EP0288777B1 - Huiles de moteur synthétiques hydrocarbonées - Google Patents

Huiles de moteur synthétiques hydrocarbonées Download PDF

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Publication number
EP0288777B1
EP0288777B1 EP88105305A EP88105305A EP0288777B1 EP 0288777 B1 EP0288777 B1 EP 0288777B1 EP 88105305 A EP88105305 A EP 88105305A EP 88105305 A EP88105305 A EP 88105305A EP 0288777 B1 EP0288777 B1 EP 0288777B1
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Prior art keywords
oligomer
oil
sae
oligomers
engine
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German (de)
English (en)
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EP0288777A2 (fr
EP0288777A3 (en
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Bruce J. Beimesch
James E. Davis
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Ethyl Corp
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Ethyl Corp
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M107/00—Lubricating compositions characterised by the base-material being a macromolecular compound
    • C10M107/02—Hydrocarbon polymers; Hydrocarbon polymers modified by oxidation
    • C10M107/10—Hydrocarbon polymers; Hydrocarbon polymers modified by oxidation containing aliphatic monomer having more than 4 carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • 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
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
    • C10M2205/028—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
    • C10M2205/028—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms
    • C10M2205/0285—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms 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
    • C10M2207/02—Hydroxy compounds
    • C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/027—Neutral salts thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/02—Hydroxy compounds
    • C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/028—Overbased salts thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • 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
    • C10M2215/064—Di- and triaryl amines
    • C10M2215/065—Phenyl-Naphthyl amines
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/086—Imides
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/28—Amides; Imides
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
    • C10M2219/046—Overbasedsulfonic acid salts
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
    • C10M2219/082—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
    • C10M2219/084—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04—Phosphate esters
    • C10M2223/045—Metal containing thio derivatives
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2229/00—Organic macromolecular compounds containing atoms of elements not provided for in groups C10M2205/00, C10M2209/00, C10M2213/00, C10M2217/00, C10M2221/00 or C10M2225/00 as ingredients in lubricant compositions
    • C10M2229/04—Siloxanes with specific structure
    • C10M2229/041—Siloxanes with specific structure containing aliphatic substituents
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/04—Groups 2 or 12
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • 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
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
    • F02B—INTERNAL-COMBUSTION PISTON ENGINES; COMBUSTION ENGINES IN GENERAL
    • F02B3/00—Engines characterised by air compression and subsequent fuel addition
    • F02B3/06—Engines characterised by air compression and subsequent fuel addition with compression ignition

Definitions

  • the present invention relates to a non-polymer thickened multigrade engine oil based on synthetic hydrocarbons. More specifically, SAE 10W-30 and SAE 15W-40 engine oils derived from hydrogenated decene-1 oligomers and which do not contain viscosity index improvers are provided.
  • SAE 10W-30 is the engine oil viscosity grade recommended by most manufacturers for gasoline passenger car service whereas, for diesel truck operation, SAE 15W-40 is the most widely recommended engine oil viscosity grade. Both of these oils are multigrade or cross-graded which, in general terms, means that they are acceptable for use in either a summer or winter environment. More precisely, these oils must meet the current SAE J300 APR84 specifications.
  • a viscosity of 3.5 Pa.s (3500 centipoise) or below at -20°C as determined in accordance with ASTM D-2602 and a viscosity between 9.3 x 10 ⁇ 6 and 12,5 x 10 ⁇ 6 m2/s (9.3 and 12.5 centistokes) at 100°C as determined in accordance with ASTM D-445 is required.
  • the oil must have a borderline pumping temperature (ASTM D-3829) of -25°C or below and a stable pour point (FTMS 79lb-203) of -30°C or below.
  • An SAE 15W-40 oil must have a maximum viscosity of 3,5 Pa.s (3500 centipoise) at -15°C, and a viscosity between 12.5 x 10 ⁇ 6 and 16.3 x 10 ⁇ 6 m2/s (12,5 and 16,3 centistokes) at 100°C and borderline pumping temperature of -20° or below.
  • multigrade engine oils must also meet certain service classifications of the American Petroleum Institute (API). This is accomplished by the addition of appropriate performance additives to the oil. It should be noted that the formulated oil, i.e., the base oil containing all additives, must meet the SAE J-300 APR84 viscosity criteria.
  • VI improvers are polymeric materials, such as ethylene-propylene copolymers, hydrogenated styrene-diene block copolymers, polyalkyl methacrylates, polyisobutylenes or ethylene-vinyl acetate copolymers, which modify the rate of change of viscosity of the basestock with temperature when added thereto. While the polymeric VI improvers are necessary to achieve cross-grading with petroleum basestocks, the addition of these polymers is not without problem.
  • VI improvers can undergo shear, i.e., breakdown, under conditions of thermal and mechanical stress. Breakdown of the VI improver alters the viscosity characteristics of the formulated motor oil and can also contribute to the formation of sludge and engine deposits.
  • Field studies have shown, for example, that a SAE 15W-40 diesel engine oil can drop to SAE 15W-30 after only several thousand miles of service. This presents a very real problem with heavy duty over-the-road trucks where it is not uncommon to accumulate 30,000 miles between service intervals.
  • VI improvers One approach to overcoming the problems associated with the use of VI improvers is to develop improved polymers which are more resistant to shear under conditions of thermal and mechanical stress. While the development of new polymeric thickeners is a viable approach, it would be even more desirable and advantageous if VI improvers could be totally eliminated from multigrade motor oil formulations.
  • European Patent Applications 88.453; 119,069; and 119,070 disclose multigrade lubricants which are combinations of synthetic fluids having different viscosities.
  • the lubricants consist of blends of high viscosity ethylene-alphaolefin copolymers with lower viscosity synthetic hydrocarhons, such as an alkylated benzene or polyalphaolefin, or enter, such as a monoester, diester or polyester. 5W-40 and 10W-40 oils indicated as being suitable for use as diesel crankcase lubricants obtained by blending different synthetic products are disclosed.
  • US-A-4587368 discloses a process for producing a synthetic lubricant material useful as a base for high performance motor oils. This process minimizes the production of trimer by first forming an intermediate oligomeric mixture and then adding additional monomer thereto in a controller manner for an additional period of time.
  • the multigrade engine oils of the invention are mixtures of conventional oligomers of decene-1 with higher decene-1 oligomers, said oligomers being present in specific proportions.
  • the oligomeric composite is formulated with performance additives to meet the desired API service classification.
  • the present invention provides a non-polymer thickened multi-grade engine oil comprising 80 to 95% by weight of a hydrogenated decene-1 oligomer mixture and 0,5 to 20% by weight of engine performance additives, characterized in that the oligomer mixture contains 0,5% to 20% of C30 oligomer, 43% to 68% of C40 oligomer, 14% to 34% C50 oligomer, 3% to 16% of C60 oligomer and 3% to 16% C70+ oligomers having a viscosity from 9,3 x 10 ⁇ 6 to 12,5 x 10 ⁇ 6 m2/s (9, 3 to 12,5 centistokes) at 100°C for a 10 W-30 oil or a viscosity from 12,5 x 10 ⁇ 6 to 16,3 x 10 ⁇ 6 m2/s (12,5 to 16,3 centistokes) at 100°C for a 15 W-40 oil.
  • SAE 15W-40 diesel engine or universal engine oils contain from 10% to 20% by weight diesel or universal performance additives which meet the requirements set forth in the appropriate API Engine Service Classification System with 80% to 90% by weight of a hydrogenated decene-1 oligomer mixture containing up to 2.5% C30 oligomer, 44% to 56% C40 oligomer, 23% to 34% C50 oligomer, 7% to 16% C60 oligomer, and 7% to 16% C70+ oligomers.
  • cross-graded motor oils suitable for passenger car and diesel truck service are obtained using a single synthetic hydrocarbon basestock, namely polyalphaolefins comprised of specific decene-1 oligomers present in specified amounts.
  • the multigrade engine oils of the invention are obtained without the use of polymeric VI improvers.
  • SAE 10W-30 and SAE 15W-40 engine oils are obtained simply by addition of appropriate performance additives, i.e., additives which meet the designated API service classification, to the oligomer mixture.
  • oligomer composite(s) specific mixtures of decene-1 oligomers, also referred to as oligomer composite(s), which contain substantial amounts of C60 and higher oligomers are employed.
  • the useful oligomer mixtures are obtained by oligomerizing decene-1 using an alcohol-promoted boron trifluoride catalyst in accordance with the conventional procedures known to the art. It is especially advantageous for the present invention to utilize oligomer mixtures obtained from the oligomerization of decene-1 wherein the catalyst is boron trifluoride promoted with propanol. It will, however, be understood by those skilled in the art that any oligomerization procedure whereby compositions having the hereinafter specified oligomer distributions can be employed.
  • oligomeric composites utilized herein are mixtures of decene-1 oligomers
  • oligomeric products derived from other alpha-olefins in the C8 ⁇ 12 range can also be utilized.
  • the ranges specified herein for the oligomer composites derived from decene-1 will not, however, apply to oligomers derived from other olefins.
  • the oligomer composite which is combined with the performance additives to obtain the multigrade engine oils of the invention are blends of two or more fractions having different oligomer distributions.
  • a friction rich in lower oligomers is typically blended with a friction rich in higher oligomers to achieve the desired oligomer distribution: however, any combination of fractions which will yield a composite having the required distribution of oligomers is acceptable.
  • the fractions employed for such blending may be different distillation cuts from the same process or may be obtained from entirely different oligomerization processes.
  • a particular fraction may be used in the blending of both SAE 10W-30 and SAE 15W-40 oils.
  • a friction rich in higher oligomers can be blended in one operation with a first fraction rich in lower oligomers to obtain a composite for SAE 10W-30 usage and in another operation with a different lower-oligomer-rich fraction to produce a composite acceptable for SAE 15W-40 usage. If the same lower-oligomer-rich fraction is employed, it is apparent that the proportions of the fractions must be different to produce SAE 10W-30 and SAE 15W-40 oils or that a different high-oligomer-rich fraction must be used.
  • the composite obtained after blending can be hydrogenated or the individual fractions can be hydrogenated before they are blended.
  • Pressures can range from about several hundred kPa up to about 13790 kPa (several hundred up to about 2000 psig) and temperatures range from about 50°C to about 3000°C.
  • the hydrogenation is terminated when the desired bromine number is achieved, typically less than 1.
  • Oligomer composites having specific oligomer distributions are necessary if engine oils which are cross-graded without the addition of VI improvers are to be obtained. Additionally, performance additives must be included in the formulation to obtain the desired service rating.
  • An SAE 10W-30 or SAE 15W-40 engine oil which meets the manufacturer's specifications therefore requires both the proper selection of oligomers and additives -- the oligomer combination to impart the desired viscosity characteristics and the additives to impart the necessary service characteristics. Acceptable formulations cannot be obtained when either the specified oligomer composite or the specified additives are not used.
  • SAE 10W-30 engine oils which do not contain polymeric viscosity index improvers and which meet the appropriate API "S" Service Classification for gasoline engines are provided.
  • These Service Categories include, most notably, SC, SD, SE, and SF. Oils meeting API Service Classification SF are the most important since they may be used where API Service Categories SE, SD or SC are recommended. Thus, where a specific Service Category is referred to herein, all prior Service Categories which have less stringent engine test requirements are also included.
  • the SAE 10W-30 engine oils suitable for use in gasoline engines contain 5% to 10% by weight gasoline engine performance additives so that the oil meets the API "S" Service requirements and 90% to 95% by weight of a hydrogenated decene-1 oligomer mixture containing 0.5% to 20% C30 oligomer, 43% to 66% C40 oligomer, 16% to 26% C50 oligomer, 5% to 11% C60 oligomer and 5% to 11% C70+ oligomers. Percentages reported herein for oligomers are area percentages determined by conventional gas-liquid chromatographic methods.
  • these engine oils are formulated with a performance additive package which meets the desired API "S" Service Rating, most typically, API Service Rating SF.
  • Performance additive packages are commercially available and widely used in the manufacture of engine oils. These packages are formulated to contain the necessary corrosion inhibitors, detergents, dispersants, antiwear additives, defoamers, antioxidants, metal passivators and other adjuvants required to obtain a useful motor oil of the desired quality, i.e., meeting the desired API Service Rating. The use of these additive packages greatly simplifies the task of the formulator.
  • oligomer composite contains 2% to 17% C30 oligomer, 45% to 63% C40 oligomer, 18% to 24% C50 oligomer, 6% to 10% C60 oligomer, and 6% to 10% C70+ oligomers.
  • non-polymer thickened SAE 10W-30 engine oils suitable for use in diesel engines i.e., meeting the appropriate API "C” Commercial Classification.
  • the most common oils of this type are those having API Service Ratings CC and CD.
  • these SAE 10W-30 oils can also meet API "S" Service requirements.
  • These latter types of “dual service” or “universal” engine oils have API Service Designations CD/SD, CD/SE, CC/SE, CC/SF, and CD/SF.
  • Such universal oils are widely used by individuals with mixed fleets, i.e., gasoline engine vehicles and lighter duty diesel engine vehicles, such as automobile diesel engines.
  • the SAE 10W-30 diesel and universal engine oils contain 10% to 20% by weight performance additives so that the formulated oil meets the appropriate API Service requirements and 80% to 90% by weight of a hydrogenated decene-1 oligomer mixture containing 0.5% to 16% C30 oligomer, 55% to 68% C40 oligomer, 14% to 23% C50 oligomer, 3% to 9% C60 oligomer, and 3% to 9% C70+ oligomers.
  • the oligomer composite will contain 2% to 13% C30 oligomer, 57% to 65% C40 oligomer, 16% to 21% C50 oligomer, 4% to 8% C60 oligomer, and 4% to 8% C70+ oligomers.
  • the performance additives are most generally incorporated into the oil by the addition of an available additive package.
  • the oil may, however, be formulated by the addition of the individual additive components. In either case the result is the same, that is, the engine oil contains the requisite amount of the necessary additives to achieve the desired API Services Rating.
  • the useful additive packages and the individual additives are known and commercially available.
  • HiTEC Ethyl Petroleum Additives Division provides a complete line of products which are sold under the trademark HiTEC.
  • Similar additive packages are available from other manufacturers.
  • TLA-654A (SF/CD), TLA-668 (SF/CC) , and TLA-679 (SF/CD) manufactured by Texaco Chemical Company
  • OLA 8150A (SF/CD), OLA 8363C (SF/CC), OLA 8373 (SF/CC), OLA 8718 (SF/CD) , and OLA 8730 (SF/CD) manufactured by Chevron Chemical Company, Oronite Additives Division
  • Lubrizol trademark) 7574 (SF/CC) and Lubrizol 3978 (SF/CD) manufactured by The Lubrizol Corporation
  • Other additive packages with different API service ratings are available from the aforementioned manufacturers and other suppliers.
  • detergents and dispersants include polyalkenylsuccinimides and oil-soluble metal soaps, such as Ca, Ba, Mg and Al carboxylates, phenates and sulfonates.
  • Useful metal passivators include benzotriazole, 2-mercaptobenzotriazole, 2,5-dimercaptothiadiazole, salts of salicylaminoguanidine, quinizarin and propyl gallate.
  • Useful rust/corrosion inhibitors include primary, secondary or tertiary aliphatic or cycloaliphatic amines and amine salts of organic and inorganic acids; oil-soluble alkylammonium carboxylates; substituted imidazolines and oxazolines; alkali metal and alkaline earth metal carbonates; alkali metal and alkaline earth metal salts of alkylbenzene sulfonic acids, such as barium dinonylnaphthalenesulfonates, calcium petroleumsulfonates; esters, anhydrides, and metal salts of organic acids, such as sorbitan monooleate, lead naphthenate, and dodecylsuccinic anhydride.
  • Set point reducers can include alkylated naphthalenes, alkylated phenols and polymethacrylates.
  • Anti-wear additives can include sulfur, phosphorus, and halogen-containing compounds, such as sulfurised vegetable oils, zinc dialkyl dithiophosphates, chlorinated paraffins, alkyl and aryl disulfides.
  • Multifunctional additives such as those described in U.S. Patent Nos. 3,652,410, 4,162,224, and 4,534,872 can also be utilized for the formulation of these engine oils.
  • the amount of the individual additives will vary and is dictated by the particular application and the service requirement desired. The total amount of the additives, however, falls within the above-prescribed weight percent limits specified for each of the engine oils.
  • the oven temperature was increased at a rate of 15°C/min over the range 140°C to 350°C and then maintained at 350°C for 10 minutes. Separation of decene-1 oligomers above C70 is not possible employing this technique. For this reason, the last oligomer fraction is reported as C70+ since it may also contain small amounts of oligomers higher than C70, primarily C80 and C90 oligomers.
  • Viscosities reported in the examples and identified as the Cold Crank Simulator (CCS) viscosity and 100°C viscosity are determined in accordance with ASTM D-2602 and ASTM D-445 per SAE J300 APR84 specifications. CCS viscosities are reported in Pa ⁇ s (centipoise) at the specified temperatures (°C) whereas 100°C viscosities are reported in m2/s (centistokes).
  • Non-polymer thickened SAE 10W-30 SF/CD universal engine oils suitable for use in both gasoline and diesel engines were prepared.
  • 86.31 parts polyalphaolefin synthetic hydrocarbon basestocks comprised of mixtures of decene-1 oligomers were combined with 13.69 parts performance additive package meeting API SF/CD service requirements [Lubrizol (trademark) 3978].
  • the oligomer distribution of each basestock and the 100°C and CCS (-20°C) viscosities for the resulting formulated engine oils were as follows: EX. VI EX. VII E. VIII EX. IX EX.

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

Claims (9)

  1. Huile moteur multi-grade non-épaissie par polymère comprenant de 80 à 95 % en poids d'un mélange d'oligomères hydrogénés du décène-1 et de 0,5 à 20 % en poids d'additifs de performances pour moteurs, caractérisée en ce que le mélange d'oligomères contient :
    de 0,5 % à 20 % d'un oligomère en C₃₀,
    de 43 % à 68 % d'un oligomère en C₄₀,
    de 14 % à 34 % d'un oligomère en C₅₀,
    de 3 % à 16 % d'un oligomère en c₆₀, et
    de 3 % à 16 % d'oligomères en C₇₀₊,
    avec une viscosité de 9,3 x 10⁻⁶ à 12,5 x 10⁻⁶ m²/s (9,3 à 12,5 centistokes) à 100°C pour une huile 10 W-30 ou une viscosité de 12,5 x 10⁻⁶ à 16,3 x 10⁻⁶ m²/s (12,5 à 16,3 centistokes) à 100°C pour une huile 15 W-40.
  2. Huile moteur non-épaissie par polymère selon la revendication 1, laquelle huile est une huile pour moteur à essence SAE 10W-30 comprenant de 90 à 95 % en poids d'un mélange d'oligomères hydrogénés du décène-1 et de 5 à 10 % en poids d'additifs de performances pour moteurs à essence, ce mélange d'oligomères contenant :
    de 0,5 % à 20 % d'un oligomère en C₃₀,
    de 43 % à 66 % d'un oligomère en C₄₀,
    de 16 % à 26 % d'un oligomère en C₅₀,
    de 5 % à 11 % d'un oligomère en C₆₀, et
    de 5 % à 11 % d'oligomères en C₇₀₊.
  3. Huile moteur non-épaissie par polymère selon la revendication 1 ou 2, laquelle huile satisfait aux spécifications de la Catégorie de Service API SF.
  4. Huile moteur non-épaissie par polymère selon la revendication 1 ou 2, dans laquelle le mélange d'oligomères contient
    de 2 % à 17 % d'un oligomère en C₃₀,
    de 45 % à 63 % d'un oligomère en C₄₀,
    de 18 % à 24 % d'un oligomère en C₅₀,
    de 6 % à 10 % d'un oligomère en C₆₀, et
    de 6 % à 10 % d'oligomères en C₇₀₊.
  5. Huile moteur non-épaissie par polymère selon la revendication 1, qui est une huile moteur universelle ou diesel SAE 10W-30 comprenant de 80 à 90 % en poids d'un mélange d'oligomères hydrogénés du décène-1 et de 10 à 20 % en poids d'additifs de performances pour moteurs universels ou diesels, ce mélange d'oligomères contenant :
    de 0,5 % à 16 % d'un oligomère en C₃₀,
    de 55 % à 68 % d'un oligomère en C₄₀,
    de 14 % à 23 % d'un oligomère en C₅₀,
    de 3 % à 9 % d'un oligomère en C₆₀, et
    de 3 % à 9 % d'oligomères en C₇₀₊.
  6. Huile moteur non-épaissie par polymère selon la revendication 5, qui satisfait aux spécifications de la Catégorie de Service API CD.
  7. Huile moteur non-épaissie par polymère selon la revendication 5, qui satisfait aux spécifications des Catégories de Service API SF et CD.
  8. Huile moteur non-épaissie par polymère selon l'une quelconque des revendications 5 à 7, dans laquelle le mélange d'oligomères contient :
    de 2 % à 13 % d'un oligomère en C₃₀,
    de 57 % à 65 % d'un oligomère en C₄₀,
    de 16 % à 21 % d'un oligomère en C₅₀,
    de 4 % à 8 % d'un oligomère en C₆₀, et
    de 4 % à 8 % d'oligomères en C₇₀₊.
  9. Utilisation de l'huile moteur non-épaissie par polymère selon la revendication 1 en tant qu'huile multigrade.
EP88105305A 1987-04-01 1988-03-31 Huiles de moteur synthétiques hydrocarbonées Expired - Lifetime EP0288777B1 (fr)

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US3343687A 1987-04-01 1987-04-01
US33436 1987-04-01

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EP0288777A2 EP0288777A2 (fr) 1988-11-02
EP0288777A3 EP0288777A3 (en) 1989-03-08
EP0288777B1 true EP0288777B1 (fr) 1994-05-11

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JP (1) JPS63260990A (fr)
KR (1) KR960006008B1 (fr)
BR (1) BR8801426A (fr)
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DE (1) DE3889492T2 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0413315A1 (fr) * 1989-08-15 1991-02-20 Ethyl Corporation Huile multigrade synthétique hydrocarbonée améliorée pour moteur
EP0475391A1 (fr) * 1990-09-12 1992-03-18 Ethyl Corporation Huile lubrifiante à base de produits de réaction d'oligomère d'alpha-oléfine et de phénol
US5207940A (en) * 1990-09-12 1993-05-04 Ethyl Corporation α-olefin oligomer-phenol lubricant oil adducts
EP0468109B2 (fr) † 1990-07-24 2001-06-27 Ethyl Petroleum Additives Limited Lubrifiants et fluides fonctionnels biodégradables

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0288698A (ja) * 1988-09-26 1990-03-28 Honda Motor Co Ltd 良好な極圧性能を有する低粘度エンジン油

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4282392A (en) * 1976-10-28 1981-08-04 Gulf Research & Development Company Alpha-olefin oligomer synthetic lubricant
US4587368A (en) * 1983-12-27 1986-05-06 Burmah-Castrol, Inc. Process for producing lubricant material

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0413315A1 (fr) * 1989-08-15 1991-02-20 Ethyl Corporation Huile multigrade synthétique hydrocarbonée améliorée pour moteur
EP0468109B2 (fr) † 1990-07-24 2001-06-27 Ethyl Petroleum Additives Limited Lubrifiants et fluides fonctionnels biodégradables
EP0475391A1 (fr) * 1990-09-12 1992-03-18 Ethyl Corporation Huile lubrifiante à base de produits de réaction d'oligomère d'alpha-oléfine et de phénol
US5207940A (en) * 1990-09-12 1993-05-04 Ethyl Corporation α-olefin oligomer-phenol lubricant oil adducts

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Publication number Publication date
DE3889492T2 (de) 1994-08-25
CA1311465C (fr) 1992-12-15
EP0288777A2 (fr) 1988-11-02
KR960006008B1 (ko) 1996-05-06
EP0288777A3 (en) 1989-03-08
BR8801426A (pt) 1988-11-01
KR880012743A (ko) 1988-11-28
DE3889492D1 (de) 1994-06-16
JPS63260990A (ja) 1988-10-27

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