain a primary (preferred) or secondary amino group.
  • the amino acids or esters must have at least one active hydrogen atom on the nitrogen, i.e., the tertiary amines cannot be used in the practice of this invention,
  • the amino acids will have from 2 to 31 carbon atoms (including the carboxylated carbon atoms), preferably from 6 to carbon atoms and more preferably from 6 to 12 carbon atoms.
  • the esters of the above will contain from 1 to 6 carbon atoms and preferably 2 carbon atoms in the ester group.
  • Typical amino monocarboxylic acids which may be used in this invention include 4-aminobenzoic acid, 4-amino-o toluic acid, 4-amino-m-toluic acid, 4-amino-p-toluic acid, 4-arnino-salicyclic acid, anthranilic acid, B-aminobenzoic acid, p-amino-a-toluic acid, 1-ethyl-3-aminobenzoic acid, 1-ethyl-4-amino-benzoic acid, glycine, ,B-alanine, S-aminovaleric acid, 6-amino-caproic acid, 8-minocaprylic acid, IO-aminocapric acid, l2-aminolauric acid, l4-aminomyristic acid 16-aminopalmitic acid, IS-aminostearic acid, 18- aminooleic acid, IS-aminolinoleic acid, l8-aminolinolenic acid
  • Typical aminodicarboxylic acids which may be suitable for use in this invention include aspartic acid, 3-aminoglutaric acid, 3-aminoadipic acid, 4-azninosuberic acid, 5- aminosebacic acid, 2-arninoterephthalic acid, etc.
  • Other types include nitrilo diacetic acid, nitrilo dibenzoic acid, nitrilo dipropionc acid, etc.
  • Exemplary amino diesters include diethyl 3-arnino-glutamate, diethyl 3-aminoadipate, methylethyl S-aminosebacate, etc.
  • Exemplary aminocarboxylic mono and diesters include methyl p-aminobenzoate, ethyl p-aminobenzoate, propyl p-aminobenzoate, ethyl 4-amino-p-methylbenzoate, propyl-6-aminocaproate, ethyl anthranilate dipropyl aspartate, dipropylglutamate, etc.
  • Esters of the mono carboxylic acids are preferred.
  • Amino amides which may be used as reactants will have from 2 to carbon atoms and preferably 3 to 12 carbon atoms.
  • Typical amino amides which may be employed herein are the aminoacyclic amides such as 6-aminocapryl amide, 8-aminocapryl amide, IZ-aminolauryl amide, p-
  • the most preferred carboxyl group source is the cyclic amides and preferaby the lactams having from 5 to 8 members in the heterocyclic structure.
  • Typical lactams which may be used herein include Z-pyrrolidone, S-methyl-Z-pyrrolidone, 3,3-dimethyl-2-pyrrolidone, 2-piperidone, 3-methyl 2 piperidone, gamma-caprolactam, etc.
  • Caprolactam is the most preferred.
  • the metal salt of an amino carboxyl or sulfonic acid which may be employed in the practice of this invention typically have one of the following general formulae:
  • R is selected from hydrogen or a hydrocarbyl having from 1 to 20 carbons and preferably from 2 to 12 carbons;
  • R is a hydrocarbylene having from 1 to 20 carbons and preferably from 6 to 16 carbons;
  • M is a metal atom described supra.
  • d is an integer from 1 to 2 and sufficient to make the compound electro-neutral.
  • Exemplary metal salt include sodium-p-aminobenzoate, potassium p-aminobenzoate, lithium p-aminobenzoate, sodium aminoacetate, monosodium glutamate, monopotassium glutamate, disodium glutamate, sodium 4-amino-pmethylbenzoate, potassiumpiperidinate, monosodium aspartate, monosodium p-aminoisophthalate, sodium p-aminobenzyl sulfonate, sodium amino ethyl sulfonate, etc.
  • the preferred amino metal salts are the alkali metal salts of monocarboxylic acids and preferably aromatic monocarboxylic acids.
  • the metal salts of amino carboxyl and sulfonic acids are generally highly insoluble within the typical lubricating oil reaction medium. In the event that solubility is problemsome, a mutual solvent having appreciable solubility for the polyurea precursors and for the amino metal salt may be employed.
  • the basic metal compounds which may be employed in the practice of this invention to form the polyurea metal salt are hydroxides, oxides, carbonates and alcoholates of Groups I and II metals of the Periodic Table. These include hydroxides, oxides, carbonates and alcoholates of the alkaline (Group I) metals, such as lithium, potassium, sodium, rubidium, and cesium; the alkaline earth metals (Group II) such as beryllium, magnesium, calcium, strontium and barium.
  • the preferred compounds are the alkali metal hydroxides, and most preferred are those of the low molecular weight alkali metals, such as, lithium, sodium and potassium, and particularly sodium.
  • Typical compounds which may be employed herein include NaOI-I, KOH, LiOH, Ca(OH) CaO, CaHCO CaCO Mg(OH) Ba(OH) etc.
  • an intermediate polyurea compound having a terminal amine group is prepared. These may be prepared in substantially the same manner as described supra with the deletion of the carboxyl or sulfonic acid group source and by employing an excess of the polyamine reactant. If a polyurea having a terminal isocyanate group is prepared, this group may be hydrolyzed by an aqueous base to form a polyurea having a terminal amine group. The polyurea amine intermediate is then reacted with an anhydride, lactone or sultone to form a polyurea having a terminal carboxyl or sulfonic acid group. This polyurea acid is then saponi fied with a basic metal compound, described supra, to form the polyurea metal salt product. More specifically, in this preparation the desired reactants (diisocyanate,
  • polyamine, and monoamine or monoisocyanate are mixed within a suitable reaction vessel in the proper proportions.
  • the reaction may proceed without the presence of a catalyst and is initiated by merely contacting the reactants under conditions conducive for the reaction. Typical reaction temperatures range from 100 to 300 F. and preferably from 150 to 260 F. In most cases, the reaction will be exothermic and the temperature will rise during the course of the reaction. Regardless of the exothermicity of the reaction, external heating or cooling may be used as required.
  • the reaction as before, is preferably carried on within an inert solvent and typically the lubricating oil to be thickened. It is also necessary to agitate the mixture during the reaction to provide intimate contacting of the reactants.
  • the reaction time is not critical but will generally range from 30 to 120 minutes; however, longer times (more than 3 hours) may be employed.
  • a dilute aqueous solution of an alkali metal hydroxide is charged to the reaction vessel and intimately contacted with the polyurea compound.
  • the temperature of the reaction vessel is preferably maintained from 200 to 360 F. and more preferably to 200 to 320 F. during the reaction.
  • the presence of the dilute caustic effects a decarbonation of the polyurea compound to form a polyurea amine from the terminal isocyanate group.
  • the reaction is conducted until the diisocyanate is completely consumed.
  • the reaction medium is dehydrated and the vessel charged with an anhydride, lactone or sultone having from 3 to 24 carbons and preferably from 4 to 12 carbons.
  • the anhydride, lactone or sultone reacts with one of the hydrogen atoms on the amine group forming a secondary amine having a free carboxylic or sulfonic acid group.
  • the reaction may proceed without the presence of a catalyst and is initiated by merely contacting the anhydride, lactone or sultone with the polyurea amine under conditions conducive for the reaction. Typical reaction temperatures vary from 100 to 300 F. and more preferably from 150 to 200 F.
  • the reaction is conducted at substantially atmospheric pressure; however, elevated pressures may be employed.
  • the polyurea acid is contacted with a basic metal compound and converted to the polyurea metal salt.
  • the amount of lactone, anhydride or sultone employed in the above reaction should be the stoichiometric amount, i.e., one mol of reactant per mol of polyurea amine present.
  • the amount of basic metal compound employed varies depending upon how many carboxyl or sulfonic acid groups are present on the polyurea compound and on the valence of the basic metal compound. Generally, however, the amount of metal base is present in an amount from 1 to percent excess over that stoichiometrically required to produce the polyurea metal salt.
  • Exemplary anhydrides which may be employed in the practice of this invention include malonic anhydride, succinic anhydride, glutaric anhydride, adipic anhydride pimelic anhydride, maleic anhydride, phthalic anhydride, 3,3,4,4'-benzophenanetetracarboxylic anhydride, etc.
  • Exemplary lactones include gamma-butyrolactone, gammavalerolactone, fl-propiolactone, delta-valerolactone, etc.
  • Exemplary sultones which may be employed include propane sultone, butane sultone, naphthsultone, etc.
  • the polyurea metal salt compositions are useful as grease thickeners, to produce greases with good lubricating properties. They are also useful as gellants for a variety of fluids, particularly hydrocarbons, of low viscosity to form fire starters, paints, and the like.
  • the compositions described herein are used in oils of lubricating viscosity in amount sufiicient to thicken the oil to the consistency of grease when combined with the alkaline earth metal carboxylate.
  • the amount ranges from 2 to 15 10 weight percent, preferably from 3 to 10 weight percent based on the weight of the final grease composition.
  • the second component of the grease composition is an alkaline earth metal aliphatic monocarboxylate having from 1 to 3 carbon atoms.
  • Any of the alkaline earth metals can be employed herein, e.g., magnesium, calcium, strontium, barium, etc. However, calcium is the most preferred.
  • the carboxylate group preferably has from 1 to 3 carbon atoms and more preferably 2 carbon atoms. Exemplary compounds which may be successfully employed herein include calcium formate, barium formate, magnesium formate, magnesium acetate, calcium acetate, strontium acetate, barium acetate, calcium propionate, barium propionate, magnesium propionate, etc.
  • the amount of alkaline earth metal carboxylate present within the grease composition may vary depending upon the lubricating property desired, the particular polyurea constituent selected, the type of alkaline earth metal carboxylate selected, etc. However, generally the metal carboxylate will range from 3 to 30 weight percent of the final grease composition and preferably between about 4 and 15 weight percent.
  • the ratio of alkaline earth metal carboxylate to the polyurea constituent will also vary depending upon the aforementioned conditions, but will generally range on a weight basis from 1 to 15 parts of metal carboxylate per part of polyurea and preferably from 3 to 7 parts per part of polyurea.
  • the third component which must necessarily be present in the composition of this invention is a liquid base oil.
  • the base oils which may be employed herein include a wide variety of lubricating oils such as naphthenic-base, paraflin-base, and mixed-base lubricating oils.
  • hydrocarbon oils include lubricating oils derived from coal products and synthetic oils, e.g., alkylene polymers (such as, polymers of propylene, butylene, etc., and mixture thereof), alkylene oxide-type polymers (e.g., alkylene oxide polymers prepared by polymerizing alkylene oxide, e.g., propylene oxide polymers, etc., in the presence of water or alcohols, e.g., ethyl alcohol), carboxylic acid esters (e.g., those which were prepared by esterifying such carboxylic acids as adipic acid, azelaic acid, suberic acid, sebacic acid, alkenyl succinic acid, fumaric acid, maleic acid, etc., with the alcohols such as butyl alcohol, hexyl alcohol, 2-ethylhexyl alcohol, pentaerythritol, etc.), liquid esters of acids of phosphorus, alkyl benzenes, polyphenols (
  • the greases exhibiting the superior properties of this invention can be prepared by the in situ production of the polyurea metal salt within a lubricating oil.
  • the lubricating oil is charged to a grease mixer along with the polyurea precursors, i.e., the reactants which combine to form the polyurea salt.
  • the mixer contents are agitated and the process conditions and steps conducted in a manner discussed supra for the preparations of the polyurea metal salt.
  • the polyurea metal salts produced within the lubricating oil are generally mixtures of compounds, wherein n and n; in the Formulae vary from 0 to 3 and polyureas with different degrees of polymerization exist within the grease composition at the same time.
  • the grease composition may concurrently contain metal salts of diurea, triurea, tetraurea, pentaurea, hexaurea, octaurea, etc.
  • particularly good results have been realized when the polyurea compound is comprised of a combination of diurea salts and tetraurea salts of the 3 ureido groups.
  • cross-linking between polymer chains through a divalent or trivalent metal atom may also be present in minor amounts within the reaction mixture.
  • the grease mixer is charged with an alkaline earth metal hydroxide or oxide and a carboxylic acid.
  • the ratio of alkaline earth metal hydroxide to carboxylic acid on an equivalent basis can vary from 1 to 4:1 and is preferably between 1 and 2:1.
  • the mixer is maintained at a temperature between 70 F. and 150 F. during the process to effect the neutralization reaction of the alkaline earth metal hydroxide or oxide and carboxylic acid.
  • During the reaction water is released and is removed from the system by heating above 212 F. or alternatively applying a slight vacuum on the mixer of 20 to 29 inches of mercury and heating to about 212 F. and higher.
  • the grease composition can be further processed by subjecting it to shear hardening.
  • Shear hardening is performed by milling the grease in an extrusion of stator rotor mill under elevated pressures. The milling improves the dispersion of the polyurea metal salt and metal carboxylate throughout the base oil resulting in a grease of greatly improved consistency.
  • additives may be successfully employed within the grease composition of this invention without affecting its high stability and performance over a wide temperature scale.
  • One type of additive is an antioxidant or oxidation inhibitor. This type of additive is employed to prevent varnish and sludge formation on metal parts and to inhibit corrosion of alloyed bearings.
  • Typical antioxidants are organic compounds containing sulfur. phosphorus or nitrogen, such as organic amines, sulfides, hydroxy sulfides, phenols, etc., alone or in combination with metals like Zinc, tin or barium.
  • Particularly useful grease antioxidants include phenyl-alpha-naphthyl amine, bis(alkylphenyl)amine, N,N-diphenyl-p-phenylenediamine, 2,2,4 trimethyldihydroquinoline oligomer, bis(4-isopropylaminophenyl)ether, nacyl-p-aminophenol, N-acyl-phenothiazines, alkylphenolformaldehyde-amine.
  • Another additive which may be incorporated into the grease composition of this invention is an anti-corrodant.
  • the anti-corrodant is employed to suppress attack by acidic bodies and to form films over the metal surfaces which decrease the effect of corrosive materials on exposed metallic parts.
  • a particularly effective corrosion inhibitor is an alkali metal nitrite, preferably sodium nitrite. When an alkali metal nitrite is employed, it is used at a concentration ranging from 0.1 to 5 weight-percent and preferably from 0.2 to 2 weight percent.
  • a metal deactivator Another type of additive which may be employed herein is a metal deactivator. This type of additive is employed to prevent or counteract catalytic effects of metal on oxidation generally by forming catalytically inactive complexes with soluble or insoluble metal ions.
  • Typical metal deactivators include complex organic nitrogen and sulfur-containing compounds such as certain complex amines and sulfides.
  • An exemplary metal deactivator is mercaptobenzothiazole.
  • grease additives may be employed in the practice of this invention and include stabilizers, tackiness agents, dropping point improvers, lubricating agents, color correctors, odor control agents, etc.
  • EXAMPLE 1 In this example, a diureido and a tetraureido sodium salt thickening agent and a grease containing the same are prepared.
  • a 45 liter staniless steel mixer equipped with a stirrer is charged with 10,000 grams of 480 neutral oil, 1780 grams of tall oil fatty amine and 740 grams of caprolactam. The mixture is stirred at 210 F. to disperse the amine and caprol'actam within the netural oil. Thereafter, it is cooled to F. and 188 grams of ethylene diamine are added to the mixture.
  • the mixture is then charged with a blend of 1712 grams of tolylene diisocyanate in 8000 grams of 480 neutral oil.
  • the diisocyanate-oil blend is added slowly to the previously prepared mixture over a period of 45 minutes.
  • the reaction mixture is diluted with an additional 10,000 grams of neutral oil to reduce the degree of thickening.
  • the mixture is stirred and recycled in the mixer for a period of two hours.
  • a sample of the grease is calculated to contain 11 weight percent of thickening agent and has a theoretical content of about 54 weight parts of diureido sodium salt CH3 i H l TNHGNH NH-CNH(oH -d-oNa and about 46 weight parts of tetraureido sodium salt O t t TNH NH NH -NHCH,CH,NH-o- 0 it t NE NH NH(CHa)5 ONa EXAMPLE 2
  • This example is presented to demonstrate the effectiveness of a representative grease to this invention containing the polyurea metal salt in long term performance as compared to a typical lithium stearate grease and a typical polyurea grease.
  • the polyurea metal salt grease to be tested is prepared by the method of Example 1.
  • the lithium grease is -a commercially available grease and is composed essentially of the following:
  • LITHIUM GREASE COMPOSITION Component Amount, wt. percent Lithium hydroxy stearate 9 Lubricating oil 83 Commercial E.P. agent 7.5 Commercial rust inhibitor 0.4
  • the lithium grease has an ASTM work penetration after 60 strokes (P of 320.
  • *T is tall oil fatty amine radical.
  • Test Grease Bearing life, hrs.
  • a mixture of a diisocyau-ate in a 480 neutral oil is so slowly added to the above reaction mixture over a minute period.
  • the rewherein T is tau 011 fatty amme radlcal' action mixture is diluted with additional oil to reduce the
  • the polyurea grease has an ASTM work penetration degree of thickening.
  • the mixture is stirred and recycled ft 60 strokes (.P of 280, in the reaction vessel for an additional 1-2 hours.
  • the three greases are subjected to a high-speed bear- To the mixture is then added an aqueous 50 percent ing life test to determine the maximum bearing life of metal hydroxide solution. The mixture is thereafter heated each of the greases. The test procedure is set forth in to 320 F. for 1 hour with stirring to remove the water. Federal Test Method 331.1 (Navy High Speed Bearing The mixture is then cooled and milled.
  • AAA p-Amino-acetanilide.
  • BPM Bis(p-phenylisocyanate)methane.
  • BZC Benzoeaine (ethyl ester of p-aminobenzoic acid).
  • CPLT e-Caprolactam.
  • DPA Dipropyl aspartate.
  • DTH 1,6diamino-2,2,4-trimethylhexane.
  • DAIP Dimethyl fi-aminoisophthalate.
  • EDA Ethylene diamine.
  • HDA 1,6-hexanediamine.
  • MPDA Metapheny1ene diamine.
  • ODA Octadecylamine
  • PYD 2-pyrrolidinone
  • TDI Tolylene diisocyanate
  • TOFA Tall oil fatty amine.
  • XDA Xylene diamine. 2 The average number of polyurea groups in entire composition. 3 Conducted at 10,000 r.p.rn. at 350 F.
  • the above table demonstrates the practice of the instant invention in the preparation of numerous representative polyurea metal salts and corresponding greases containing the salts.
  • the 27 compositions amply illustrate the broad range of diamines, diisocyanates, monoamines and carboxyl group sources which can be successfully employed to prepare the polyurea salts. Also illustrated is the wide range of concentrations for the various reactants as well as for the total thickener content which may be employed.
  • EXAMPLE 4 This example is presented to demonstrate the practice of this invention wherein a. variety of metal moieties can be used in the preparation of the polyurea salt.
  • a process identical to that described in Example 1 is used with the exception that LiOH, Ba(OH) or Ca(OH) is substituted for NaOH in the neutralization of the polyurea caprolactam adduct.
  • the properties of the various greases are given in the following Table V. A sample of the lithium and sodium greases are tested under Federal Test Methods Standards 791a, Method 331, and the bearing life determined. The following Table V also presents the results from this test.
  • a 50 percent osmium 58mm 18 i k5 40 aqueous solution of sodium hydroxide is charged to the gififi gg jj i3 4 290 2""11'2615865' g mixer and intimately contacted with the carboxylated poly- Sodium salt 11 3 291 2, 436, 2, 874 469, 48 urea.
  • the temperature of the system is maintained at 190 1 Test conducted at 350 F. at 10,000 r.p.rn. F d thi ri d a h o 9 Bearing life test conducted at 325 F. at 10,000 r.p.m.
  • SA Suceinic anhydride
  • BL Gamma-butyrolactone
  • PL Beta-propiolactone
  • PA Phthalic anhydn'de
  • MA Malelc anhydride
  • BTCA 3,3,4,4-benzophenene tetra carboxylic anhydride.
  • compositions illustrated in the above Table VI are calculated to have the following structures:
  • This example thus illustrates the preparation of various representative polyurea metal salts having the structure set forth in Formula 2 and the effectiveness of these compositions in thickening a lubricating oil to the consistency of grease. Also illustrated is the excellent bearing life of one of the representative greases.
  • EXAMPLE 6 This example is presented to demonstrate the preparation of a polyurea metal salt having the structure presented in Formula 2 and prepared from neutralizing a polyurea sulfonic acid with sodium hydroxide.
  • a 600 ml. glass beaker is charged with approximately 100 grams of a 600 neutral oil, 0.05 mol of tall oil fatty amine and 0.025 mol of ethylene diamine.
  • the contents of the beaker are stirred and heated to a temperature of about 150 F. to uniformly disperse the reactants within the oil reaction medium.
  • approximately 65 grams of 600 neutral oil and 0.075 mol of tolylene diisocyanate are charged to the glass beaker reaction, the beaker is heated to F. and 25 grams of 10 percent sodium hydroxide solutions are admixed with the beaker contents. The admixture is agitated at the above temperature for a period of 45 minutes and thereafter dehydrated at a final temperature of 310 F.
  • a 50 percent aqueous solution of sodium hydroxide (0.05 mol) is charged to the beaker and intimately contacted With polyurea sulfonic acid.
  • the temperature is maintained at 190 F. for a period of approximately 30 minutes.
  • the water is stripped from the system by heating to a temperature of about 310 F.
  • the polyurea metal salt is calculated to have the following structure and is present within the oil in an amount of 11 weight percent based on the weight of total grease composition.
  • T is a tall oil fatty amine radical
  • EXAMPLE 7 This example is presented to demonstrate the preparation of a representative polyurea metal salt having the structure presented in Formula 4.
  • a 600 ml. flask is charged with 100 grams of 600 neutral oil and 5.65 grams of caprolactam. The contents are heated to 150 F. and 3 grams of ethylene diamine with 5 grams of oil are charged to the flask. Thereafter, 23 grams of 600 neutral oil and 8.7 grams of tolylene diisocyanate and 14.75 g. of octadecylisocyanate are admixed with the fiask contents. During the reaction, the temperature of the flask rises to 180 F. and is stirred for 90 minutes. An additional 0.9 grams of EDA are added to insure that all of the diisocyanate has reacted.
  • the contents of the flask are transferred to a 600 ml. glass beaker and 4 grams of sodium hydroxide in 4 grams of water are charged to the beaker.
  • the oil in the beaker is calculated to contain 21 weight percent of polyurea sodium salt.
  • the ASTM work penetration (P is measured to be 294.
  • the structure of the polyurea compound is calculated to be as follows:
  • EXAMPLE 8 This example is presented to demonstrate the preparation of a representative polyurea metal salt having the structure presented in Formula 4.
  • the grease exhibits an ASTM worked penetration after 60 strokes of 261.
  • the polyurea metal salt is calculated It is apparent that many widely different embodiments of this invention may be made without departing from the scope and spirit thereof; and these embodiments are considered to be within the scope of this invention.
  • EXAMPLE 9 This example is presented to illustrate the preparation of a grease containing a polyurea metal salt and alkaline earth metal aliphatic monocarboxylate.
  • a grease mixer is charged with 14,000 grams of 600 neutral mineral oil, 1200 grams of tall oil fatty amine, 500 grams of caprolactam and 132 grams of ethylene diamine.
  • the mixer is cooled to 140 F. and charged with 1148 grams of tolylene diisocyanate in 6000 grams of 600 neutral mineral oil.
  • the lines are flushed and the mixer charged with an additional 1000 grams of 600 neutral oil.
  • an additional 10 grams of ethylene diamine are added to the mixer to assure the elimination of any unreacted isocyanate groups.
  • the product has an ASTM worked penetration after 60 strokes (P of 287 and an ASTM dropping point of 465.
  • the product contains about 9 wt. percent of polyurea metal salt of the formula shown in Example 1, and 15 wt. percent of calcium acetate.
  • Timken load had passed lbs. with no failure before the test was discontinued. This illustrates an excellent extreme pressure property.
  • the Timken load for a similar polyurea calcium acetate grease is 50 pounds.
  • the product was further subjected to a modified ASTM D1743 rust test in 3% synthetic sea Water (ASTM 665) and 97% distilled water.
  • the rust rating is 0 no rust and 5 very rusty with intermediate values between 0 and 5 representing increasing degrees of rust.
  • the rating system is more fully described in IP 220 (British Institute of Petroleum).
  • the ratings as determined after the bearing is stored for 1 day at 77 F.
  • the rust rating for the above product polyurea metal salt-calcium acetate
  • the rust rating for the above product is 0 and at 5% synthetic sea water and distilled water is 0. Similar polyurea and polyurea calcium acetate greases containing these additives will not pass these sea water tests.
  • EXAMPLE 10 In this example the preparation of a polyurea calcium salt-calcium acetate grease is illustrated. The steps of Example 9 are followed except that lime is used in place of the sodium hydroxide. The following amounts are used:
  • the product contains about 8 wt. percent of a calcium polyurea salt and about 13 wt. percent of calcium acetate.
  • the product has an ASTM worked penetration (P of 272 and a dropping point of 450.
  • a grease composition comprising a major portion of a lubricating oil and minor grease thickening portions of (1) an alkali or alkaline earth metal salt of a polyurea sulfonate or carboxylate compound having at least 2 ureido groups and having a molecular weight between about 250 and 2500 and (2) an alkaline earth metal aliphatic monocarboxylate having from 1 to 3 carbons.
  • composition of matter comprising a major portion of a lubricating oil and an amount sufiicient to thicken said oil'to the consistency of grease of 1) an alkaline earth metal aliphatic carboxylate having from 1 to 3 carbon atoms, and (2) a polyurea metal salt having a structure presented in one of the following formulae:
  • AJWWI G is a divalent polyamino group of the formula:
  • M is a metal selected from Groups I and II of the Periodic Table
  • n is an integer from to 3;
  • n is an integer from 1 to 3;
  • n is an integer from 0 to 1;
  • w is an integer from 1 to 2 and suincient to make the compound 'electroneutral;
  • z is an integer from 0 to 2;
  • v is an integer from 0 to 1;
  • t is an integer equal to 1 when v is 0 and 0 when v is 1;
  • R is the same or different hydrocarbylene having from 2 to 30 carbons
  • R is the same or difierent hydrocarbylene having from 2 to 12 carbons
  • R is the same or difierent components selected from hydrogen or a C -C alkyl;
  • A is a divalent radical selected from the group consisting of:
  • R is the same or different trivalent hydrocarbon radical having from 1 to 30 carbons; and A is a divalent radical selected from:
  • composition defined in Claim 5 wherein said polyurea metal salt has a structure defined by Formula 1 or 2.
  • composition defined in Claim 10 wherein said alkylene diamino is ethylene diamino.
  • composition defined in Claim 11 wherein said metal aliphatic monocarboxylate is calcium acetate.
  • a composition of matter comprising a major portion of a lubricating oil and an amount suflicient to thicken said oil to the consistency of grease of (1) from 4 to 15 weight percent of calcium acetate and (2) from 3 to 10 weight percent of a polyurea metal salt prepared by reacting one molar part of ethylene diamine with two molar parts of tolylene diisocyanate, one molar part of a C to C monoamine and one molar part of caprolactam followed by saponification of the reaction product with sodium hydroxide.

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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)
  • Polyurethanes Or Polyureas (AREA)
US00374212A 1973-06-27 1973-06-27 Grease thickened with polyurea metal salts and alkaline earth metal aliphatic monocarboxylate Expired - Lifetime US3846315A (en)

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US00374212A US3846315A (en) 1973-06-27 1973-06-27 Grease thickened with polyurea metal salts and alkaline earth metal aliphatic monocarboxylate
CA194,321A CA1036147A (en) 1973-06-27 1974-03-07 Grease composition
GB1465674A GB1457316A (en) 1973-06-27 1974-04-02 Grease composition
BE143703A BE814283A (fr) 1973-06-27 1974-04-26 Compostion de graisse perfectionnee
JP5063474A JPS5628960B2 (OSRAM) 1973-06-27 1974-05-07
FR7421315A FR2235189B1 (OSRAM) 1973-06-27 1974-06-19
IT24329/74A IT1019664B (it) 1973-06-27 1974-06-24 Composizione di grasso con pro prieta lubrificanti ad alte tem perature e per lunghi periodi e procedimento relativ
DE2430505A DE2430505A1 (de) 1973-06-27 1974-06-25 Fettzusammensetzung
NL7408691A NL7408691A (OSRAM) 1973-06-27 1974-06-27

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5000862A (en) * 1989-03-31 1991-03-19 Amoco Corporation Process for protecting bearings in steel mills and other metal processing mills
US5011617A (en) * 1990-02-09 1991-04-30 Chevron Research And Technology Company Complex tolylene polurea grease composition and process
US5223161A (en) * 1989-06-27 1993-06-29 Amoco Corporation Extreme pressure and wear resistant grease with synergistic sulfate and carboxylate additive system
US6214778B1 (en) 1995-08-24 2001-04-10 The Lubrizol Corporation Polyurea-thickened grease composition
US20120046436A1 (en) * 2009-04-21 2012-02-23 Huntsman International Llc Polyisocyanate composition

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3920571A (en) * 1974-09-16 1975-11-18 Chevron Res Grease composition and method of preparing the same

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1495428A (fr) * 1965-04-20 1967-09-22 Mobil Oil Corp Nouvelles compositions de graisses lubrifiantes
US3537997A (en) * 1968-09-16 1970-11-03 Gen Electric Methyl alkyl silicone grease composition and method of making same

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5000862A (en) * 1989-03-31 1991-03-19 Amoco Corporation Process for protecting bearings in steel mills and other metal processing mills
US5158694A (en) * 1989-03-31 1992-10-27 Amoco Corporation Railroad grease
US5223161A (en) * 1989-06-27 1993-06-29 Amoco Corporation Extreme pressure and wear resistant grease with synergistic sulfate and carboxylate additive system
US5011617A (en) * 1990-02-09 1991-04-30 Chevron Research And Technology Company Complex tolylene polurea grease composition and process
US6214778B1 (en) 1995-08-24 2001-04-10 The Lubrizol Corporation Polyurea-thickened grease composition
US20120046436A1 (en) * 2009-04-21 2012-02-23 Huntsman International Llc Polyisocyanate composition
US9018333B2 (en) * 2009-04-21 2015-04-28 Huntsman International Llc Polyisocyanate composition

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DE2430505A1 (de) 1975-02-13
IT1019664B (it) 1977-11-30
FR2235189A1 (OSRAM) 1975-01-24
JPS5023404A (OSRAM) 1975-03-13
FR2235189B1 (OSRAM) 1977-10-07
BE814283A (fr) 1974-08-16
NL7408691A (OSRAM) 1974-12-31
GB1457316A (en) 1976-12-01
JPS5628960B2 (OSRAM) 1981-07-04
CA1036147A (en) 1978-08-08

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