Classifications

• • 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
  • C10M169/02—Mixtures of base-materials and thickeners
• • 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
  • C10M2205/028—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • 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
• • 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
• • 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
  • C10M2217/045—Polyureas; Polyurethanes
• • 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
  • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
  • C10N2020/01—Physico-chemical properties

Definitions

• This invention relates to grease compositions and, in one of its aspects, relates to improved grease compositions which are suitable for use over wide temperature ranges and which exhibit good oxidation stability under varying operational conditions. More particularly in this aspect, the invention relates to improved grease compositions which contain a combination of certain hydrogenated olefin polymer vehicles and polyurea thickening agents, rendering these greases particularly effective in operations in which the aforementioned conditions are normally encountered.
• Greases heretofore prepared by the processes of the prior art, have generally comprised a vehicle, such as petroleum hydrocarbon lubricating oils, refined mineral oils or synthetic esters, in which various thickening agents, such as metal salts or soaps, are dispersed in grease-form ing quantities in such degree as to impart to the resulting grease composition the desired consistency.
• a vehicle such as petroleum hydrocarbon lubricating oils, refined mineral oils or synthetic esters, in which various thickening agents, such as metal salts or soaps, are dispersed in grease-form ing quantities in such degree as to impart to the resulting grease composition the desired consistency.
• various thickening agents such as metal salts or soaps
• the hydrogenated olefin polymer is prepared from olefins having less than about 6 carbon atoms per molecule, the resulting grease composition will deteriorate rapidly at elevated temperatures due to loss of vehicle by volatilization.
• the hydrogenated olefin polymer is prepared from olefins having more than 12 carbon atoms per molecule, the resulting grease composition will not possess suitable low torque values at relatively low temperatures.
• the presence of the above-described polyurea thickening agent makes possible the formulation of greases which, in general, exhibit dropping points in excess of 400 F. and more usually in excess of 450 F.
• the preparation of the lubricating vehicles of the improved greases of the present invention can be carried out in accordance with the process described in U.S. Pat. 3,514,401.
• the preparation of the lubricating vehicle may be carried out, in general, by distilling a liquid polymerized normal alpha-monoolefin synthetic lubricant to obtain a fraction which contains dimer, and a residual fraction which is essentially free from dimer, and then completely saturating the residual fraction by hydrogenation under catalytic hydrogenation conditions,
• the thermally polymerized olefins that are utilizable in producing the synthetic lubricating vehicle in the improved greases of the present invention include, for example, l-hexene, l-heptene, l-octcne, l-nonene, l-decene, 1-undecene and l-dodecene.
• the olefin reactant can be substantially pure normal alpha-monoolefins, mixtures of olefins and/or paraflins containing substantial amounts of normal alpha-monoolefins, having between about 6 and about 12 carbon atoms per molecule.
• the aforementioned polymerization procedure can, in general, be carried out over a wide temperature range. More specifically, when catalytic polymerization is to be conducted, polymerization temperatures from about 0 F. to about 450 F. are preferably employed. When thermal polymerization is to be conducted, polymerization temperatures from about 500 F. to about 700 F. are preferably employed. The polymerization period may vary from about 1 hour to as high as about 20 hours, or longer.
• the above-indicated polymerization procedures are more fully described in U.S. Pat. 3,149,178.
• the aforementioned normal alpha-monoolefins employed for producing the polymer oil vehicles of the greases of the present invention, may be polymerized in the presence of ditertiary alkyl peroxide catalysts, such as are described in U.S. Pat. 2,937,129. Particularly preferred are the di-tertiary lower alkyl peroxides as catalysts. Of these, the most outstanding catalyst is di-tertiary butyl peroxide.
• the amount of peroxide catalyst employed is from about 0.01 to about 0.3 mole per mole of normal alpha-monoolefin reactant.
• the temperature employed is the activation temperature of the peroxide catalyst, and can vary from about C. to about 200 C. In general the reaction time will vary from about one to about six hours.
• polymerized normal alpha-monoolefin oils utilizable in obtaining the lubricating vehicles of the present invention can also be readily prepared in the presence of Friedel-Crafts catalysts under relatively mild conditions, as described in US. Pat. 3,149,178. To a great extent, the choice of catalyst and of reaction conditions can be made in order to produce polymer lubricants of desired viscosity.
• a BF -catalyzed polymerization procedure when a BF -catalyzed polymerization procedure is carried out, pressure or a catalyst promoter is necessary in order to produce synthetic lubricants of high quality.
• Suitable promoters include BF -decanol complex, decanol, acetic acid, and acetic acid-BF complex.
• the polymerization is carried out at temperatures below about 60 C. for a total reaction time in the order of about 2 to about 4 hours.
• BF polymerization is carried out under pressure, a reaction time of 2 to 4 hours is employed.
• the pressure measured in terms of BF pressure, can vary between about pounds per square inch gauge and about 500 pounds per square inch gauge, or higher.
• polymerized normal alpha-monoolefin synthetic lubricant as used herein, is intended to denote synthetic lubricants improved by polymerizing the aforementioned normal alpha-monoolefins, having from about 6 to about 12 carbon atoms per molecule, either thermally or catalytically, in the presence of a di-tertiary alkyl peroxide or in the presence of a Friedel-Crafts catalyst, which includes boron trifiuoride and aluminum chloride under mild polymerization conditions, as previously indicated.
• the aforementioned term is intended to exclude polymers which are produced in the presence of other peroxides, such as diacyl peroxides, which polymers contain structural elements of the peroxy catalyst. It has been found, in this respect, that polymers produced in the presence of a di-tertiary alkyl peroxide do not contain structural elements of the peroxide catalyst. In this respect, the latter polymers are the substantial equivalent of thermally polymerized olefins. As previously indicated, when Friedel-Crafts catalysts are employed, the polymerization conditions must be relatively mild.
• the polymerized normal alphamonoolefin synthetic lubricant to be employed as a vehicle in the novel grease compositions of the present invention, is subjected to saturation by hydrogenation.
• a more detailed description for conducting such hydrogenation will be found in US. Pat. 3,149,178, the subject matter of which is incorporated, in its entirety, in this application, by reference.
• the hydrogenation treatment is carried out under catalytic hydrogenation conditions, effective to produce the desired hydrogenated polymer wherein the polymer, as previously indicated, was prepared from an olefin having from about 6 to about 12 carbon atoms per molecule.
• these procedures are more fully described in US. Pat. 2,937,129 and US. Pat. 3,149,178, the subject matter of which is incorporated, in its entirety, in this application, by reference.
• R and R' may be the same or different and are hydrocarbylene of from 2 to 30 carbon atoms
• hydrocarbylene is a divalent organic radical composed solely of carbon and hydrogen which may be aliphatic, alicyclic or aromatic or combinations thereof, e.g., alkaryl, aralkyl, etc., having its two free valences on different carbon atoms
• R and R" may be the same or different and are hydrocarbyl of from 1 to 30 carbon atoms
• hydrocarbyl is a monovalent organic radical composed solely of carbon and hydrogen which may be aliphatic, aromatic, or alicyclic or combinations thereof, e.g., aralkyl alkaryl, etc.
• the polyureas of the above formula are readily prepared by mixing diisocyanates and diamines with monoisocyanates or monoamines in the proper proportions to form the desired polyurea.
• the greases thickened with the polyureas are useful at temperatures from about -l00 F. to 500 F. and remain unctuous after long use, not, becoming hard or brittle.
• the grease compositions thus formed are extremely resistant to emulsification in water.
• x is an integer from 1 to 3, preferably, l, R and R are the same or different and are hydrocarbyl of from 5 to 28 carbon atoms, preferably of from 6 to 25 carbon atoms and R and R may be the same or different and will be hydrocarbylene of from 2 to 26 carbon atoms, more usually of from 2 to 18 carbon atoms. It is further preferred that in the tetraureas, the sum of the carbon atoms of [R and R is in the range of 10 to 30 and the sum of the carbon atoms of R and R is in the range of 12 to 40.
• the monoamine or monoisocyanate used in the formation of the polyurea will form the terminal end group.
• these terminal end groups will be of from 1 to 30 carbon atoms, but are preferably of from 5 to 28 carbon atoms and more desirably of from 6 to 25 carbon atoms.
• the substituent on the nitrogen is a hydrocarbon radical, which may be aliphatic,
• aromatic or alicyclic may be aliphatically saturated or unsaturated, or may be combinations of the various types of hydrocarbon radicals.
• Illustrative of various monoamines are pentylamine, hexyla'mine, heptylamine, octylamine, decylamine, dodecylamine, tetradecylamine, hexadecylamine, octadecylamine, eicosylamine, dodecenylamine, hexadecenylamine, octadecenylamine, octadecadienylamine, abietylamine, aniline, toluidine, naphthylamine, cumylamine, bornylamine, fenchylamine, tert.-butyl aniline, benzylamine, beta-phenethylamine, etc.
• monoisocyanates are hexylisocyanate, decylisocyanate, dodecylisocyanate, tetradecylisocyanate, hexadecylisocyanate, phenylisocyanate, cyclohexylisocyanate, tolueneisocyanate, xyleneisocyanate, cumene- 'isocyanate, abietylisocyanate, cyclooctylisocyanate, etc.
• the preferred aromatic terminal end groups are those of from 6 to 12 carbon atoms.
• the preferred aliphatic terminal end groups are those of from 10 to 20 carbon atoms.
• the diamines and diisocyanates which form the internal hydrocarbon bridges between the ureas are, as indicated, of from 2 to 30 carbon atoms, preferably from 2 to 26 carbon atoms and more desirably of from 2 to 18 carbon atoms.
• Illustrative of various diamines are ethylenediamine, propanediamine, butanediamine, hexanediamine, dodecanedia'mine, octanediamine, hexadecanediamine, cyclohexanediamine, cyclooctanediamine, phenylenediarnine, toluenediamine, xylenediamine, dianilinemethane, ditoluidinemethane, bisaniline, bistoluidine, etc.
• diisocyanates are hexanediisocyanate, decanediisocyanate, octadecanediisocyanate, phenylenediisocyanate, toluenediisocyante, bis (diphenylisocyanate) methylene bis(phenylisocyanate), etc.
• the aromatic hydrocarbylene or bridging groups will generally be of from about 6 to 18 carbon atoms.
• the aliphatic hydrocarbylene or bridging groups will generally be of from about 2 to 10 carbon atoms.
• the polyurea grease thickeners have a polar/nonpolar balance. That is, there will be at least about 6 carbon atoms per urea group and more usually about 8 carbon atoms per urea group, but fewer than 20 carbon atoms per urea group and more usually fewer than 16 carbon atoms per urea group.
• the tetraureas used in this invention have the following formula:
• the quantity of polyurea employed is in such amount as is sufficient to thicken the hydrogenated olefin polymer to the desired grease consistency.
• the amount of thickener may, for most practical purposes, range from about 1 to about 50% and preferably from about 5 to about 25%, by weight.
• the monoamines or isocyanates are merely brought together with the diisocyanates and diamines in the proper proportion, preferably in the presence of an inert diluent.
• the vehicle to be thickened or gelled will be the preferred diluent. It is not necessary that the diluent be a solvent for all the reactants. With a heterogeneous system, efficient stirring helps to insure smooth reaction between the various reactants.
• the temperature of the reaction will generally vary from about 20 C. to about 100 C., more usually from about 20 C. to 75 C.
• the reaction itself is exothermic and by starting at room temperature, elevated temperatures are obtained. However, external heating or cooling may be desirable.
• the concentration of polyurea in the final product may vary as hereinbefore indicated from about 1 to 50 weight percent, depending on the various reactants, the particular product desired, etc.
• the grease of Example 2 exhibited the lowest starting torque at 40 F. and also a very satisfactory evaporation loss of 5.6% at 350 F. These values are compared with maximum readings for an acceptable wide temperature range grease of 2000 gm. cm. maximum torque at -40 F. and 10% maximum evaporation loss at 350 F.
• the grease of Example 1 employing the C hydrogenated olefin polymer vehicle, was found to exhibit an unacceptably high temperature range reading.
• the grease of Example 3 employing the C hydrogenated olefin polymer vehicle exhibited an unsatisfactory reading at low temperature, although the amount of evaporation loss was satisfactory.
• Example 2 having the polyurea thickener in the preferred C hydrogenated olefin polymer oil, is compared with this same oil vehicle, employing a lithium soap thickener in Example 4 and also compared with a non-soap thickener (Baragel clay and stabilizer) in Example 5.
• the C hydrogenated polymer oil in combination with the above-described polyurea thickener exhibits an Endurance Life at 350 F. of 500 hours as compared with an Endurance Life of less than 200 hours with the lithium soap and clay thickeners of Examples 4 and 5.
• a grease composition comprising a hydrogenated olefin polymer vehicle, said polymer having been prepared from an olefin having from about 6 to about 12 carbon atoms per molecule, and a grease-forming quantity of a thickening agent comprising a polyurea having the following formula:
• R, R and R are hydrocarbon radicals containing from 1 to 30 carbon atoms, and R is a hydrocarbon radical containing from 2 to 30 carbon atoms.
• a grease composition as defined in claim 1 wherein the polyurea thickener has the following formula:
• the polyurea thickener is present in an amount from about 5 to about 25 percent, by weight.
• a grease composition as defined in claim 1 wherein the polyurea thickener has the following formula:
• R and R" are hydrocarbon radicals of from 5 to 28 carbon atoms
• R' and R are hydrocarbon radicals of from 2 to 26 carbon atoms, wherein the ratio of carbon atoms to the number of urea groups is at least about 6:1.
• a grease composition as defined in claim 1 wherein the polyurea thickener has the following formula:
• R and R are hydrocarbyl of from 5 to 28 carbon atoms, and R and R are hydrocarbylene of from 2 to 26 carbon atoms, wherein the ratio of carbon atoms to the number of urea groups is at least about 6: 1.
• R and R are from 6 to 25 carbon atoms and R and R are from 2 to 18 carbon atoms.

Landscapes

• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Organic Chemistry (AREA)
• Lubricants (AREA)

Applications Claiming Priority (1)

Publications (1)

Family

ID=22048436

Family Applications (1)

Country Status (7)

Cited By (7)

• 1970
  • 1970-08-12 US US00063324A patent/US3725279A/en not_active Expired - Lifetime
• 1971
  • 1971-04-27 GB GB1163971*[A patent/GB1310184A/en not_active Expired
  • 1971-05-24 ZA ZA713345A patent/ZA713345B/xx unknown
  • 1971-08-03 DE DE19712138843 patent/DE2138843A1/de active Pending
  • 1971-08-11 AT AT701471A patent/AT314713B/de not_active IP Right Cessation
  • 1971-08-11 FR FR7129405A patent/FR2102214A1/fr not_active Withdrawn
  • 1971-08-11 NL NL7111085A patent/NL7111085A/xx unknown

Also Published As

Similar Documents