US3843535A - Lubricating compositions - Google Patents
Lubricating compositions Download PDFInfo
- Publication number
- US3843535A US3843535A US00364066A US36406673A US3843535A US 3843535 A US3843535 A US 3843535A US 00364066 A US00364066 A US 00364066A US 36406673 A US36406673 A US 36406673A US 3843535 A US3843535 A US 3843535A
- Authority
- US
- United States
- Prior art keywords
- carbon atoms
- oils
- acids
- composition
- lubricating
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- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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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
- C10M1/00—Liquid compositions essentially based on mineral lubricating oils or fatty oils; Their use as lubricants
- C10M1/08—Liquid compositions essentially based on mineral lubricating oils or fatty oils; Their use as lubricants with additives
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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
- C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
- C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
- C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
- C10M2203/102—Aliphatic fractions
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- C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
- C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
- C10M2203/108—Residual fractions, e.g. bright stocks
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- C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
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- 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
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- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/28—Esters
- C10M2207/281—Esters of (cyclo)aliphatic monocarboxylic acids
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- C10M2207/282—Esters of (cyclo)aliphatic oolycarboxylic acids
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- C10M2207/283—Esters of polyhydroxy compounds
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- C10M2207/286—Esters of polymerised unsaturated acids
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- C10M2207/287—Partial esters
- C10M2207/289—Partial esters containing free hydroxy groups
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- 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
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- C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
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- C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
- C10M2209/104—Polyethers, i.e. containing di- or higher polyoxyalkylene groups of alkylene oxides containing two carbon atoms only
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- C10M2209/105—Polyethers, i.e. containing di- or higher polyoxyalkylene groups of alkylene oxides containing three carbon atoms only
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- C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
- C10M2209/106—Polyethers, i.e. containing di- or higher polyoxyalkylene groups of alkylene oxides containing four carbon atoms only
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- C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
- C10M2209/107—Polyethers, i.e. containing di- or higher polyoxyalkylene groups of two or more specified different alkylene oxides covered by groups C10M2209/104 - C10M2209/106
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- C10M2209/109—Polyethers, i.e. containing di- or higher polyoxyalkylene groups esterified
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- C10M2209/11—Complex polyesters
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- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions
- C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
- C10M2215/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
- C10M2215/068—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings having amino groups bound to polycyclic aromatic ring systems, i.e. systems with three or more condensed rings
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- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions
- C10M2215/086—Imides [having hydrocarbon substituents containing less than thirty carbon atoms]
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- 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
- C10M2215/28—Amides; Imides
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- C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
- C10N2020/01—Physico-chemical properties
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- C10N2040/042—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives for automatic transmissions
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- C10N2040/046—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives for traction drives
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- C10N2040/22—Metal working with essential removal of material, e.g. cutting, grinding or drilling
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- C10N2040/241—Manufacturing joint-less pipes
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- C10N2040/245—Soft metals, e.g. aluminum
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- C10N2040/246—Iron or steel
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- C10N2040/244—Metal working of specific metals
- C10N2040/247—Stainless steel
Definitions
- Lubricating compositions particularly useful for manufacturing multigrade oils, hydraulic fluids, oils for industrial gears and cutting oils, comprise (A) a hydrocarbon oil produced according to a conventional process and (B) at least one compound complying with the formula:
- m is 2 or 3, x is from 0.15 m. tom inclusive; when m is 2, R is a divalent aliphatic hydrocarbon radical and when m is 3, R is a trivalent aliphatic hydrocarbon radical; R is selected from the alkylene radicals having 2-5 carbon atoms, 12 is an integer from 2 to 50 and each of R and R is a monovalent hydrocarbon radical, the proportion of said compound (B) with respect to said hydrocarbon oil (A) being sufficient to impart to said composition the desired viscosimetric characteristics.
- This invention relates to new lubricating compositions consisting of mixtures of conventional hydrocarbon oils and derivatives of polyalkyleneglycols.
- the conventional base oils are prepared according to different methods.
- the main processes for manufacturing these oils are the acid or solvent refining of vacuum distillates or deasphalted vacuum residues from crude oils, the hydrotreatment of the same petroleum cuts and the oligomerization of olefinic hydrocarbons.
- a vacuum distillate or deasphalted vacuum residue can be subjected to a solvent extraction for example by means of furfurol or phenol, so as to eliminate from the petroleum cut the aromatic compounds contained therein, then to a series of treatments such as dewaxing, clay bleaching and moderate hydrogenation, at a temperature of from 250 to 350 C., under a hydrogen pressure of to 80 kg./cm. in the presence of a catalyst.
- the second process the hydrotreatment of the abovementioned petroleum cuts, may be achieved, for example, according to the teaching of U.S. Pat. No. 3,560,370, in the name of the applicant.
- the hydrotreatment is conducted at a temperature of from 350 to 450 C., under a hydrogen pressure of from 80 to 240 kg./cm. and in the presence of a catalyst.
- the oil is manufactured by oligomerizing olefini-c hydrocarbons having from 2 to 20 and preferably from 9 to 16 carbon atoms per molecule.
- This oligomerization may be achieved by the action of catalysts consisting of aluminum halides, or by the action of heat, in the presence of organic peroxides acting as initiators.
- the oils prepared according to the above-described processes generally exhibit viscosity indexes of from 50 to 160 and, more particularly, from 50 to for solvent refined oils, from 50 to for the hydrorefined oils 'and from 110 to for the oligomerization oils.
- oils obtained in the two last above-described processes already exhibit must better characteristics than those obtained by the first process.
- all these oils require the addition, besides the conventional additives such as detergents or antioxidants, of more or less substantial amounts of viscosity additives, which however exhibit inherent disadvantages such as poor thermal stability and/or mechanical stability.
- the present invention relates to new lubricating compositions which contain generally a compound (A) consisting of a hydrocarbon oil and a compound (B) selected amongst the esters of polyalkyleneglycol others.
- the hydrocarbon oil (A) is selected among the mineral oils obtained either by solvent refining or by acid treatment, or by severe hydrotreatment of vacuum distillates or deasphalted vacuum residues from crude oils and the synthetic oils obtained by oligomerizing olefinic hydrocarbons having from 2 to 20 carbon atoms per molecule.
- compound (B) results from the esterifioation of a dior ztri-oarboxy1ic acid by at least one ether of a polyalkyleneglycol and a monoalcohol or monophenol, said ether being used either alone or in admixture with at least one monoalcohol or monophenol.
- compound (B) complies with the general formula:
- m is 2 or 3; x is from 0.15 m. to m inclusive, preferably from 0.30 m. to m inclusive; when m is 2, R is the divalent aliphatic hydrocarbon radical of a dicarboxylic acid and when m is 3, R is the trivalent aliphatic hydrocarbon radical of a tricarboxylic acid; R is selected from the alkylene radicals having 2-5 carbon atoms, preferably ethylene or propylene; n is an integer from 2 to 50, preferably 5 to 30 and each of R and R' is the monovalent hydrocarbon radical of a monoalcohol or monophenol.
- the dicarbxylic acids particularly contemplated in this invention are: saturated or unsaturated aliphatic dicarboxylic acids having 3 to carbon atoms, as well as the saturated or unsaturated aliphatic dicarboxylic acids having 28-44 carbon atoms, such as those resulting from di-merization of unsaturated fatty acids of 14-22 carbon atoms, optionally followed with a hydrogenation.
- dicarboxylic acids can be cited as examples: malonic, succinic, maleic, fumaric, glutaric, adipic, pimelic, suberic, azelaic, sebacic, dodecanedioic and isononadecanedioic acids as well as the saturated or unsaturated dicarboxylic acids obtained from dimerization of unsaturated fatty acids such as the following: tetradecenoio acids (e.g. myristoleic acid), hexadecenoic acids .(e.g. palmitoleic acid), octadecenoic acids (e.g. oleic acid), octadecadienoic acids (e.g.
- linoleic acid octadecatrienoic acids (e.g. linolenic acid), eicosenoic acids and docosenoic acids (e.g. crucic and brassidic acids) and natural or synthetic mixtures thereof.
- Natural mixtures of such unsaturated fatty acids are, for example, fatty acids from soya-bean, linseed oil, spermacetic oil or colza oil.
- the tricarboxylic acids particularly contemplated in this invention are the saturated or unsaturated aliphatic tricarboxylic acids having 42-66 carbon atoms, such as those resulting from trimerization of unsaturated fatty acids of 14-22 carbon atoms, optionally followed with a hydrogenation.
- these carboxylic acids are those obtained from the trimerization of the specific unsaturated fatty acids or mixtures thereof as cited hereinabove.
- di- (or tri-) carboxylic acids resulting from the di- (or tri)merization of unsaturated fatty acids of 14-22 carbon atoms particularly preferred are those which result from dimerization or trimerization of one or more G -unsaturated fatty acids, such as oleic, linoleic and linolenic acids, or natural or synthetic mixtures containing them in noticeable proportions.
- the di and tricarboxylic acids respectively contain 36 and 54 carbon atoms.
- the monoalcohols are particularly aliphatic monoalcohols of 1-25 carbon atoms such as, for example, methanol, ethanol, n-butanol, 2-ethylhexanol, isononanol, isodecanol, dodecanol, isotridecanol or isopentadecanol, or alicyclic monoalcohols of 3-25 carbon atoms, such as, for example: cyclopropanol, cyclobutanol, cyclohexanol or methylcyclohexanol.
- the monophenols particularly contain 6-25 carbon atoms. Examples are: phenols unsubstituted or substituted with one or more alkyl radicals such as heptylphenol, nonylphenol or dodecylphenol.
- the manufacture of compounds of formula (I) may be achieved, according to known methods, by the total esterification of the dior tri-carboxylic acid with one or more ether of a poly-alkyleneglycol and a monoalcohol or monophenol, said ether having the formula:
- R R and n are as defined hereinabove, or with a mixture of one or more ether of such a type with one or more monoalcohol or monophenol having the formula:
- R is as defined hereinabove, said mixture con taining at least 15% by mole, preferably at least by mole, of compound of formula (2).
- the esterification reaction may be carried out in the presence of a convenient catalyst, the water produced being removable by azeotropic entrainement by means of a solvent.
- the remaining acidic products may be removed either by washing with a hydroalcoholic potash solution and then with water or by clay treatment.
- the solvent is then expelled under vacuum and the residue, consisting in the ester of polyalkyleneglycol ether, may be recovered without having to be distilled.
- ethers of polyalkyleneglycol and monoalcohol (or monophenol) of formula (2) they may be obtained, according to known methods, by the condensation of one or more alkylene oxide (particularly ethylene oxide or propylene oxide or mixtures thereof) on the convenient monoalcohol (or monophenol).
- the so-obtained ethers of polyalkyleneglycol and monoalcohol (or monophenyl) have generally an average molecular weight of about to 2500, varying with the monoalcohol (or monophenol) used and the polycondensation grade of the alkylene oxide (n from 2 to 50, preferably from 5 to 30).
- Compounds of formula (1) as defined hereinabove are liquids, the viscosity of which is generally from 20 to 500 cst. at 98.9 C., more particularly from 40 to 200 cst., and their density is generally around 1. Most of them are miscible with mineral or synthetic oils in rather large proportions, their miscibility being better with fluid oils than with more viscous oils, and better with naphthenic mineral oils than with paraflinic mineral oils.
- R O'- groups are particularly derived from ethylene oxide and propylene oxide, as the derivatives of ethylene oxide are generally less miscible with a given oil than those of propylene oxide, there are preferably used compounds in which all -R -O groups are derived from propyleneoxide or still mixed compounds in which the ratio of -R -O groups derived from ethylene oxide to groups derived from propylene oxide does not exceed l/ 1. Still further, are also preferred compounds (B) of formula 1) in which radical R and/or the major part of radicals R and R';,, if any, contain at least 10 carbon atoms.
- decanedioates of ethers obtained by condensation of propylenc oxide on decanol.
- dodecanedioates of ethers obtained by condensation of propylene oxide on n-butanol.
- dodecanedioates of ethers obtained by condensation of propylene oxide on Z-ethylhexanol.
- dodecanedioates of ethers obtained by condensation of a mixture (25/75 by weight) of ethylene oxide and propylene oxide on decanol.
- dodecanedioates of ethers obtained by condensation of propylene oxide on cyclohexanol.
- dodecanedioates of ethers obtained by condensation of propylene oxide on dodecylphenol.
- esters of C dimeric fatty acids with ethers obtained by condensation of propylene oxide on 2-ethylhexanol.
- dodecanedioates of mixtures (15-85 by moles) of ethers obtained by condensation of propylene oxide on 2- ethylhexanol with C1345 saturated aliphatic monoalcohols.
- esters of C dimeric fatty acids with mixtures (30-70 by moles) of ethers obtained by condensation of propylene oxide on 2-ethylhexanol with C saturated aliphatic monoalcohols.
- esters of C dimeric fatty acids with mixtures (50-50 by moles) of ethers obtained by condensation of propylene oxides on 2-ethylhexanol with C saturated aliphatic monoalcohols.
- esters of C trimeric fatty acids with ethers obtained by condensation of propylene oxide on n-butanol.
- esters of C trimeric fatty acids with ethers obtained by condensation of propylene oxide on C saturated aliphatic mono-alcohols.
- esters of C trimcric fatty acids with mixtures (30-70 by moles) of ethers obtained by condensation of propylene oxide on 2-ethyl hexanol with C1345 saturated aliphatic monoalcohols.
- esters of C trimeric fatty acids with mixtures (7030 by moles) of ethers obtained by condensation of propylene oxide on C saturated aliphatic monoalcohols and dodecanol.
- At least one compound (B) of formula (1) is added to a conventional hydrocarbon oil in such a proportion that the mixture exhibits the desired Viscosimetric characteristics.
- the hydrocarbon oil may be selected among the mineral oils (solvent-refined paraflinic oils or hydrorefined oils) having for example a viscosity at 37.8 C. of at least about 100 SSU, more particularly from about 150 to 350 SSU.
- One or more compound (B) is added thereto until the desired viscosimetric characteristics are reached or approached as near as possible.
- the convenient proportion of compound (B) so added may amount for example to 595% by weight of the resulting mixture. If necessary to adjust more closely the viscosimetric characteristics of the mixture, a conventional Vi-improver may be added thereto, this addition being made, however, in a very small amount, far lower in any case than that it would be necessary to add to a conventional mineral oil, in the absence of compound (B), in order to reach the same viscosimetric characteristics.
- compositions according to the invention may contain the hydrocarbon oil (A) in a major proportion (50 to 95% by weight) as compared with the ester of polyalkyleneglycol ether (B) (S to 50% by weight), or, on the contrary, the compound (B) may be present in a major proportion (50 to 95% by weight) as compared with the compound (A) (5 to 50% by weight).
- an amount of about 2 to by weight, in some cases as high as 30 by weight, of a third solvent such as an ester of an aliphatic dicarboxylic acid with an aliphatic monoalcohol or an ester of an aliphatic monocarboxylic acid with an aliphatic polyalcohol may be added to the composition.
- third solvents are: isodecyl adipate trimethyl-hexyl azelate, Z-ethylhexyl sebacate, neopentylglycol pelargonate or trimethylolpropane pelargonate.
- compositions of the invention may be used for manufacturing motor oils and particularly multigrade oils
- Ether I.-Ether from condensation of propylene oxide on n-butanol, having a viscosity at 37.8 C. of about 40 cst. Said ether contains about 8 propylene oxide units per molecule.
- esters A to F were the following: Ester A.Dodecanedioate of Ether I Viscosity at 37.8 C.l SSU Viscosity index (VI )l90 Ester B.Ester of dimeric acid with a mixture (SO- 50 by moles) of Ether III and Z-ethylhexanol.
- Ester C.Ester of trimeric acid with Ether II Ester D.Ester of trimeric acid with Ether III. Ester B.Ester of trimeric acid with a mixture (67- 33 by moles) of Ether III and a mixture of saturated aliphatic C alcohols.
- Esters B to F Some physical characteristics of Esters B to F are given hereinafter.
- lubricating compositions have been prepared by determining the proportions of Ester A to be added to various hydrocarbon oils so as to obtain multigrade oils having given viscosity characteristics. In some cases, a minor amount of a Vi-improver (polymethacrylate) had to be added.
- R is the divalent hydrocarbon radical of a dicarboxylic acid selected from the group consisting of unsaturated dicarboxylic acids having 28-44 carbon atoms resulting from dimerization of unsaturated fatty acids of 14-22 carbon atoms, and the corresponding saturated dicarboxylic acids, and when m is 3, R is a trivalent hydrocarbon radical of a tricarboxylic acid selected from the group consisting of unsaturated tricarboxylic acids having 42-66 carbon atoms resulting from trimerization of unsaturated fatty acids of 14-22 carbon atoms, and the cordesponding saturated tricarboxylic acids; R is selected from the alkylene radicals having 2-5 carbon atoms, n
- Multigrade oils have been prepared by adding Esters B-F to hydrocarbon oils.
- a third solvent isodecyladipate has been added to improve the miscibility of the Ester in the hydrocarbon oil, when necessary, a minor amount of a Vi-irnprover has also been added (polymethacrylate To each of the base mixtures, 0.5% by Weight of an anti-gelling additive and 5% by weight of a detergent additive have also been added.
- composition and some physical characteristics of 30 the multigrade oils are given in the following Table II,
- compositions acgether constituting the redominant component of said cording to this invention is reduced with respect to volacomposition.
- tility of commercial multigrade oils of the same SAE- 60 2- A mp i n as fin y l im 1, wh r in h category, formula of compound (B), R is selected from the group From the foregoing description, one skilled in the art C H IStmg of ethylene and propylene.
- hydrocarbon oil (A) is selected from the group consisting of solvent-refined paraffim'c mineral oils and hydrorefined oils having a viscosity at 37.8 C. of at least 100 SSU.
- composition as defined by claim 1 wherein the hydrocarbon oil (A) represents from to 95% by weight and compound (B) from 95 to 5% by weight.
- composition as defined by claim 10 wherein x 12.
- a multigrade oil comprising a major part of a lubricating composition as defined by claim 12.
- a multigrade oil comprising a major part of a lubricating composition as defined by claim 14.
- a multigrade oil comprising a major part of a lubricating composition as defined by claim 16.
- composition as defined by claim 16 further comprising a minor amount of a third solvent selected from the group consisting of esters of aliphatic dicarboxylic acids with aliphatic monoalcohols and esters of aliphatic monocarboxylic acids with aliphatic polyalcohols.
- a multigrade oil comprising a major part of a lubri cating composition as defined by claim 24.
- a tricarboxylic acid selected from the group consisting of unsaturated tricarboxylic acids having 54 carbon atoms, which result from trimerization of unsaturated fatty acids of 18 carbon atoms, and the corresponding saturated tricarboxylic acids.
- composition as defined by claim 34 wherein the major part of R and R' contains at least 10 carbon atoms.
- composition as defined by claim 34 wherein at is 37.
- a composition as defined by claim 34 further comprising a minor amount of a third solvent selected from the group consisting of esters of aliphatic dicarboxylic acids with aliphatic monoalcohols and esters of aliphatic monocarboxylic acids with aliphatic polyalcohols.
- a multigrade oil comprising a major part of a lubricating composition as defined by claim 34.
- composition as defined by claim 34 wherein R is selected from the group consisting of ethylene and propylene.
- composition as defined by claim 39 wherein the ratio of R radicals consisting of ethylene to R radicals consisting of propylene is at most 1/ 1.
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Abstract
1. A LUBRICATING COMPOSITON OF HIGH VISCOSITY INDEX SUITABLE FOR USE AS BASE LIBRICANT FOR MULTIGRADE OILS COMPRISING LUBRICATING AMOUNTS OF A MIXTURE OF (A) A HYDROCARBONOIL OF LUBRICATING VISCOSITY SELECTED FROM THE GROUP CONSISTING OF THE SOLVENT-REFINED MINERAL OILS, THE ACID-REFINED MINERAL OILS, THE HYDROREFINED OILS AND THE SYNTHETIC OILS OBTAINED BY OLIGOMERIZATION OF OLEFINIC HYDROCARBONS HAVING 2-20 CARBON ATOMS AND (B) AT LEAST ONE COMPOUND COMPLYING WITH THE GENERAL FORMULA:
R1(-CO-O$R2-O$NR3)X)-CO-O-R''3)(M-X)
WHERE M IS 2 OR 3, X IS FROM 0.15 M. TO M INCLUSIVE; WHEN M IS 2, R1 IS THE DIVALENT HYDROCARBON RADDICAL OF A DICARBOXYLIC ACID SELECTED FROM THE GROUP CONSISTING OF UNSATURATED DICARBOXYLIC ACIDS HAVING 28-44 CARBON ATOMS RESULTING FROM DIMERIZATION OF UNSATURATED FATTY ACIDS OF 14-22 CARBON ATOMS, AND THE CORRESPONDING SATURATED DICARBOXYLIC ACIDS, AND WHEN M IS 3, R1 IS A TRIVALENT HYDROCARBON RADICAL OF A TRICARBOXYLIC ACID SELECTED FROM THE GROUP CONSISTING OF UNSATURATED TRICARBOXYLIC ACIDS HAVING 42-66 CARBON ATOMS RESULTING FROM TRIMERIZATION OF UNSATURATED FATTY ACIDS OF 14-22 CARBON ATOMS, AND THE CORDESPONDING SATURATRD TRICARBOXYLIC ACIDS; R2 IS SELECTED FROM THE ALKYLENE RADICALS HAVING 2-5 CARBON ATOMS, N IS AN INTEGER FROM 2 TO 50 AND EACH OF R3 AND R''3 IS THE MONOVALENT HYDROCARBON RADICAL OF A COMPOUND SELECTED FROM THE GROUP CONSISTING OF ALIPHATIC MONOALCOHOLS OF 1-25 CARBON ATOMS, ALICYCLIC MONOALCOHOLS OF 3-25 CARBON ATOMS AND UNSUBSTITUTED AND ALKYL-SUBSTITUTED MONOPHENOLS OF 6-25 CARBON ATOMS, THE PROPORTION OF SAID COMPOUND (B) WITH RESPECT TO SAID HYDROCARBON OIL (A) BEING SUFFICIENT TO IMPART TO SAID COMPOSITION THE DESIRED HIGH VISCOSITY INDEX, AND COMPONENTS (A) AND (B) TOGETHER CONSTITUTING THE PREDOMINANT COMPONENT OF SAID COMPOSITION.
R1(-CO-O$R2-O$NR3)X)-CO-O-R''3)(M-X)
WHERE M IS 2 OR 3, X IS FROM 0.15 M. TO M INCLUSIVE; WHEN M IS 2, R1 IS THE DIVALENT HYDROCARBON RADDICAL OF A DICARBOXYLIC ACID SELECTED FROM THE GROUP CONSISTING OF UNSATURATED DICARBOXYLIC ACIDS HAVING 28-44 CARBON ATOMS RESULTING FROM DIMERIZATION OF UNSATURATED FATTY ACIDS OF 14-22 CARBON ATOMS, AND THE CORRESPONDING SATURATED DICARBOXYLIC ACIDS, AND WHEN M IS 3, R1 IS A TRIVALENT HYDROCARBON RADICAL OF A TRICARBOXYLIC ACID SELECTED FROM THE GROUP CONSISTING OF UNSATURATED TRICARBOXYLIC ACIDS HAVING 42-66 CARBON ATOMS RESULTING FROM TRIMERIZATION OF UNSATURATED FATTY ACIDS OF 14-22 CARBON ATOMS, AND THE CORDESPONDING SATURATRD TRICARBOXYLIC ACIDS; R2 IS SELECTED FROM THE ALKYLENE RADICALS HAVING 2-5 CARBON ATOMS, N IS AN INTEGER FROM 2 TO 50 AND EACH OF R3 AND R''3 IS THE MONOVALENT HYDROCARBON RADICAL OF A COMPOUND SELECTED FROM THE GROUP CONSISTING OF ALIPHATIC MONOALCOHOLS OF 1-25 CARBON ATOMS, ALICYCLIC MONOALCOHOLS OF 3-25 CARBON ATOMS AND UNSUBSTITUTED AND ALKYL-SUBSTITUTED MONOPHENOLS OF 6-25 CARBON ATOMS, THE PROPORTION OF SAID COMPOUND (B) WITH RESPECT TO SAID HYDROCARBON OIL (A) BEING SUFFICIENT TO IMPART TO SAID COMPOSITION THE DESIRED HIGH VISCOSITY INDEX, AND COMPONENTS (A) AND (B) TOGETHER CONSTITUTING THE PREDOMINANT COMPONENT OF SAID COMPOSITION.
Description
United States Patent M 3,843,535 LUBRICATIN G COMPOSITIONS Jacques Denis, Ville dAvray, and Guy Parc, Rueil-Malmaison, France, assignors to Institut Francais du Petr-ole, des Carburants et Lubrifiants No Drawing. Continuation-impart of application Ser. No. 204,329 Dec. 2, 1971, now Patent No. 3,773,668. This application May 25, 1973, Ser. No. 364,066 Claims priority, application France, Dec. 3, 1970, 43,605; Apr. 15, 1971, 13,437
Int. Cl. Cm 1/26 U.S. Cl. 252-57 41 Claims ABSTRACT OF THE DISCLOSURE Lubricating compositions, particularly useful for manufacturing multigrade oils, hydraulic fluids, oils for industrial gears and cutting oils, comprise (A) a hydrocarbon oil produced according to a conventional process and (B) at least one compound complying with the formula:
where m is 2 or 3, x is from 0.15 m. tom inclusive; when m is 2, R is a divalent aliphatic hydrocarbon radical and when m is 3, R is a trivalent aliphatic hydrocarbon radical; R is selected from the alkylene radicals having 2-5 carbon atoms, 12 is an integer from 2 to 50 and each of R and R is a monovalent hydrocarbon radical, the proportion of said compound (B) with respect to said hydrocarbon oil (A) being sufficient to impart to said composition the desired viscosimetric characteristics.
CROSS-REFERENCE TO RELATED APPLICATION This application is a continuation-in-part of copending application Ser. No. 204,329, filed Dec. 2, 1971, now U.S. Pat. No. 3,773,668 Nov. 20, 1973 and is directed to a non-elected distinct invention thereof pursuant to an election of species requirement.
This invention relates to new lubricating compositions consisting of mixtures of conventional hydrocarbon oils and derivatives of polyalkyleneglycols.
The conventional base oils are prepared according to different methods. The main processes for manufacturing these oils are the acid or solvent refining of vacuum distillates or deasphalted vacuum residues from crude oils, the hydrotreatment of the same petroleum cuts and the oligomerization of olefinic hydrocarbons.
In the first of these processes, a vacuum distillate or deasphalted vacuum residue can be subjected to a solvent extraction for example by means of furfurol or phenol, so as to eliminate from the petroleum cut the aromatic compounds contained therein, then to a series of treatments such as dewaxing, clay bleaching and moderate hydrogenation, at a temperature of from 250 to 350 C., under a hydrogen pressure of to 80 kg./cm. in the presence of a catalyst.
-In the case of certain crude oils containing a small proportion of aromatic compounds, it is possible to replace the solvent extraction by an acid treatment, generally with sulfuric acid.
The second process, the hydrotreatment of the abovementioned petroleum cuts, may be achieved, for example, according to the teaching of U.S. Pat. No. 3,560,370, in the name of the applicant. In this patent, the hydrotreatment is conducted at a temperature of from 350 to 450 C., under a hydrogen pressure of from 80 to 240 kg./cm. and in the presence of a catalyst.
in the third process, the oil is manufactured by oligomerizing olefini-c hydrocarbons having from 2 to 20 and preferably from 9 to 16 carbon atoms per molecule.
3,843,535 Patented Oct. 22, 1974 This oligomerization may be achieved by the action of catalysts consisting of aluminum halides, or by the action of heat, in the presence of organic peroxides acting as initiators.
The oils prepared according to the above-described processes generally exhibit viscosity indexes of from 50 to 160 and, more particularly, from 50 to for solvent refined oils, from 50 to for the hydrorefined oils 'and from 110 to for the oligomerization oils.
It can be observed that the oils obtained in the two last above-described processes already exhibit must better characteristics than those obtained by the first process. For their various uses, all these oils require the addition, besides the conventional additives such as detergents or antioxidants, of more or less substantial amounts of viscosity additives, which however exhibit inherent disadvantages such as poor thermal stability and/or mechanical stability.
Moreover, these conventional oils necessitate a compromise between a low cold viscosity, a sufiicient viscosity at high temperature (l00150 C.) and a low volatility.
It is known that the above-mentioned drawbacks have been partly avoided by adding to the conventional base oils a certain amount of synthetic oils consisting of esters of polycarboxylic acids or of polyols. The improvement achieved by the use of these products is however very limited, with respect to the viscosity index.
It is an object of this invention to provide new lubricating compositions exhibiting viscosity-temperature characteristics so improved that the amount of viscosity additives that must be incorporated thereto is very substantially decreased (or even nullified). Consequently, their thermal stability and mechanical resistance to shearing are also improved and their volatility is reduced. Moreover, they exhibit such an exceptional lubricating power that their use makes it possible to avoid mechanical ditficulties such as seizing and pitting as well as to reduce the wear of the machines lubricated therewith. These qualities are particularly useful for lubricating engines operating under severe conditions, hydraulic circuits, gears of various types as well as in machining metals.
The present invention relates to new lubricating compositions which contain generally a compound (A) consisting of a hydrocarbon oil and a compound (B) selected amongst the esters of polyalkyleneglycol others.
The hydrocarbon oil (A) is selected among the mineral oils obtained either by solvent refining or by acid treatment, or by severe hydrotreatment of vacuum distillates or deasphalted vacuum residues from crude oils and the synthetic oils obtained by oligomerizing olefinic hydrocarbons having from 2 to 20 carbon atoms per molecule.
Generally, compound (B) results from the esterifioation of a dior ztri-oarboxy1ic acid by at least one ether of a polyalkyleneglycol and a monoalcohol or monophenol, said ether being used either alone or in admixture with at least one monoalcohol or monophenol.
More particularly, compound (B) complies with the general formula:
wherein m is 2 or 3; x is from 0.15 m. to m inclusive, preferably from 0.30 m. to m inclusive; when m is 2, R is the divalent aliphatic hydrocarbon radical of a dicarboxylic acid and when m is 3, R is the trivalent aliphatic hydrocarbon radical of a tricarboxylic acid; R is selected from the alkylene radicals having 2-5 carbon atoms, preferably ethylene or propylene; n is an integer from 2 to 50, preferably 5 to 30 and each of R and R' is the monovalent hydrocarbon radical of a monoalcohol or monophenol.
The dicarbxylic acids particularly contemplated in this invention are: saturated or unsaturated aliphatic dicarboxylic acids having 3 to carbon atoms, as well as the saturated or unsaturated aliphatic dicarboxylic acids having 28-44 carbon atoms, such as those resulting from di-merization of unsaturated fatty acids of 14-22 carbon atoms, optionally followed with a hydrogenation.
The following dicarboxylic acids can be cited as examples: malonic, succinic, maleic, fumaric, glutaric, adipic, pimelic, suberic, azelaic, sebacic, dodecanedioic and isononadecanedioic acids as well as the saturated or unsaturated dicarboxylic acids obtained from dimerization of unsaturated fatty acids such as the following: tetradecenoio acids (e.g. myristoleic acid), hexadecenoic acids .(e.g. palmitoleic acid), octadecenoic acids (e.g. oleic acid), octadecadienoic acids (e.g. linoleic acid), octadecatrienoic acids (e.g. linolenic acid), eicosenoic acids and docosenoic acids (e.g. crucic and brassidic acids) and natural or synthetic mixtures thereof. Natural mixtures of such unsaturated fatty acids are, for example, fatty acids from soya-bean, linseed oil, spermacetic oil or colza oil.
The tricarboxylic acids particularly contemplated in this invention are the saturated or unsaturated aliphatic tricarboxylic acids having 42-66 carbon atoms, such as those resulting from trimerization of unsaturated fatty acids of 14-22 carbon atoms, optionally followed with a hydrogenation. Examples of these carboxylic acids are those obtained from the trimerization of the specific unsaturated fatty acids or mixtures thereof as cited hereinabove. Among the di- (or tri-) carboxylic acids resulting from the di- (or tri)merization of unsaturated fatty acids of 14-22 carbon atoms, particularly preferred are those which result from dimerization or trimerization of one or more G -unsaturated fatty acids, such as oleic, linoleic and linolenic acids, or natural or synthetic mixtures containing them in noticeable proportions. The di and tricarboxylic acids respectively contain 36 and 54 carbon atoms.
The monoalcohols are particularly aliphatic monoalcohols of 1-25 carbon atoms such as, for example, methanol, ethanol, n-butanol, 2-ethylhexanol, isononanol, isodecanol, dodecanol, isotridecanol or isopentadecanol, or alicyclic monoalcohols of 3-25 carbon atoms, such as, for example: cyclopropanol, cyclobutanol, cyclohexanol or methylcyclohexanol. The monophenols particularly contain 6-25 carbon atoms. Examples are: phenols unsubstituted or substituted with one or more alkyl radicals such as heptylphenol, nonylphenol or dodecylphenol.
The manufacture of compounds of formula (I) may be achieved, according to known methods, by the total esterification of the dior tri-carboxylic acid with one or more ether of a poly-alkyleneglycol and a monoalcohol or monophenol, said ether having the formula:
noun-mun,
wherein R R and n are as defined hereinabove, or with a mixture of one or more ether of such a type with one or more monoalcohol or monophenol having the formula:
wherein R is as defined hereinabove, said mixture con taining at least 15% by mole, preferably at least by mole, of compound of formula (2). The esterification reaction may be carried out in the presence of a convenient catalyst, the water produced being removable by azeotropic entrainement by means of a solvent.
After the end of the reaction, the remaining acidic products may be removed either by washing with a hydroalcoholic potash solution and then with water or by clay treatment. The solvent is then expelled under vacuum and the residue, consisting in the ester of polyalkyleneglycol ether, may be recovered without having to be distilled.
As for ethers of polyalkyleneglycol and monoalcohol (or monophenol) of formula (2), they may be obtained, according to known methods, by the condensation of one or more alkylene oxide (particularly ethylene oxide or propylene oxide or mixtures thereof) on the convenient monoalcohol (or monophenol). The so-obtained ethers of polyalkyleneglycol and monoalcohol (or monophenyl) have generally an average molecular weight of about to 2500, varying with the monoalcohol (or monophenol) used and the polycondensation grade of the alkylene oxide (n from 2 to 50, preferably from 5 to 30).
Compounds of formula (1) as defined hereinabove are liquids, the viscosity of which is generally from 20 to 500 cst. at 98.9 C., more particularly from 40 to 200 cst., and their density is generally around 1. Most of them are miscible with mineral or synthetic oils in rather large proportions, their miscibility being better with fluid oils than with more viscous oils, and better with naphthenic mineral oils than with paraflinic mineral oils.
Further, among compounds (B) in which R O'- groups are particularly derived from ethylene oxide and propylene oxide, as the derivatives of ethylene oxide are generally less miscible with a given oil than those of propylene oxide, there are preferably used compounds in which all -R -O groups are derived from propyleneoxide or still mixed compounds in which the ratio of -R -O groups derived from ethylene oxide to groups derived from propylene oxide does not exceed l/ 1. Still further, are also preferred compounds (B) of formula 1) in which radical R and/or the major part of radicals R and R';,, if any, contain at least 10 carbon atoms.
As specific examples for compound (B), the following can be cited.
(a) compounds complying with formula (1) in which m is 2 and x is m, i.e.:
malonates of ethers obtained by condensation of propylene oxide on isotridecanol.
decanedioates of ethers obtained by condensation of propylenc oxide on decanol.
dodecanedioates of ethers obtained by condensation of propylene oxide on n-butanol.
dodecanedioates of ethers obtained by condensation of propylene oxide on Z-ethylhexanol.
dodecanedioates of ethers obtained by condensation of a mixture (25/75 by weight) of ethylene oxide and propylene oxide on decanol.
dodecanedioates of ethers obtained by condensation of propylene oxide on cyclohexanol.
dodecanedioates of ethers obtained by condensation of propylene oxide on dodecylphenol.
esters of C dimeric fatty acids with ethers obtained by condensation of propylene oxide on 2-ethylhexanol.
(b) compounds complying with formula (1) in which m is 2 and x is different from m, i.e.:
dodecanedioates of mixtures (15-85 by moles) of ethers obtained by condensation of propylene oxide on 2- ethylhexanol with C1345 saturated aliphatic monoalcohols.
esters of C dimeric fatty acids with mixtures (30-70 by moles) of ethers obtained by condensation of propylene oxide on 2-ethylhexanol with C saturated aliphatic monoalcohols.
esters of C dimeric fatty acids with mixtures (50-50 by moles) of ethers obtained by condensation of propylene oxides on 2-ethylhexanol with C saturated aliphatic monoalcohols.
esters of C dimeric fatty acids with mixtures {70-30 by moles) of ethers obtained by condensation of propylene oxide on C saturated aliphatic monoalcohols with 2-ethylhexanol.
(0) compounds complying with formula (1), in which m is 3 and x is m, i.e.:
esters of C trimeric fatty acids with ethers obtained by condensation of propylene oxide on n-butanol.
esters of C trimeric fatty acids with ethers obtained by condensation of propylene oxide on C saturated aliphatic mono-alcohols.
(d) compounds complying with formula (1), in which m is 3 and x is different from m, i.e.:
esters of C trimcric fatty acids with mixtures (30-70 by moles) of ethers obtained by condensation of propylene oxide on 2-ethyl hexanol with C1345 saturated aliphatic monoalcohols.
esters of C trimeric fatty acids with mixtures (7030 by moles) of ethers obtained by condensation of propylene oxide on C saturated aliphatic monoalcohols and dodecanol.
In order to prepare lubricating compositions according to this invention, at least one compound (B) of formula (1) is added to a conventional hydrocarbon oil in such a proportion that the mixture exhibits the desired Viscosimetric characteristics.
More particularly, the hydrocarbon oil may be selected among the mineral oils (solvent-refined paraflinic oils or hydrorefined oils) having for example a viscosity at 37.8 C. of at least about 100 SSU, more particularly from about 150 to 350 SSU. One or more compound (B) is added thereto until the desired viscosimetric characteristics are reached or approached as near as possible.
The convenient proportion of compound (B) so added may amount for example to 595% by weight of the resulting mixture. If necessary to adjust more closely the viscosimetric characteristics of the mixture, a conventional Vi-improver may be added thereto, this addition being made, however, in a very small amount, far lower in any case than that it would be necessary to add to a conventional mineral oil, in the absence of compound (B), in order to reach the same viscosimetric characteristics.
According to the nature of their components, the compositions according to the invention may contain the hydrocarbon oil (A) in a major proportion (50 to 95% by weight) as compared with the ester of polyalkyleneglycol ether (B) (S to 50% by weight), or, on the contrary, the compound (B) may be present in a major proportion (50 to 95% by weight) as compared with the compound (A) (5 to 50% by weight).
In order to increase the miscibility of compound (B) with the hydrocarbon oil, an amount of about 2 to by weight, in some cases as high as 30 by weight, of a third solvent such as an ester of an aliphatic dicarboxylic acid with an aliphatic monoalcohol or an ester of an aliphatic monocarboxylic acid with an aliphatic polyalcohol may be added to the composition.
Examples of third solvents are: isodecyl adipate trimethyl-hexyl azelate, Z-ethylhexyl sebacate, neopentylglycol pelargonate or trimethylolpropane pelargonate.
The compositions of the invention may be used for manufacturing motor oils and particularly multigrade oils;
The following examples illustrate the invention:
PREPARATIONS I TO HI By condensation of propylene oxide on the convenient alcohol or mixture of alcohols, the following ethers of polypropyleneglycol have been prepared:
Ether I.-Ether from condensation of propylene oxide on n-butanol, having a viscosity at 37.8 C. of about 40 cst. Said ether contains about 8 propylene oxide units per molecule.
Ether II.Ether from condensation of propylene oxide on n-butanol, having a viscosity at 37.8 C. of about 50 est. Said ether contains about 10 propylene oxide units per molecule.
Ether III.-Ether from condensation of propylene oxide on a mixture of saturated aliphatic C alcohols, having a viscosity at 37 .8 C. of about 100 cst. Said ether contains about 22 propylene oxide units per molecule.
PREPARATIONS A TO F Esters have been prepared, by a usual esterification method from the following carboxylic acids:
dodecanedioic acid. industrial dimeric acid, obtained by dimerization of unsaturated aliphatic C monocarboxylic acids (Trademark Epol 1040 of Unilever-Emery) Molecular weight565 Saponification index191197 Purity grade-9597% industrial trimeric acid, obtained by trimerization of unsaturated aliphatic C monocarboxylic acids (Trademark Empol 1040 of Unilever-Emery) Molecular weight-850 Saponification indexl92200 Purity grade-95 Esters A to F were the following: Ester A.Dodecanedioate of Ether I Viscosity at 37.8 C.l SSU Viscosity index (VI )l90 Ester B.Ester of dimeric acid with a mixture (SO- 50 by moles) of Ether III and Z-ethylhexanol.
Ester C.Ester of trimeric acid with Ether II. Ester D.Ester of trimeric acid with Ether III. Ester B.Ester of trimeric acid with a mixture (67- 33 by moles) of Ether III and a mixture of saturated aliphatic C alcohols.
Ester F.-Ester of trimeric acid with a mixture (67- 33 by moles) of Ether III and dodecanol.
Some physical characteristics of Esters B to F are given hereinafter.
EXAMPLES 1 TO 3 In these examples, lubricating compositions have been prepared by determining the proportions of Ester A to be added to various hydrocarbon oils so as to obtain multigrade oils having given viscosity characteristics. In some cases, a minor amount of a Vi-improver (polymethacrylate) had to be added.
By way of comparison, an attempt has been made to prepare multigrade oils exhibiting the same viscosity characteristics from pure hydrocarbon oils.
The viscosity characteristics required and the composition of the multigrade oils prepared have been reported in the following Table I.
To each of the base mixtures, 6% by weight of an antioxidant and detergent additive has also been added.
From this table, it is seen that the proportion of acid-refined mineral oils, the hydrorefined oils and the Vi-improver which it is necessary to add to composition synthetic oils obtained by oligomerization of olefinic according to this invention in order to reach the desired hydrocarbons having 2-20 carbon atoms and (B) at least viscosimetric characteristics is substantially reduced with one compound complying with the general formula: respect to the proportion which must be added to compo- 5 sitions consisting essentially of mineral oils. R [CO-O{R -O%,R [-CO-OR (m x) TABLE I Viscosity characteristics esired Composition VI improver Viscosity at Percent by (percent Example number 98.9 C. VIE Nature of the components weight b.w.)
Hydrorefined mineral oil 150 SSU at 37.8 0., VIE2132 10 l 5 -185 Ester A 90 9' Hydrorefined mineral oil 140 SSU at 37.8 0., VIn:l38 100 4. 5 Solvent refined mineral oil 200 SSU at 3 8 0., VIEIIOO 70 2 2 Ester A 30 -10 -150 Solvent refined mineral oil 350 SS U at 37 .8 0., VIE: l00 45 0 Ester A 55 Comparison Solvent refined mineral oil 160 SSU at 318 0., VIE: 100 100 4 EXAMPLES 4 TO 14 Where m is 2 or 3, x is from 0.15 m. to m inclusive; when m is 2, R is the divalent hydrocarbon radical of a dicarboxylic acid selected from the group consisting of unsaturated dicarboxylic acids having 28-44 carbon atoms resulting from dimerization of unsaturated fatty acids of 14-22 carbon atoms, and the corresponding saturated dicarboxylic acids, and when m is 3, R is a trivalent hydrocarbon radical of a tricarboxylic acid selected from the group consisting of unsaturated tricarboxylic acids having 42-66 carbon atoms resulting from trimerization of unsaturated fatty acids of 14-22 carbon atoms, and the cordesponding saturated tricarboxylic acids; R is selected from the alkylene radicals having 2-5 carbon atoms, n
Multigrade oils have been prepared by adding Esters B-F to hydrocarbon oils. In some cases, a third solvent isodecyladipate, has been added to improve the miscibility of the Ester in the hydrocarbon oil, when necessary, a minor amount of a Vi-irnprover has also been added (polymethacrylate To each of the base mixtures, 0.5% by Weight of an anti-gelling additive and 5% by weight of a detergent additive have also been added.
The composition and some physical characteristics of 30 the multigrade oils are given in the following Table II,
' the h ra teristics of some commercial ils 1 also b en indicated, by way of comparis iii IS an Integer from 2 to 50 i each of R3 and R3 is tha The volatility of the oils is determined according to monovalent hydrocarbon radical of a compound selected ASTM D972-56 modified by using nitrogen instead of m the group consisting of aliphatic monoalcohols of air and a duration of 6 hours instead of 22 hours. 1-25 carbon atoms, alicyclic monoalcohols of 3-25 carbon From Table II, it is seen that the proportion of atoms and unsubstituted and alkyl-substituted monoimprover which must be added to compositions according Phenols of 645 farbofl atoms, the Proportion of Said to this invention to impart thereto the viscosmetric charcofnpound With respect to Sold hydrocarbon oil acteristics corresponding to a given SAE category is very being sufliclent to impart to said composition the desired low or even nullified. high viscosity index, and components (A) and (B) to- TABLE II Composition (percent by weight) VI Viscosity atimprover Pour Volatility Example Isodecyl percent 989 0., 37.8 0., -17.8 0., point (percent number Mineral oil Percent Ester Percent adipate b-W- est. cst. poises VIE SAE C.) b.w.)
4 350neutra1 70 B 16.6 135 96 143 20w4o -30 3.0 5.---
200 neutraL- 70 B 13.2 95.9 51.5 1-16 20W40 -30 7.5 6 70 B 17.7 138 57 161 20W50 -33 9.0 7 o 13. 77 90.4. 40.5 167 20W40 -30 10.7 s 50 D 13. 75 59.1 as 168 20W40 -30 11.0 D 15. 07 102 31 165 20W40 -33 11.4 E 13.9 92.4 42.5 165 20W40 -ac 13.9 11 E 13. 05 94.5 42 2OW-i0 -3o 12 12- 55 E 15.75 106.6 53 157 2OW4O -35 7. 5 1 75 F 15. 35 122 82.5 141 20W40 -24 5 14.-. do 60 F 13.7 95. 75 50 20W40 -24 7 Commercial Multigrade 011 15.8 100 35 179 20W40 33 20.4 Commercial Multigrade oil 18.0 129 67 2 w50 30 13 It is seen further that the volatility of compositions acgether constituting the redominant component of said cording to this invention is reduced with respect to volacomposition. tility of commercial multigrade oils of the same SAE- 60 2- A mp i n as fin y l im 1, wh r in h category, formula of compound (B), R is selected from the group From the foregoing description, one skilled in the art C H IStmg of ethylene and propylene. can easily ascertain the essential characteristics of this A oomposltlofl as defined y claim wherein, in the invention, and without departing from the spirit and formula of coolllolmd IS an i t ger from 5 to 30. scope thereof, can make various changes and modifica- 69 A composmon as definod oy C131111 wherein, in th tions of the invention to adapt it to various changes and i o of compound (B), x 15 from to m modifications of the invention to adapt it to various usages c uslve' and conditions 5. A composition as defined by claim 1, wherein com- What is claimed 70 pound (B) has a viscosity of 98.9 C. of from 20' to 500 est.
1. A lubricating composition of high viscosity index suitable for use as base lubricant for multigrade oils comfi' ggg fig sz sg gg gf g iggfig'igggg prising lubricating amounts of a mixture of (A) a hyest I drocarbon oil of lubricating viscosity selected from the 7, A mulfigrade il comprising major t f a l b igroup consisting of the solvent-refined mineral oils, the 75 cating composition as defined by claim 1.
8. A composition as defined by claim 1, wherein the hydrocarbon oil (A) is selected from the group consisting of solvent-refined paraffim'c mineral oils and hydrorefined oils having a viscosity at 37.8 C. of at least 100 SSU.
9. A composition as defined by claim 8, wherein the viscosity at 37.8 C. of the hydrocarbon oil is from 150 to 350 SSU.
10. A composition as defined by claim 1, wherein the hydrocarbon oil (A) represents from to 95% by weight and compound (B) from 95 to 5% by weight.
11. A composition as defined by claim 10, wherein x 12. A composition as defined by claim 1, wherein m is 2.
13. A multigrade oil comprising a major part of a lubricating composition as defined by claim 12.
14. A composition as defined by claim 1, wherein m is 3.
15. A multigrade oil comprising a major part of a lubricating composition as defined by claim 14.
16. A composition as defined by claim 1, wherein m is 2 and R is the divalent hydrocarbon radical of a dicarboxylic acid selected from the group consisting of unsaturated dicarboxylic acids having 36 carbon atoms which result from dimerization of unsaturated fatty acids of 18 carbon atoms, and the corresponding saturated dicarboxylic acids.
17. A composition as defined by claim 16 wherein the major part of R and R' contains at least carbon atoms.
18. A multigrade oil comprising a major part of a lubricating composition as defined by claim 16.
19. A composition as defined by claim 16, wherein R is selected from the group consisting of ethylene and propylene.
20. A composition as defined by claim 19, wherein all R radicals are propylene.
21. A composition as defined by claim 19, wherein the ratio of R radicals consisting of ethylene to R radicals consisting of propylene is at most 1/ 1.
22. A composition as defined by claim 16, further comprising a minor amount of a third solvent selected from the group consisting of esters of aliphatic dicarboxylic acids with aliphatic monoalcohols and esters of aliphatic monocarboxylic acids with aliphatic polyalcohols.
23. A composition as defined by claim 22, wherein x is m.
24.. A composition as defined by claim 16 wherein at is m.
25. A composition as defined by claim 24, wherein the hydrocarbon oil (A) represents from 5 to 50% by weight and component (B) 95 to 50% by weight.
26. A composition as defined by claim 24, wherein the hydrocarbon oil (A) represents frm 50 to 95% by weight and compound (B) from 50 to 5% by weight.
27. A composition as defined by claim 24, wherein R is selected from the group consisting of ethylene and propylene.
28. A composition as defined by claim 24, wherein all R radicals are propylene.
29. A composition as defined by claim 24, wherein the ratio of R radicals consisting of ethylene to R radicals consisting of propylene is at most 1/ 1.
30. A composition as defined by claim 24, wherein the major part of R and R';; contains at least 10 carbon atoms.
31. A compositin as defined by claim 24, further comprising a minor amount of a third solvent selected from the group consisting of esters of aliphatic dicarbo-xylic acids with aliphatic monoalcohols and esters of aliphatic monocarboxylic acids with aliphatic polyalcohols.
32. A composition as defined by claim 24, wherein the hydrocarbon oil (A) represents from 5 to by weight and compound (B) from 95 to 5% by weight.
33. A multigrade oil comprising a major part of a lubri cating composition as defined by claim 24.
34. A composition as defined by claim 1, wherein m is 3 and R is the trivalent hydrocarbon radical of a tricarboxylic acid selected from the group consisting of unsaturated tricarboxylic acids having 54 carbon atoms, which result from trimerization of unsaturated fatty acids of 18 carbon atoms, and the corresponding saturated tricarboxylic acids.
35. A composition as defined by claim 34, wherein the major part of R and R' contains at least 10 carbon atoms.
36. A composition as defined by claim 34., wherein at is 37. A composition as defined by claim 34, further comprising a minor amount of a third solvent selected from the group consisting of esters of aliphatic dicarboxylic acids with aliphatic monoalcohols and esters of aliphatic monocarboxylic acids with aliphatic polyalcohols.
38. A multigrade oil comprising a major part of a lubricating composition as defined by claim 34.
39. A composition as defined by claim 34, wherein R is selected from the group consisting of ethylene and propylene.
40. A composition as defined by claim 39, wherein all R radicals are propylene.
. 41. A composition as defined by claim 39, wherein the ratio of R radicals consisting of ethylene to R radicals consisting of propylene is at most 1/ 1.
References Cited UNITED STATES PATENTS 3,197,409 7/ 1965 de Vries 252-56 DX 2,620,306 12/ 1952 Stewart et a1. 252-565 X 2,548,494 4/ 1951 Smith 260-485 P 2,570,037 10/1951 Smith et a1 260-455 P 2,435,619 2/ 1948 Young et al 252-56 R 2,424,588 7/1947 Spanks et a1 252-56 R OTHER REFERENCES Georgi Motor Oils & Engine Lubrication, (1950) pages 199; 204; 205; 206 and 207.
W. H. CA'NNON, Primary Examiner US. Cl. X.R.
252-56 D, 56 R, 56 S, 79; 260-407, 48.5 P
Claims (1)
1. A LUBRICATING COMPOSITON OF HIGH VISCOSITY INDEX SUITABLE FOR USE AS BASE LIBRICANT FOR MULTIGRADE OILS COMPRISING LUBRICATING AMOUNTS OF A MIXTURE OF (A) A HYDROCARBONOIL OF LUBRICATING VISCOSITY SELECTED FROM THE GROUP CONSISTING OF THE SOLVENT-REFINED MINERAL OILS, THE ACID-REFINED MINERAL OILS, THE HYDROREFINED OILS AND THE SYNTHETIC OILS OBTAINED BY OLIGOMERIZATION OF OLEFINIC HYDROCARBONS HAVING 2-20 CARBON ATOMS AND (B) AT LEAST ONE COMPOUND COMPLYING WITH THE GENERAL FORMULA:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US00364066A US3843535A (en) | 1970-12-03 | 1973-05-25 | Lubricating compositions |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR7043605A FR2116277A1 (en) | 1970-12-03 | 1970-12-03 | Lube oil blends - contg hydrocarbon oil and polyalkylene glycol deriv |
| FR717113437A FR2133515B2 (en) | 1970-12-03 | 1971-04-15 | |
| US00364066A US3843535A (en) | 1970-12-03 | 1973-05-25 | Lubricating compositions |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3843535A true US3843535A (en) | 1974-10-22 |
Family
ID=27249446
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US00364066A Expired - Lifetime US3843535A (en) | 1970-12-03 | 1973-05-25 | Lubricating compositions |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US3843535A (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3974081A (en) * | 1974-07-31 | 1976-08-10 | Exxon Research And Engineering Company | Biodegradable seal swell additive with low toxicity properties for automatic transmission fluids, power transmission fluids and rotary engine oil applications |
| US4036771A (en) * | 1975-04-16 | 1977-07-19 | Institut Francais Du Petrole | Lubricating bases for multigrade oils |
| US4175047A (en) * | 1978-09-25 | 1979-11-20 | Mobil Oil Corporation | Synthetic ester and hydrogenated olefin oligomer lubricant and method of reducing fuel consumption therewith |
| US4175046A (en) * | 1978-09-20 | 1979-11-20 | Mobil Oil Corporation | Synthetic lubricant |
| US4839068A (en) * | 1987-10-01 | 1989-06-13 | The Lubrizol Corporation | Polysuccinate esters and lubricating compositions comprising same |
| US5069684A (en) * | 1989-12-18 | 1991-12-03 | Mobil Oil Corporation | Fuel and lube additives from polyether derivatives of polyamine alkenyl succinimides |
| US5688750A (en) * | 1993-06-02 | 1997-11-18 | Unichema Chemie B. V. | Base fluid |
| WO2001004240A1 (en) * | 1999-07-13 | 2001-01-18 | Canadian Oil Co Sweden Ab | Hydraulic oil |
| WO2011011656A3 (en) * | 2009-07-23 | 2011-03-17 | Dow Global Technologies Inc. | Polyalkylene glycols useful as lubricant additives for groups i-iv hydrocarbon oils |
| US9850447B2 (en) | 2013-05-23 | 2017-12-26 | Dow Global Technologies Llc | Polyalkylene glycols useful as lubricant additives for hydrocarbon base oils |
-
1973
- 1973-05-25 US US00364066A patent/US3843535A/en not_active Expired - Lifetime
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3974081A (en) * | 1974-07-31 | 1976-08-10 | Exxon Research And Engineering Company | Biodegradable seal swell additive with low toxicity properties for automatic transmission fluids, power transmission fluids and rotary engine oil applications |
| US4036771A (en) * | 1975-04-16 | 1977-07-19 | Institut Francais Du Petrole | Lubricating bases for multigrade oils |
| US4175046A (en) * | 1978-09-20 | 1979-11-20 | Mobil Oil Corporation | Synthetic lubricant |
| US4175047A (en) * | 1978-09-25 | 1979-11-20 | Mobil Oil Corporation | Synthetic ester and hydrogenated olefin oligomer lubricant and method of reducing fuel consumption therewith |
| US4839068A (en) * | 1987-10-01 | 1989-06-13 | The Lubrizol Corporation | Polysuccinate esters and lubricating compositions comprising same |
| US5069684A (en) * | 1989-12-18 | 1991-12-03 | Mobil Oil Corporation | Fuel and lube additives from polyether derivatives of polyamine alkenyl succinimides |
| US5688750A (en) * | 1993-06-02 | 1997-11-18 | Unichema Chemie B. V. | Base fluid |
| WO2001004240A1 (en) * | 1999-07-13 | 2001-01-18 | Canadian Oil Co Sweden Ab | Hydraulic oil |
| WO2011011656A3 (en) * | 2009-07-23 | 2011-03-17 | Dow Global Technologies Inc. | Polyalkylene glycols useful as lubricant additives for groups i-iv hydrocarbon oils |
| US8969271B2 (en) | 2009-07-23 | 2015-03-03 | Dow Global Technologies Llc | Polyakylene glycols useful as lubricant additives for groups I-IV hydrocarbon oils |
| US9850447B2 (en) | 2013-05-23 | 2017-12-26 | Dow Global Technologies Llc | Polyalkylene glycols useful as lubricant additives for hydrocarbon base oils |
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