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WO2000029520A1 - Compositions d'huiles lubrifiantes contenant des esters de phtalate - Google Patents

Compositions d'huiles lubrifiantes contenant des esters de phtalate Download PDF

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Publication number
WO2000029520A1
WO2000029520A1 PCT/US1998/024139 US9824139W WO0029520A1 WO 2000029520 A1 WO2000029520 A1 WO 2000029520A1 US 9824139 W US9824139 W US 9824139W WO 0029520 A1 WO0029520 A1 WO 0029520A1
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WIPO (PCT)
Prior art keywords
phthalate
ester
composition
phthalic acid
oil
Prior art date
Application number
PCT/US1998/024139
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English (en)
Inventor
Alexander B. Boffa
Thomas R. Bidwell
Joe R. Noles, Jr.
Original Assignee
Exxon Chemical Patents Inc.
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Filing date
Publication date
Application filed by Exxon Chemical Patents Inc. filed Critical Exxon Chemical Patents Inc.
Publication of WO2000029520A1 publication Critical patent/WO2000029520A1/fr

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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
    • C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
    • C10M169/04—Mixtures of base-materials and additives
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
    • C10M105/08—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen
    • C10M105/32—Esters
    • C10M105/36—Esters of polycarboxylic 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
    • C10M107/00—Lubricating compositions characterised by the base-material being a macromolecular compound
    • C10M107/02—Hydrocarbon polymers; Hydrocarbon polymers modified by oxidation
    • 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
    • C10M111/00—Lubrication compositions characterised by the base-material being a mixture of two or more compounds covered by more than one of the main groups C10M101/00 - C10M109/00, each of these compounds being essential
    • C10M111/04—Lubrication compositions characterised by the base-material being a mixture of two or more compounds covered by more than one of the main groups C10M101/00 - C10M109/00, each of these compounds being essential at least one of them being a macromolecular organic compound
    • 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
    • C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
    • C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
    • C10M129/68—Esters
    • C10M129/72—Esters of polycarboxylic 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
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • 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
    • C10M2205/0206—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/282—Esters of (cyclo)aliphatic oolycarboxylic 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
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/282—Esters of (cyclo)aliphatic oolycarboxylic acids
    • C10M2207/2825—Esters of (cyclo)aliphatic oolycarboxylic acids used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/285—Esters of aromatic polycarboxylic 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
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/285—Esters of aromatic polycarboxylic acids
    • C10M2207/2855—Esters of aromatic polycarboxylic acids used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/286—Esters of polymerised unsaturated 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
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/34—Esters having a hydrocarbon substituent of thirty or more carbon atoms, e.g. substituted succinic acid derivatives
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • 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
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • C10N2040/251—Alcohol-fuelled engines
    • 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
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • C10N2040/252—Diesel engines
    • 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
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • C10N2040/252—Diesel engines
    • C10N2040/253—Small diesel engines
    • 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
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • C10N2040/255—Gasoline engines
    • 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
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • C10N2040/255—Gasoline engines
    • C10N2040/28—Rotary engines

Definitions

  • Hydrocarbon oil compositions typically comprise a mixture of at least one hydrocarbon base oil and one or more additives, where each additive is employed for the purpose of improving the performance and properties of the base oil in its intended application; e.g., as a lubricating oil, heating oil, diesel oil, middle distillate fuel oil, and so forth.
  • Lubricating oil composition face rather stringent viscosity requirements, as set, for example, by ASTM specifications. Such compositions must meet a minimum viscosity requirement at high temperature (i.e., at least about 100°C) and a maximum viscosity requirement at low temperature (about -5° to -30°C). Oil viscosity decreases with increasing temperature.
  • a straight line drawn through viscosities of an oil at any two temperatures permits the estimation of viscosity at any other temperature, down to just above the cloud point.
  • Such a straight line relates kinematic viscosity v in mm 2 /sec ( ⁇ cSt) to absolute temperature T (K) by the Walther equation,
  • VI The dimensionless viscosity index (VI), although empirical, is the most common measure of the relative decrease in oil viscosity with increasing temperature.
  • a series of Pennsylvania petroleum oils exhibiting a relatively small decrease in viscosity with increasing temperature is arbitrarily assigned a VI of 100, whereas a series of Gulf Coast oils having viscosities that change relatively rapidly is assigned a VI of 0. From viscosity measurements at 40 and 100°C, the VI of any oil sample can be obtained from detailed tables published by ASTM (ASTM D2270).
  • Oils having a VI above 80 to 90 are generally desirable. These oils are composed primarily of saturated hydrocarbons of the paraffinic and alicyclic types which give long life, freedom from sludge and varnish, and generally satisfactory performance when they are compounded with proper additives for a given application. Lower VI oils sometimes are useful in providing low pour point for outdoor applications in cold climates and for some refrigeration and compressor applications. Although the viscosity index is useful for characterizing petroleum oils, other viscosity-temperature parameters are employed periodically. Viscosity temperature coefficients (VTCs) give the fractional drop in viscosity as temperature increases from 40 to 100°C and is useful in characterizing behavior of silicones and some other synthetics. With petroleum base stocks, VTC tends to remain constant as increasing amounts of VI improvers are added.
  • the minimum viscosity requirement at high temperature is intended to prevent the oil from thinning during engine operation to the point at which excessive engine wear and increased oil consumption would result.
  • the maximum viscosity requirement at low temperature facilitates engine start-up in cold weather and also ensures that the cold oil has sufficient pumpability and flowability to avoid engine damage due to insufficient lubrication.
  • a minimum low temperature viscosity requirement must be maintained.
  • a formulator can use a single lubricating base oil of desired viscosity or a blend of oils of different viscosities, and he can manipulate the kinds and amounts of additives that must be present to achieve not only the viscosity requirements, but also requirements specified for other properties, such as dispersancy, pour point and cloud point.
  • the mere blending of oils having different viscosity characteristics does not enable the formulator to meet the low and high temperature viscosity requirements of lubricating oil compositions.
  • the primary tool for meeting the requirements has been so far the use of viscosity index improving additives, hereinafter referred to as viscosity index improvers or, more simply, VI improvers.
  • Fuel economy is another important property to be considered when formulating oil. It is strongly dependent on base oil viscometrics. Many synthetic basestocks, in particular poly alpha olefins (PAO), have a high viscosity index and low cold cranking viscosity (ccs). Oils with these basestocks will have an elevated basestock viscosity at high temperature when blended to a given ccs viscosity grade limit (i.e. 5W). However, increased basestock viscosity leads to poor fuel economy.
  • PAO poly alpha olefins
  • Engineers 12-3, pgs 171-189 discloses the use of esters and the influence of viscosity on fuel efficiency.
  • the article discloses that the chemical composition of the ester is an important factor in fuel efficiency.
  • this article does not disclose the use of phthalates, nor suggests that the phthalates have improved fuel economy and wear performance.
  • This invention comprises a lubricating oil composition comprising at least 10% by weight of the total oil composition of an ester of phthalic acid having a viscosity index less than 100.
  • a preferred embodiment of this invention is phthalic acid esters selected from the group consisting of: dioctyl phthalate, didecyl phthalate, diidodecyl phthalate, diisoctyl phthalate, diisononyl phthalate, diidodecyl phthalate, ditridecyl phthalate, di-n-butyl phthalate, diisobutyl phthalate and mixtures thereof.
  • the invention also discloses a method of improving fuel economy and wear of an internal combustion engine by treating the moving surfaces with a lubricating composition comprising at least 10% by weight of the total lubricating composition of an ester of phthalic acid having a viscosity index less than 100.
  • the present invention provides a lubricating oil composition comprising at least about 10%to 50%), preferably about 15%> to 40%>, and more preferably about 20%> to 35% by weight of the total oil composition of an ester of phthalic acid having a viscosity index less than 100, preferably less than 95, and more preferably less than 90.
  • the inventors have discovered that the combination of lubricating base oil with phthalic acid esters of viscosity index less than 100 results in improved fuel efficiency and wear performance.
  • the ester of phthalic acid is selected from the group consisting of: dioctyl phthalate, didecyl phthalate, diidodecyl phthalate, diisoctyl phthalate, diisononyl phthalate, diidodecyl phthalate, ditridecyl phthalate, di-n-butyl phthalate, diisobutyl phthalate and mixtures thereof.
  • This composition may further comprise a mineral base oil such as mineral oils having a viscosity index above 110.
  • a mineral base oil such as mineral oils having a viscosity index above 110.
  • compositions of the present invention find their utilities in lubricating compositions where additives are dissolved or dispersed and where at least 10% of the total composition comprises an ester of phthalic acid.
  • Lubricants of the present invention can be prepared from a variety of natural and synthetic base stocks admixed with various additive packages and solvents depending upon their intended application.
  • the base stocks typically include natural oils, highly refined mineral oils, poly alpha olefins (PAO), polyalkylene glycols (PAG), and silicone oils.
  • this invention involves a method of improving fuel economy and wear of an internal combustion engine by treating the moving surfaces thereof with a lubricating composition comprising at least 10%> by weight of the total oil composition of an ester of phthalic acid having a viscosity index less than 100.
  • Natural oils include animal oils and vegetable oils (e.g., castor, lard oil) liquid petroleum oils and hydrorefined, solvent-treated or acid-treated mineral lubricating oils of the paraffinic, naphthenic and mixed Paraffinic-naphthenic types. Oils of lubricating viscosity derived from coal or shale are also useful base oils.
  • animal oils and vegetable oils e.g., castor, lard oil
  • mineral lubricating oils of the paraffinic, naphthenic and mixed Paraffinic-naphthenic types.
  • Oils of lubricating viscosity derived from coal or shale are also useful base oils.
  • Properties provided by the branched hydrocarbon chain structure of poly alpha olefin-containing fluids include high viscosity index in the 130-150 range, pour points of -50 to -60°C for ISO 32 to 68 viscosity range (SAE 10W and SAE 20W, respectively), and high temperature stability superior to commercial petroleum products.
  • SAE 10W and SAE 20W pour points of -50 to -60°C for ISO 32 to 68 viscosity range
  • the lubricating oil of the present invention may also comprise polyalkylene glycols have a number of characteristics that make them desirable as lubricants. Compared to petroleum lubricants, they have lower pour points, a higher viscosity index, and a wider range of solubilities including water, compatibility with elastomers, less tendency to form tar and sludge, and lower vapor pressure. Silicon Oils
  • Silicon-based oils such as the polyalkyl-, polyaryl-, polyalkoxy-, or polyaryloxysiloxane oils and silicate oils comprise another useful class of synthetic lubricants; they include tetraethyl silicate, tetraisopropyl silicate, tetra-(2- ethylhexyl)silicate, tetra-(4-methyl-2-ethylhexyl)silicate, tetra-(p-tert- butylphenyl)silicate, hexa-(4-methyl-2-pentoxy)disiloxane, poly(methyl)siloxanes and poly(methylphenyl)siloxanes.
  • Other synthetic lubricating oils include liquid esters of phosphorous-containing acids (e.g., tricresyl phosphate, trioctyl phosphate, diethyl ester of decylphosphonic acid) and polymeric tetrahydrofurans.
  • the synthetic lubricating oils of the present invention may comprise an alkylate compound.
  • These lubricating oils may also include hydrocarbon oils and halosubstituted hydrocarbon oils such as polymerized and interpolymerized olefins (e.g., polybutylenes, polypropylenes, propylene-isobutylene copolymers, chlorinated polybutylenes, etc.) poly(hexenes), poly(l-octenes), poly(l-decenes), etc.
  • alkylbenzenes e.g., dodecyl-benzenes, tetradecylbenzenes, dinonylbenzenes, di- (2-ethylhexyl)-benzenes, etc.
  • polyphenyls e.g., biphenyls, terphenyls, alkylated diphenyl ethers and alkylated diphenyl sulfides and the derivatives, analogs and homologs thereof and the like.
  • the lubricating composition of the present invention can be used in the formulation of crankcase lubricating oils (i.e. passenger car motor oils, heavy duty diesel motor oils, and passenger car diesel oils) for spark-ignited and compression-ignited engines.
  • crankcase lubricating oils i.e. passenger car motor oils, heavy duty diesel motor oils, and passenger car diesel oils
  • the additives listed below are typically used in such amounts so as to provide their normal attendant functions. Typical amounts for individual components are also set forth below. All the values listed are stated as mass percent active ingredient in the total lubricating oil composition.
  • each of the components may be added directly to the base stock by dispersing or dissolving it in the base stock at the desired level of concentration. Such blending may occur at ambient temperature or at an elevated temperature.
  • all the additives except for the viscosity modifier and the pour point depressant are blended into a concentrate or additive package described herein as the additive package, that is subsequently blended into base stock to make finished lubricant.
  • a concentrate or additive package described herein as the additive package that is subsequently blended into base stock to make finished lubricant.
  • Use of such concentrates is conventional.
  • the concentrate will typically be formulated to contain the additive(s) in proper amounts to provide the desired concentration in the final formulation when the concentrate is combined with a predetermined amount of base lubricant.
  • the concentrate is conveniently made in accordance with the method described in US 4,938,880. That patent describes making a pre-mix of ashless dispersant and metal detergents that is pre-blended at a temperature of at least about 200°C. Thereafter, the pre-mix is cooled to at least 85°C and the additional components are added.
  • the final crankcase lubricating oil formulation may employ from 2 to 20 mass %> and preferably 5 to 10 mass %, more preferably about 7 to 8 mass %> of the concentrate or additive package with the remainder being base stock containing at least 10% by weight phthalic acid esters.
  • the ashless dispersant comprises an oil soluble polymeric hydrocarbon backbone having functional groups that are capable of associating with particles to be dispersed.
  • the dispersants comprise amine, alcohol, amide, or ester polar moieties attached to the polymer backbone often via a bridging group.
  • the ashless dispersant may be, for example, selected from oil soluble salts, esters, amino-esters, amides, imides, and oxazolines of long chain hydrocarbon substituted mono and dicarboxylic acids or their anhydrides; thiocarboxylate derivatives of long chain hydrocarbons; long chain aliphatic hydrocarbons having a polyamine attached directly thereto; and Mannich condensation products formed by condensing a long chain substituted phenol with formaldehyde and polyalkylene polyamine.
  • the viscosity modifier functions to impart high and low temperature operability to a lubricating oil.
  • the VM used may have that sole function, or may be multifunctional.
  • Multifunctional viscosity modifiers that also function as dispersants are also known.
  • Suitable viscosity modifiers are polyisobutylene, copolymers of ethylene and propylene and higher alpha-olefins, polymethacrylates, polyalkylmethacrylates, methacrylate copolymers, copolymers of an unsaturated dicarboxylic acid and a vinyl compound, inter polymers of styrene and acrylic esters, and partially hydrogenated copolymers of styrene/isoprene, styrene/butadiene, and isoprene/butadiene, as well as the partially hydrogenated homopolymers of butadiene and isoprene and isoprene/divinylbenzene.
  • Metal-containing or ash-forming detergents function both as detergents to reduce or remove deposits and as acid neutralizers or rust inhibitors, thereby reducing wear and corrosion and extending engine life.
  • Detergents generally comprise a polar head with long hydrophobic tail, with the polar head comprising a metal salt of an acid organic compound.
  • the salts may contain a substantially stoichiometric amount of the metal in which they are usually described as normal or neutral salts, and would typically have a total base number (TBN), as may be measured by ASTM D-2896 of from 0 to 80. It is possible to include large amounts of a metal base by reacting an excess of a metal compound such as an oxide or hydroxide with an acid gas such as carbon dioxide.
  • the resulting overbased detergent comprises neutralized detergent as the outer layer of a metal base (e.g., carbonate) micelle.
  • Such overbased detergents may have a TBN of 150 or greater, and typically from 250 to 450 or more.
  • Detergents that may be used include oil-soluble neutral and overbased sulfonates, phenates, sulfurized phenates, thiophosphonates, salicylates, and nephthenates and other oil-soluble carboxylates of a metal, particularly the alkali or alkaline earth metals, e.g., sodium, potassium, lithium, calcium, and magnesium.
  • a metal particularly the alkali or alkaline earth metals, e.g., sodium, potassium, lithium, calcium, and magnesium.
  • the most commonly used metals are calcium and magnesium, which may both be present in detergents used in a lubricant, and mixtures of calcium and/or magnesium with sodium.
  • Particularly convenient metal detergents are neutral and overbased calcium sulfonates having TBN of from 20 to 450 TBN, and neutral and overbased calcium phenates and sulfurized phenates having TBN of from 50 to 450.
  • Dihydrocarbyl dithiophosphate metal salts are frequently used as anti-wear and antioxidant agents.
  • the metal may be an alkali or alkaline earth metal, or aluminum, lead, tin, molybdenum, manganese, nickel or copper.
  • the zinc salts are most commonly used in lubricating oil in amounts of 0.1 to 10, preferably 0.2 to 2 wt. %, based upon the total weight of the lubricating oil composition. They may be prepared in accordance with known techniques by first forming a dihydrocarbyl dithiophosphoric acid (DDPA), usually by reaction of one or more alcohol or a phenol with P 2 S 5 and then neutralizing the formed DDPA with a zinc compound.
  • DDPA dihydrocarbyl dithiophosphoric acid
  • a dithiophosphoric acid may be made by reacting mixtures of primary and secondary alcohols.
  • multiple dithiophosphoric acids can be prepared where the hydrocarbyl groups on one are entirely secondary in character and the hydrocarbyl groups on the others are entirely primary in character.
  • any basic or neutral zinc compound could be used but the oxides, hydroxides and carbonates are most generally employed.
  • Commercial additives frequently contain an excess of zinc due to use of an excess of the basic zinc compound in the neutralization reaction.
  • Oxidation inhibitors or antioxidants reduce the tendency of base stocks to deteriorate in service which deterioration can be evidenced by the products of oxidation such as sludge and varnish-like deposits on the metal surfaces and by viscosity growth.
  • oxidation inhibitors include hindered phenols, alkaline earth metal salts of alkylphenolthioesters having preferably C 5 to C 12 alkyl side chains, calcium nonylphenol sulfide, ashless oil soluble phenates and sulfurized phenates, phosphosulfurized or sulfurized hydrocarbons, phosphorous esters, metal thiocarbamates, oil soluble copper compound as described in US 4,867,890, and molybdenum containing compounds.
  • Friction modifiers may be included to improve fuel economy.
  • Oil-soluble alkoxylated mono- and di-amines are well known to improve boundary layer lubrication.
  • the amines may be used as such or in the form of an adduct or reaction product with a boron compound such as boric oxide, boron halide, metaborate, boric acid or a mono-, di- or tri-alkyl borate.
  • Copper and lead bearing corrosion inhibitors may be used, but are typically not required with the formulation of the present invention.
  • such compounds are the thiadiazole polysulfides containing from 5 to 50 carbon atoms, their derivatives and polymers thereof.
  • Derivatives of 1,3,4 thiadiazoles such as those described in U.S. Patent Nos. 2,719,125; 2,719,126; and 3,087,932; are typical.
  • Other similar materials are described in U.S. Patent Nos. 3,821,236; 3,904,537; 4,097,387; 4,107,059; 4,136,043; 4,188,299; and 4,193,882.
  • additives are the thio and polythio sulfenamides of thiadiazoles such as those described in UK Patent Specification No. 1,560,830. Benzotriazoles derivatives also fall within this class of additives. When these compounds are included in the lubricating composition, they are preferably present in an amount not exceeding 0.2 wt. % active ingredient.
  • a small amount of a demulsifying component may be used.
  • a preferred demulsifying component is described in EP 330,522. It is obtained by reacting an alkylene oxide with an adduct obtained by reacting a bis-epoxide with a polyhydric alcohol.
  • the demulsifier should be used at a level not exceeding 0.1 mass % active ingredient.
  • a treat rate of 0.001 to 0.05 mass %> active ingredient is convenient.
  • Pour point depressants otherwise known as lube oil improvers, lower the minimum temperature at which the fluid will flow or can be poured.
  • Such additives are well known. Typical of those additives which improve the low temperature fluidity of the fluid are Cg and C 18 dialkyl fumarate/vinyl acetate copolymers, polyalkylmethacrylates and the like.
  • Foam control can be provided by many compounds including an antifoamant of the polysiloxane type, for example, silicone oil or polydimethyl siloxane.
  • an antifoamant of the polysiloxane type for example, silicone oil or polydimethyl siloxane.
  • Some of the above-mentioned additives can provide a multiplicity of effects; thus for example, a single additive may act as a dispersant-oxidation inhibitor. This approach is well known and does not require further elaboration.
  • the Sequence VIA fuel economy procedure has six operational stages and a 16 hour pre-aging of the oil.
  • the engine is a Ford 4.6L V-8.
  • Fuel economy is determined relative to a base case oil using a weighted sum of the fuel consumption which includes operating power and a scaling factor for each stage.
  • the screener runs Stages 1 and 4 and a 3 hour aging as given below:
  • Each oil was blended to viscometric targets of 3500 cP ccs at -30°C and 10.1 cSt kinematic viscosity at 100°C.
  • a 3250 cP ccs is the lower limit of the 5W viscosity range.
  • All of the candidate blends except the tri-methylolpropane octanoate/decanoate allowed for reductions in the ratio of PAO6 to PAO4 relative to the all PAO base case oil. Reductions in the amount of PAO6 are expected to give credits in the hydrodynamic stages of the Sequence VIA.
  • Wear performance is evaluated as the loss in dimension length of valve lifters and diameters on cam lobes.
  • the average wear reported below in Table 3 is the average lobeAifler wear loss of 12 lobe/lifter location pairs.
  • the maximum wear loss is the largest wear loss measured on one lobe/lifter location pair.
  • the operating conditions are as follows.
  • the ASTM Sequence HIE test operates for 64 hours in a GM 3.8 liter V-6 gasoline engine under high load and temperature conditions. After a 4-hour break-in, test operation is steady state at 3000 RPM, 67.8 horsepower, 149° C oil temperature and 155° C coolant temperature.
  • Table 3 shows the wear results comparing high hydroxyl esters with diisodecyl phthalate (DIDP). Both compositions contain the same additive package and have the same oil weight (0W30).
  • the wear performance results show that the phthalate ester significantly improves the wear performance of the engine compared to the high hydroxyl esters. Therefore, the phthalate ester synthetic oil has improved fuel efficiency over the non- ester based synthetic oil and significantly superior wear performance over the high hydroxyl esters.

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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)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Lubricants (AREA)

Abstract

L'invention se rapporte à une composition d'huile lubrifiante comportant au moins 10 %, par rapport au poids total de la composition, d'un ester d'acide phtalique doté d'un indice de viscosité inférieur à 100. Cette composition d'huile lubrifiante présente des caractéristiques améliorées de comportement à l'usure et elle permet d'économiser le carburant.
PCT/US1998/024139 1998-11-12 1998-11-12 Compositions d'huiles lubrifiantes contenant des esters de phtalate WO2000029520A1 (fr)

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US96809698A 1998-11-12 1998-11-12
US08/968,096 1998-11-12

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002024840A1 (fr) * 2000-09-20 2002-03-28 Exxonmobil Research And Engineering Company Composition lubrifiante pour moteur diesel

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4111821A (en) * 1972-02-07 1978-09-05 Tenneco Chemicals, Inc. Lubricants for reciprocating compressors for oxygen-free gases
GB2081299A (en) * 1980-07-29 1982-02-17 Exxon Research Engineering Co Two-stroke Fuel-lubricant Composition
US4790957A (en) * 1986-10-18 1988-12-13 Basf Aktiengesellschaft Polycarboxylic acid esters and lubricants containing these esters
US4826614A (en) * 1985-10-21 1989-05-02 Violet Co., Ltd. Lubrication boosting additives and lubricating oil compositions comprising the same
EP0461435A1 (fr) * 1990-06-09 1991-12-18 Hoechst Aktiengesellschaft Utilisation d'esters d'acides aromatiques pour compresseur pour machines frigorifiques

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4111821A (en) * 1972-02-07 1978-09-05 Tenneco Chemicals, Inc. Lubricants for reciprocating compressors for oxygen-free gases
GB2081299A (en) * 1980-07-29 1982-02-17 Exxon Research Engineering Co Two-stroke Fuel-lubricant Composition
US4826614A (en) * 1985-10-21 1989-05-02 Violet Co., Ltd. Lubrication boosting additives and lubricating oil compositions comprising the same
US4790957A (en) * 1986-10-18 1988-12-13 Basf Aktiengesellschaft Polycarboxylic acid esters and lubricants containing these esters
EP0461435A1 (fr) * 1990-06-09 1991-12-18 Hoechst Aktiengesellschaft Utilisation d'esters d'acides aromatiques pour compresseur pour machines frigorifiques

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002024840A1 (fr) * 2000-09-20 2002-03-28 Exxonmobil Research And Engineering Company Composition lubrifiante pour moteur diesel
JP2004510017A (ja) * 2000-09-20 2004-04-02 エクソンモービル　リサーチ　アンド　エンジニアリング　カンパニー ディーゼルエンジン潤滑剤組成物
AU2000275214B2 (en) * 2000-09-20 2006-04-27 Exxonmobil Research And Engineering Company Diesel engine lubricant composition

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