US20030186824A1 - Environmentally friendly lubricants - Google Patents

Environmentally friendly lubricants Download PDF

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US20030186824A1
US20030186824A1 US10/253,126 US25312602A US2003186824A1 US 20030186824 A1 US20030186824 A1 US 20030186824A1 US 25312602 A US25312602 A US 25312602A US 2003186824 A1 US2003186824 A1 US 2003186824A1
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oil
environmentally friendly
ester
lubricant
friendly lubricant
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I-Ching Chiu
Selda Gunsel
Paul Lacey
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Pennzoil Quaker State Co
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Pennzoil Quaker State Co
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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
    • C10M169/044—Mixtures of base-materials and additives the additives being a mixture of non-macromolecular and macromolecular compounds
    • 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
    • C10M101/00—Lubricating compositions characterised by the base-material being a mineral or fatty oil
    • C10M101/04—Fatty oil fractions
    • 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
    • C10M105/38—Esters of polyhydroxy compounds
    • 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
    • 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
    • C10M2203/1006—Petroleum or coal fractions, e.g. tars, solvents, bitumen 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
    • 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
    • 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
    • C10M2205/022—Ethene
    • 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
    • C10M2207/283—Esters of polyhydroxy compounds
    • C10M2207/2835—Esters of polyhydroxy compounds 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
    • C10M2207/40—Fatty vegetable or animal oils
    • 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
    • C10M2207/40—Fatty vegetable or animal oils
    • C10M2207/401—Fatty vegetable or animal oils used as base material
    • 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
    • C10N2040/255—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
    • C10N2060/00—Chemical after-treatment of the constituents of the lubricating composition

Definitions

  • This invention relates to environmentally friendly engine lubricant compositions suitable for internal combustion engines, and in particular for use in gasoline-fueled and diesel-fueled engines.
  • Vegetable oil triglycerides are available for use in food products and cooking. Many such vegetable oils contain natural antioxidants such as phospholipids and sterols that prevent oxidation during storage. Triglycerides are considered the esterification product of glycerol with three molecules of carboxylic acids. The amount of unsaturation in the carboxylic acid affects the susceptibility of the triglyceride to oxidze. Oxidation can include reactions that link two or more triglycerides together through reactions of atoms near the unsaturation. These reactions may form higher molecular weight material which can become insoluble and discolored e.g. sludge.
  • Oxidation can also result in cleavage of the ester linkage or other internal cleavage of the triglycerides.
  • the fragments of the triglyceride from the cleavage being lower in molecular weight, are more volatile.
  • Carboxylic acid groups generated from the oxidation of triglyceride make the lubricant acidic. Aldehyde groups may also be generated.
  • Carboxylic acid groups have attraction for oxidized metals and can solubilize them in oil promoting metal removal from some surfaces of lubricated metal parts.
  • Synthetic ester lubricants having little or no unsaturation in the carbon to carbon bonds are used in premium quality motor oils due to their desirable properties.
  • acids and alcohols used to make synthetic esters usually are derived from petroleum distillates and are thus not from a renewable source.
  • Synthetic lubricants are also more costly and less biodegradable than natural triglycerides.
  • oils high in natural oleic acid levels such as safflower, sunflower, corn, soybean and rapeseed oils. These polyunsaturated oils have lower oxidative stability, whereas fully saturated oils tend to crystallize at low temperatures.
  • oils with a high preponderance of the monounsaturated fat, oleic acid provides a reasonable compromise between these two extremes.
  • an oil for use in internal combustion engines should also satisfy the most current requirements of the GF-3/API SL minimum performance standards, including a gelation index of less than about 12; high temperature TEOST (thermo-oxidative engine oil simulation) of total deposits of 45 mg maximum; remain homogeneous and miscible when mixed with SAE reference mineral oils; low volatility; phosphorous level of 0.1% maximum; and has to pass foam, filterability and ball rust test.
  • TEOST thermo-oxidative engine oil simulation
  • an environmentally friendly lubricant comprises a transesterified triglyceride oil and a synthetic ester different from the triglyceride oil, the lubricant having a gelation index less than about 12 and being at least 60% biodegradable.
  • the lubricant can be used as an automobile engine oil and may further include viscosity index improvers and/or detergent inhibitor (DI) packages.
  • the automobile engine oil may also include other additives, such as a pour point depressant, antioxidant, friction modifier, rust inhibitor, corrosion inhibitor and anti-foaming agent. Additional embodiments are explained in the following description.
  • FIG. 1 is a graph of gelation index (Gi) against the weight percent of viscosity modifier (VII) for various lubricants made in embodiments of the invention.
  • Embodiments of the invention provide an environmentally friendly lubricant for use under a variety of operating conditions in automobiles, trucks, vans, buses, and off-highway farm, industrial, and construction equipment.
  • the oil is at least about 60% biodegradable according to ASTM D5864-95 and meets one or more of the current standards according to the Society of Automotive Engineers (SAE), American Petroleum Institute (API) and the International Lubricant Standardization and Approval Committee (ILSAC), which are incorporated by reference herein in their entirety.
  • R R L +k*(R U ⁇ R L ), wherein k is a variable ranging from 1 percent to 100 percent with a 1 percent increment, i.e., k is 1 percent, 2 percent, 3 percent, 4 percent, 5 percent, . . . , 50 percent, 51 percent, 52 percent, . . . , 95 percent, 96 percent, 97 percent, 98 percent, 99 percent, or 100 percent.
  • any numerical range defined by two R numbers as defined in the above is also specifically disclosed.
  • ASTM stands for American Society for Testing and Materials which provides standard protocols for material evaluation.
  • BIODEGRADABILITY is a measure of a lubricants biodegradability.
  • ASTM D 5864 determines lubricant biodegradation. The test determines the rate and extent of aerobic aquatic biodegradation of lubricants when exposed to an inoculum under laboratory conditions. The degree of biodegradability is measured by calculating the rate of conversion of the lubricant to CO 2 . A lubricant is classified as readily biodegradable when 60 percent or more of the test material carbon is converted to CO 2 in 28 days, as determined using this test method. In some embodiments, the lubricants have a biodegradability of at least 65%, 70%, 75%, 80%, 85%, 90%, or 95%.
  • BROOKFIELD VISCOSITY is viscosity, in centipoises, as determined on the Brookfield viscometer.
  • the operating principle for the Brookfield viscometer is the torque resistance on a spindle rotating in the fluid being tested.
  • Brookfield viscosities are most frequently associated with low temperature properties of gear oils and transmission fluids, they are in fact determined for many other types of lubricants.
  • COLD CRANKING STIMULATOR is an intermediate shear rate viscometer and measures the resistance of an oil to engine cranking at low temperatures. CCS is controlled largely by the additives in the oil and the viscosity index of the base oil.
  • GELATION INDEX is defined as the largest rate of change of viscosity increase when slowly cooled from ⁇ 5° C. to the lowest test temperature.
  • the gelation index is a number indicating the oil's tendency to form a gelated structure in the oil at colder temperatures. Numbers above 6 indicate some gelation-forming tendencies. Numbers above 12 are of concern to engine makers. Numbers above 15 have been associated with field-failing oils.
  • Gelation index is determined in accordance with ASTM D-5133, which is incorporated by reference herein in its entirety. The gelation index can be measured by the Scanning Brookfield Technique in accordance with ASTM D5133. In this test, a tube of oil containing a rotor driven at 0.3 RPM is slowly cooled at 1° C.
  • the viscosity is measured by the increasing torque generated by a spindle rotating in the oil at constant speed. A plot of the overall viscosity curve is generated. The gelation index is determined accordingly.
  • GELATION POINT also known as GELATION TEMPERATURE is defined as the temperature at which the gelation index occurs. Gelation temperature is determined in accordance with ASTM D-5133, which is incorporated by reference herein in its entirety.
  • KINEMATIC VISCOSITY is viscosity now commonly reported in centistokes (cSt), measured at either 40° C. or 100° C.
  • YIELD STRESS AND Apparent LOW TEMPERATURE VISCOSITY measures the borderline pumping temperature for engine oils.
  • An engine oil is held at 80° C. in a mini-rotary viscometer and slowly cooled at a programmed cooling rate to a final test temperature, a low torque is applied to the rotor shaft to measure yield stress, then a higher torque is applied to determine the apparent viscosity of the sample.
  • POISE is the CGS unit of absolute viscosity. This is the shear stress (in dynes per square centimeter) required to move one layer of fluid along another over a total layer thickness of one centimeter at a shear rate of one centimeter per second. Dimensions are dyne-sec/cm 2 .
  • the centipoise (cP) is 1/100 of a poise and is the unit of absolute viscosity most commonly used. Whereas ordinary viscosity measurements depend on the force of gravity on the fluid to supply the shear stress and are thus subject to distortion by differences in fluid density, absolute viscosity measurements are independent of density and are directly related to resistance to flow.
  • POUR POINT is a widely used low-temperature flow indicator defined as the lowest temperature at which an oil or distillate fuel is observed to flow when cooled under conditions prescribed by test method ASTM D97.
  • the pour point is 3° C. (5° F.) above the temperature at which the oil in a test vessel shows no movement when the container is held horizontally for five seconds.
  • TESS TAPERED BEARING SIMULATOR
  • VISCOSITY INDEX measures the rate of change of viscosity with temperature, determined by formula from the viscosities at 40° C. and 100° C. in accordance with ASTM D567 (or D2270 for VI's above 100).
  • VISCOSITY is a measure of a fluid's resistance to flow. It is ordinarily expressed in terms of the time required for a standard quantity of the fluid at a certain temperature to flow through a standard orifice. The higher the value, the more viscous the fluid. Since, viscosity varies inversely with temperature, its value is meaningless unless accompanied by the temperature at which it is determined. With petroleum oils, viscosity is now commonly reported in Centistokes (cSt), measured at either 40° C. or 1 00C (ASTM Method D445—Kinematic Viscosity).
  • VOLATILITY is a property of a liquid that defines its evaporation characteristics. Of two liquids, the more volatile boils at a lower temperature, and it evaporates faster when both liquids are at the same temperature.
  • the volatility of petroleum products can be evaluated by tests for Flash Point, Simulation Distillation and volatility weight loss (NOACK).
  • the environmentally friendly lubricant in accordance with embodiments of the invention is a mixture of transesterified vegetable oil and esters.
  • the lubricant has a gelation index of less than about 12. In some embodiments, the gelation index is less than about 10, less than about 8, less than about 6, less than about 4, or less than about 2.
  • the lubricant meets one or more of the current standards of the Society of Automotive Engineers (SAE), American Petroleum Institute (API) and the International Lubricant Standardization and Approval Committee (ILSAC) and is at least about 60% biodegradable according to the ASTM D 5864 test which defines the lubricant as readily biodegradable.
  • SAE Society of Automotive Engineers
  • API American Petroleum Institute
  • IVSAC International Lubricant Standardization and Approval Committee
  • Various types of vegetable oils may be present in the lubricant.
  • the transesterified vegetable oil may be a mixture of transesterified corn, rapeseed, soybean, and sunflower oil.
  • the transesterified vegetable oil is mixed with esters that lower the gelation index and improve viscosity.
  • Table 2 indicates various compositions of environmentally friendly lubricant compositions in accordance with embodiments of the invention. TABLE 2 Preferred More Preferred Most Preferred Possible Component Range (wt. %) Range (wt. %) Range (wt. %) Range (wt. %) Range (wt. %) Range (wt. %) Range (wt. ).
  • the environmentally friendly lubricant is a mixture of a transesterified vegetable oil in an amount from about 30 to about 85%, more preferably from about 35 to about 75%, and most preferred from about 40 to about 65%; a synthetic ester in an amount from about 10 to about 30%, more preferred from about 12 to about 25%, and most preferred from about 15 to about 20%.
  • an ester type viscosity index improver may be added in an amount from about 0.1 to about 3.0%, more preferred from about 0.2 to about 2.5%, most preferred from about 0.5 to about 2%; further, an olefin copolymer type viscosity index improver is optionally added in an amount from about 0.1 to about 6.0%, more preferred from about 1 to about 5%, most preferred from about 2 to about 4%.
  • the environmental lubricant further optionally includes a dispersant/inhibitor package in an amount from about 8 to about 14%, more preferred from about 10 to about 12%; and other additives, such as a pour point depressant, antioxidant, friction modifier, rust inhibitor, corrosion inhibitor, and anti-foaming agent, in the amount from about 0.1 to about 5%, more preferred from about 0 to about 2%.
  • the environmentally friendly lubricant is formulated to have a gelation index of less than about 12 and is at least about 60% biodegradable in the ASTM D-5864-95 biodegradability test.
  • the environmentally friendly lubricant also meets all ILSAC GF-3/API SL bench tests.
  • transesterified vegetable oils in the environmentally friendly lubricant are in the amount from about 30 to about 85 wt %, more preferably from about 35 to about 75 wt %, and most preferred from about 40 to about 65 wt %.
  • Suitable transesterified vegetable oils include, but are not limited to those described in the following U.S. Patents which are incorporated by reference herein in their entirety: U.S. Pat. Nos. 6,420,322; 6,414,223; 6,291,409; 6,281,375; 6,278,006; 6,271,185; and 5,885,643.
  • one such transesterified vegetable oil comprises a glycerol polyol ester having the following formula, as disclosed in U.S. Pat. No. 6,278,006:
  • R 1 , R 2 , and R 3 are aliphatic hydrocarbyl groups having from about 4 to about 24 carbon atoms inclusive, wherein at least one of R 1 , R 2 , and R 3 have a saturated aliphatic hydrocarbyl moiety having about 4 to about 10 carbon atoms inclusive, and wherein at least one of R 1 , R 2 , and R 3 have an aliphatic hydrocarbyl moiety having from about 12 to about 24 carbon atoms inclusive.
  • These triglycerides are available from a variety of plants or their seeds and are commonly referred to as vegetable oils.
  • R 1 , R 2 and R 3 may be different moieties or the same moiety.
  • hydrocarbyl group having at least 60 percent monounsaturated character and containing from about 6 to about 24 carbon atoms.
  • hydrocarbyl group denotes a radical having a carbon atom directly attached to the remainder of the molecule.
  • the aliphatic hydrocarbyl groups include the following:
  • Aliphatic hydrocarbon groups that is, alkyl groups such as heptyl, nonyl, undecyl, tridecyl, heptadecyl; alkenyl groups containing a single double bond such as heptenyl, nonenyl, undecenyl, tridecenyl, heptadecenyl, heneicosenyl; alkenyl groups containing 2 or 3 double bonds such as 8,11-heptadecadienyl and 8,11,14-heptadecatrienyl. All isomers of these are included, but straight chain groups are preferred.
  • Substituted aliphatic hydrocarbon groups that is groups containing non-hydrocarbon substituents which do not alter the predominantly hydrocarbon character of the group.
  • substituents examples are hydroxy, carbalkoxy (especially lower carbalkoxy), and alkoxy (especially lower alkoxy).
  • lower denoting groups containing not more than 7 carbon atoms.
  • Hetero groups that is, groups which, while having predominantly aliphatic hydrocarbon character contain atoms other than carbon present in a chain or ring otherwise composed of aliphatic carbon atoms. Suitable hetero atoms will be apparent to those skilled in the art and include, for example, oxygen, nitrogen and sulfur.
  • Naturally occurring triglycerides are vegetable oil triglycerides.
  • Transesterified triglycerides may be formed by the reaction of one mole of glycerol with three moles of a fatty acid or mixture of fatty acids or by the chemical modification of a naturally occurring vegetable oil. Regardless of the source of the triglyceride oil, the fatty acid moieties are such that the triglyceride has a monounsaturated character of at least about 60 percent, preferably at least about 70 percent and most preferably at least about 80 percent.
  • the transesterified triglyceride may also have a monounsaturated character of at least about 85, 90, or 95%.
  • Preferred transesterified vegetable oils have relatively high oxidative stability and good low temperature viscosity properties.
  • Oxidative stability is related to the degree of unsaturation in the oil and can be measured, e.g., with an Oxidative Stability Index instrument, Omnion, Inc., Rockland, Mass. according to AOCS Official Method Cd 12b-92 (revised 1993).
  • Oxidative stability is often expressed in terms of “AOM” hours.
  • oxidative stability of oils can range from about 40 AOM hours to about 120 AOM hours or from about 80 AOM hours to about 120 AOM hours.
  • the transesterified vegetable oils used in some embodiments have excellent low temperature viscosity properties.
  • a higher viscosity index value indicates that the viscosity of the oil changes less with a change in temperature.
  • the higher the viscosity index the greater the resistance of the lubricant to thicken at low temperatures and thin out at high temperatures.
  • Transesterified vegetable oils used in certain embodiments have a pour point from about 0° C. to about ⁇ 30° C.
  • the vegetable oils are liquid at room temperature and have a melting point of about 6° C. or less.
  • the vegetable oils may be genetically modified such that they contain a higher than normal oleic acid content.
  • High oleic vegetable oils contain at least about 60% oleic acid. These high oleic oils have lower oxidative stability, whereas fully saturated oils tend to crystallize at low temperatures.
  • Normal sunflower oil has an oleic acid content of 25-30 percent. By genetically modifying the seeds of sunflowers, a sunflower oil can be obtained wherein the oleic acid content is from about 60 percent up to about 90 percent.
  • U.S. Pat. No. 4,627,192 and No. 4,743,402 are herein incorporated by reference for their disclosure to the preparation of high oleic sunflower oil and its method of measuring the oleic acid content.
  • High oleic vegetable oils can be high oleic safflower oil, high oleic corn oil, high oleic rapeseed oil, high oleic sunflower oil, high oleic soybean oil, high oleic cottonseed oil, high oleic lesquerella oil, high oleic meadowfoam oil and high oleic palm olein.
  • a preferred oil is the AGRI-PURE 560TM which is a transesterified high oleic acid sunflower oil with short saturated fatty acid esters.
  • AGRI-PURE 560TM is a synthetic polyolester TAG base oil by CARGILL (Minneapolis, Minn.).
  • AGRI-PURE 560TM The specifications according to the manufacturer for AGRI-PURE 560TM are: TABLE 3 AGRI-PURE 560 TM PROPERTY AGRI-PURE 560 TEST METHOD Viscosity at 40° C. 28.76 cSt ASTM D445 Viscosity at 100° C. 6.47 cSt ASTM D445 Viscosity Index 189 ASTM D2270 Noack volatility 3.5% ASTM D6375-99A Specific Gravity 0.924 g/ml ASTM D1298 Density 7.39 lbs/gal By conversion Flash Point 247° C. ASTM D92 Oxidative Stability >1500 hrs ASTM D943 Dry PDSC, 180° C. 38 minutes ASTM D6186-98 Biodegradability >95% CEC L33-A-94 Biodegradability >80% ASTM D5864-95
  • Additional preferred TAG base oils include a high oleic sunflower oil available as SUNYL 80TM and a high oleic rapeseed oil available as RS-80TM, both from SVO ENTERPRISES (Eastlake, Ohio).
  • Other high oleic oils include high oleic sunflower oils available from DOW, DUPONT, or Instituto de la Grasa, high oleic canola oils from CARGILL or DUPONT, high oleic soybean oils from DUPONT or MONSANTO, high oleic corn oils from DUPONT, and high oleic peanut oils from MYCOGEN or the University of Fla.
  • Non-genetically modified vegetable oils are sunflower oil, safflower oil, corn oil, soybean oil, rapeseed oil, meadowfoam oil, lesquerella oil, castor oil or olive oil. It is to be noted that olive oil is naturally high in oleic acid. The oleic acid content of olive oil typically ranges from about 65 to about 85 percent.
  • Any vegetable oil can be transesterified by the addition of a saturated ester, preferably a short chain fatty acid or a polyol ester. This addition results in random esterification of the short chain fatty acids to the glycerol backbone of the vegetable oil.
  • transesterification can be performed by adding a short chain fatty acid ester to a vegetable oil in the presence of a suitable catalyst and heating the mixture.
  • Esters of short chain fatty acids include methyl esters and polyol esters. Methyl esters can be produced, for example, by esterification of fatty acids.
  • Polyol esters also can be used in the transesterification of vegetable oils.
  • polyol esters refers to esters produced from polyols containing from two to about 10 carbon atoms and from two to six hydroxyl groups. Preferably, the polyols contain two to four hydroxyl moieties.
  • transesterification of a polyol ester with a vegetable oil results in the short fatty acid chains of the polyol and the long fatty acid chains of the TAG being randomly distributed among both the polyol and glycerol backbones.
  • transesterified vegetable contain TAGs having a structure as defined above, and/or a non-glycerol polyol ester having the following structure:
  • R 4 and R 5 are independently aliphatic hydrocarbyl groups having from about 4 to about 24 carbon atoms inclusive, wherein at least one of R 4 and R 5 have a saturated aliphatic hydrocarbyl moiety having about 4 to about 10 carbon atoms inclusive, and wherein at least one of R 4 and R 5 have an aliphatic hydrocarbyl moiety having from about 12 to about 24 carbon atoms inclusive.
  • These triglycerides are available from a variety of plants or their seeds and are commonly referred to as vegetable oils.
  • R 6 and R 7 are independently a hydrogen, an aliphatic hydrocarbyl moiety having one to four carbon atoms, or the following formula:
  • X is an integer of about 0 to about 6, and wherein R 8 is an aliphatic hydrocarbyl moiety having four to 24 carbon atoms.
  • transesterified vegetable oils are disclosed in U.S. Pat. No. 6,278,006, which is incorporated in its entirety herein.
  • Other triaglycerol oils that may be used are disclosed in U.S. Pat. Nos. 5,990,055 and 6,281,375, which are incorporated by reference in their entirety.
  • the transesterified vegetable oil may include the glycerol polyol ester (shown above) alone or the non-glycerol polyol ester (shown above) alone, or a mixture of both.
  • Vegetable oils tend to crystallize at low temperature because the triacyl structures tend to be quite regular and subject to packing. This causes the viscosity to abruptly increase at lower temperatures, resulting in the failure of gelation index tests.
  • a low gelation index saturated synthetic ester (which is different from the vegetable oil) is added. For example, from about 10 to about 30% of a saturated synthetic ester was blended in the formulation. It was discovered that the synthetic ester, particularly saturated esters, lowered the gelation index significantly.
  • the synthetic ester may be a dibasic ester such as adipate, a sebacate ester, a tribasic ester such as trimethylol ethane (TME), a trimethylol propane (TMP) ester, or a polyol ester, such as pentaerythritol ester.
  • the gelation index of the first ester added to the transesterified triglyceride oil should be less than about 10, less than about 8, or less than about 6.
  • the first ester used to lower the gelation index of the lubricant has a gelation index of less than about 5, such as about 4 or less, about 3 or less, about 2 or less, or about 1 or less.
  • Dibasic or dibasic acid esters are the products from a C 4 -C 12 dicarboxylic acid (such as succinic, glutaric acid, adipic acid, and sebacic acid) reacting with 2 moles of C 1 -C 12 alcohols.
  • a dicarboxylic acid such as succinic, glutaric acid, adipic acid, and sebacic acid
  • the dibasic ester should have a viscosity index of at least about 120 in order to function adequately.
  • Dibasic esters are of the formula:
  • R 1 and R 2 are a hydrocarbyl group having from about 1 to about 20 carbon atoms and n is an integer from about 1 to about 20.
  • a preferred dibasic ester is EMKARATE 1130TM which is the diester of a C 10 alcohol with sebacic acid by UNIQEMA PERFORMANCE CHEMICALS (New Castle, Del.).
  • R 1 and R 2 may be different moieties or the same moieties.
  • Dibasic esters having similar characteristics as those in the following talbe are also useful: Property Value Flash Point, ° C. 230 (closed cup) 260 (open cup) Auto Ignition Temperature, ° C. 385 Density, g/ml 0.909 Pour Point, ° C. ⁇ 60 Kinematic Viscosity, cSt 20.2 @ 40° C. 4.8 @ 100° C.
  • Tribasic esters are the products from a C 4 -C 12 tricarboxylic acid reacting with 3 moles of C 1 -C 20 alcohols or made by a fatty acid condensing with a polyol (tri-ol).
  • the tribasic ester should have a viscosity index of at least about 120 in order to function adequately.
  • Tribasic esters are of the formula:
  • R 1 , R 2 , R 3 and R 4 are a hydrocarbyl group having from about 1 to about 20 carbon atoms.
  • a preferred tribasic ester is EMKARATE 1550TM made by UNIQEMA PERFORMANCE CHEMICALS (New Castle, Del.).
  • R1, R2, R3 and R4 may be different moieties or the same moieties.
  • R 1 , R 2 , R 3 , and R 4 are a hydrocarbyl group having from about 1 to about 20 carbon atoms.
  • R 4 is CH 3
  • the resulting synthetic ester is a trimethylol ethane ester.
  • R 4 is CH 3 CH 2
  • the resulting synthetic ester is a trimethylol propane ester.
  • Suitable synthetic esters include EMKARATE 1700TM which is a pentaerythritol ester of a C 5 -C 7 alcohol, PRIOLUBE 3960TM, PRIOLUBE 3939TM, PRIOLUBE 1831TM which are polymers made from a dimer acid with a di-alcohol by UNIQEMA PERFORMANCE CHEMICALS (New Castle, Del.)
  • R 1 , R 2 , R 3 and R 4 may be different moieties or the same moieties.
  • viscosity index improvers were added to the formulation.
  • viscosity modifier or viscosity index improver.
  • One is the relative polar ester-type, such as LUBRIZOL 7671TM, which is a long chain ester of maleic anhydride styrene copolymer (see also, LUBRIZOL 7764TM and LUBRIZOL 7783TM which are polymethacrylate copolymers).
  • OCP non-polar hydrogenated olefin copolymer
  • OCP non-polar hydrogenated olefin copolymer
  • LUBRIZOL 7075TM also included are hydrogenated styrene-diene copolymers, such as INFINEUM SV 200TM and INFINEUM SV 150TM, etc.
  • INFINEUM SV 200TM and INFINEUM SV 150TM etc.
  • a preferred polar ester-type viscosity modifier is LUBRIZOLTM 7671 made by LUBRIZOL (Wickliffe, Ohio).
  • LUBRIZOLTM 7671 is a polymethacrylate type thickener and also acts as a pour point depressant for vegetable oils.
  • Other polar ester-type viscosity modifiers include LUBRIZOLTM 7764, LUBRIZOLTM 7776, LUBRIZOLTM 7785, LUBRIZOLTM 7786, from LUBRIZOL (Wickliffe, Ohio) which are polymethacrylate copolymer viscosity index improvers.
  • Polar ester-type viscosity modifiers having similar properties as those in the following table are also useful: Property Value Flash Point, ° C. 165 Specific Gravity 0.90 Viscosity, cSt 8500 @ 40° C. 1500 @ 100° C.
  • a preferred non-polar hydrogenated olefin copolymer-type viscosity modifier is the LUBRIZOL 7075TM Series made by LUBRIZOL (Wickliffe, Ohio). This series is Lubrizol's next generation nondispersant olefin copolymer (OCP) viscosity modifier.
  • Hydrogenated olefin copolymers are the most widely used type of viscosity modifier for passenger car motor oils and heavy-duty diesel engine oils. Developed in the mid-1960s, hydrogenated olefin copolymers differ mainly in molecular weight and the ratio of ethylene to propylene. These polymers effectively minimize viscosity variations over typical engine operating temperatures. They are cost-effective and are suitable for formulating nearly any mainline engine oil. The polymers provide a cost-effective way to meet the latest international and original equipment manufacturer (OEM) specifications for passenger car and heavy-duty diesel engine oils.
  • OEM original equipment manufacturer
  • Non-polar hydrogenated olefin copolymer-type viscosity modifiers having the following characteristics may also be useful in embodiments: Property Value Flash Point, ° C. 190 Specific Gravity 0.87 Viscosity, cSt 825 @ 100° C.
  • LUBRIZOL 7075DTM is a preferred olefin copolymer type viscosity modifier from LUBRIZOL (Wickliffe, Ohio).
  • Other olefin copolymer type viscosity modifiers include the LUBRIZOL 7070TM series, 7077TM series, 7740TM series; INFINEUM SV140TM, SV145TM, SV200TM, SV205TM, SV300TM, SV305TM, (EXXONMOBIL, TX) and PARATONETM 8900 series by (CHEVRON,CA).
  • the ester type viscosity modifiers contribute to the lowering of the gelation index.
  • the maximum amount of ester viscosity modifiers allowable in the formulation without failing the gelation index specification is from about 1.7 to about 2.0%, see FIG. 1.
  • the viscosity grade of the formulated oil is a SAE 30 grade or lower.
  • Ester type viscosity modifiers having the following characteristics may also be useful in embodiments: Property Value Flash Point, ° C. 161 Specific Gravity 0.90 Viscosity, cSt 20.5 @ 100° C.
  • the solubility of the hydrogenated olefin copolymer-type viscosity modifier in vegetable oil is about 4 to about 6 wt % due to the polarity difference.
  • the formulation of the lubricant is a viscosity grade SAE 30 grade oil.
  • the ester type viscosity index improver may be added in an amount from about 0 to about 3.0%, more preferred from about 0.2 to about 2.5%, most preferred from about 0.5 to about 2% and the hydrogenated olefin copolymer type viscosity index improver may be added in an amount from about 0 to about 6.0%, more preferred from about 1 to about 5%, most preferred from about 2 to about 4%.
  • olefin polymers such as polybutene, hydrogenated polymers and copolymers and terpolymers of styrene with isoprene and/or butadiene, polymers of alkyl acrylates or alkyl methacrylates, copolymers of alkyl methacrylates with N-vinyl pyrrolidone or dimethylaminoalkyl methacrylate. These are used as required to provide the viscosity range desired in the finished oil, in accordance with known formulating techniques.
  • Esters obtained by co-polymerizing styrene and maleic anhydride in the presence of a free radical initiator and thereafter esterifying the copolymer with a mixture of C 4 -C 18 alcohols, are also useful as viscosity modifying additives.
  • the styrene esters generally are considered to be multi-functional premium viscosity modifiers.
  • the styrene esters in addition to their viscosity-modifying properties also are pour point depressants and exhibit dispersancy properties when the esterification is terminated before its completion leaving some unreacted anhydride or carboxylic acid groups. These acid groups can then be converted to amides by reaction with a primary amine.
  • SMA copolymer
  • Some SMA polymers that are commercially available from ROHMAX USA include VISCOPLEXTM 2-360, VISCOPLEXTM 2-500, VISCOPLEXTM 3-540, VISCOPLEXTM 4-671, and VISCOPLEXTM 6-054.
  • a dispersant/inhibitor additive package may be added to the lubricant to break insoluble particles already formed and to inhibit the formation of particles. Particles are kept finely divided so that they can remain dispersed or colloidally suspended in the oil.
  • the dispersant/inhibitor additive package is preferably in an amount from about 6 to about 18 wt %, more preferred from about 8 to about 16 wt %, and most preferred from about 10 to about 14 wt %.
  • Detergents and dispersants are polar materials that serve a cleaning function.
  • Detergents include metal sulfonates, metal salicylates and metal thiophosphonates.
  • Dispersants include polyamine succinimides, hydroxy benzyl polyamines, polyamine succinamides, polyhydroxy succinic esters and polyamine amide imidazolines.
  • Detergents are generally combined with dispersant additives in crankcase oils. Detergents chemically neutralize acidic contaminants in the oil before they become insoluble and fall out of the oil, forming a sludge. Neutral or basic compounds are created which can remain in suspension in the oil.
  • Lubricating oils typically contain from about 2 to about 5 wt % of detergent.
  • Suitable ashless dispersants may include, but are not limited to, polyalkenyl or borated polyalkenyl succinimide where the alkenyl group is derived from a C 3 -C 4 olefin, especially polyisobutenyl having a number average molecular weight of about 7,000 to 50,000.
  • Other well known dispersants include the oil soluble polyol esters of hydrocarbon substituted succinic anhydride, e.g.
  • polyisobutenyl succinic anhydride and the oil soluble oxazoline and lactone oxazoline dispersants derived from hydrocarbon substituted succinic anhydride and di-substituted amino alcohols, post-grafted polymers of ethylenepropylene with an active monomer such as maleic anhydride which may be further reacted with alcohol or an alkylene polyamine, styrene-maleic anhydride polymers post-reacted with alcohols and amines and the like.
  • an active monomer such as maleic anhydride which may be further reacted with alcohol or an alkylene polyamine, styrene-maleic anhydride polymers post-reacted with alcohols and amines and the like.
  • Dispersants typically contain a hydrocarbon chain attached to an amine or alcohol-containing polar group.
  • the hydrocarbon “tail” serves to solubilize the molecule in the lubricant base stock, while the polar group serves to attract the polar contaminants resulting from the lubricant breakdown.
  • the dispersant forms millions of micellar structures in the lubricant base stock which contain a highly polar core and disperse enormous amounts of polar contaminants.
  • These contaminants are products of oxidation which serve as precursors to varnish/carbon/sludge formation as well as already-formed varnish/carbon/sludge deposits.
  • the dispersed contaminants are held in “solution” in the basestock while already-formed deposits are cleaned off the metal and elastomer surfaces. Both the suspended precursors and deposits readily pass through commonly used filters.
  • the dispersant can no longer pick up contaminants, so the oil must be drained. However, the oil is usually drained well before this happens.
  • Lubricant oxidation is a chain reaction caused by the reaction of the oxygen in air with the lubricant base stock. Oxidation results in the formation of high molecular weight oil-insoluble polymers. These can settle out as sludges, varnishes and gums. They also cause an increase in the viscosity of the lubricant.
  • the function of the inhibitors is the prevention of the deterioration from the oxygen attack on the lubricant.
  • the oxidation inhibitors function either to destroy free radicals (phenolics or amines) or to decompose the peroxides (amines or ZDDPs) which are involved in the oxidation mechanism. As a result, the lubricant retains its cleanliness and viscosity allowing it to function properly over its drain interval.
  • a preferred dispersant/inhibitor additive package is LUBRIZOL 9850UTM from LUBRIZOL (Wickliffe, Ohio), or LUBRIZOL 9850TM.
  • the contents of DI packages are generally a proprietary secret, but usually contain an antiwear agent, such as ZDDP (Zinc dialkyl dithiophosphate); an antioxidant-phenolic and/or amine type antioxidant; a detergent (Mg and/or Ca sulfonate or phenate); a dispersant (polyisobutylene succinamide); a corrosion inhibitor; a rust inhibitor, a friction modifier; an anti-foaming agent, etc.
  • Suitable dispersant/inhibitor additive packages for gasoline and diesel engine oils are ORONITETM (CHEVRON, CA) and INFINEUMTM (EXXON-MOBIL, TX).
  • GF-3 DI packages include, for example, OLOA 55007TM and OLOA 59029TM (CHEVRON, CA), INFINEUM 5063TM, INFINEUM 3421TM, INFINEUM 3422TM (EXXON-MOBIL, TX), and LUBRIZOL 20,000TM and LUBRIZOL 20,000ATM (LUBRIZOL, OH).
  • Dispersant/inhibitor additive packages having similar characteristics as those listed below are also be useful: Property Value Flash Point, ° C. 146-167 Specific Gravity 0.96-0.97 Viscosity, cSt 1350-1400 @ 40° C. 100-125 @ 100° C.
  • the environmentally friendly lubricant may further include one or more additives.
  • additives include, but are not limited to antioxidants, pour point depressants, detergents, dispersants, friction modifiers, rust inhibitors, corrosion inhibitors and anti-foaming agents.
  • Typical antioxidants are aromatic amines, phenols, compounds containing sulfur or selenium, dithiophosphates, sulfurized polyalkenes, and tocopherols.
  • Hindered phenols are particularly useful, and include for example, 2,6-di-tert-butyl-p-cresol (DBPC), tert-butyl hydroquinone (TBHQ), cyclohexylphenol, and p-phenylphenol.
  • DBPC 2,6-di-tert-butyl-p-cresol
  • TBHQ tert-butyl hydroquinone
  • cyclohexylphenol and p-phenylphenol.
  • amine-type antioxidants include phenyl- ⁇ -napthylamine, alkylated diphenylamines and unsymmetrical diphenylhydrazine.
  • IRGANOX L-64 (Ciba Specialty Chemicals, Tarrytown, N.Y.) provides a mixture of antioxidants that is particularly useful.
  • Antioxidants are typically present in amounts from about 0.001 to about 10 weight %. In preferred embodiments, from about 0.01% to about 3.0% of an antioxidant is added to the lubricant.
  • U.S. Pat. Nos. 5,451,334 and 5,773,391 further disclose additional antioxidants and are hereby incorporated in their entirety by reference.
  • Pour point depressants lower the pour point of petroleum products containing wax by reducing the tendency of the wax to collect into a solid mass. Pour point depressants permit flow of the oil formulation below the pour point of the unmodified lubricant.
  • Common pour point depressants include polymethacrylates, wax alkylated naphthalene polymers, wax alkylated phenol polymers and chlorinated polymers.
  • U.S. Pat. Nos. 5,451,334 and 5,413,725 further disclose additional pour point depressants and are hereby incorporated in their entirety by reference.
  • pour point depressants are used generally in amounts of from about 0.01 to about 5 wt %, more typically from about 0.1 to about 1 wt %.
  • Illustrative of pour point depressants which are normally used in lubricating oil compositions are polymers and copolymers of n-alkyl methacrylate and n-alkyl acrylates, copolymers of di-n-alkyl fumarate and vinyl acetate, alpha-olefin copolymers, alkylated naphthalenes, copolymers or terpolymers of alpha-olefins and styrene and/or alkyl styrene, styrene dialkyl maleic copolymers and the like.
  • a preferred pour point depressant is ACRYLOID 3004 Oil Additive available by ROHMAX USA (Horsham, Pa.) that uses the commercial name VISCOPLEX 1-3004TM.
  • the chemistry is based on polymethacrylate (PMA).
  • Other VISCOPLEX series 1 wax modifiers that can be used include VISCOPLEX 1-6004, VISCOPLEX 1-331, and VISCOPLEX 1-600.
  • the VISCOPLEX series 10, such as VISCOPLEX 10-130, and 10-171 can also be used.
  • Suitable metal detergent additives are known in the art and may include one or more of overbased oil-soluble calcium, magnesium and barium phenates, sulfurized phenates, and sulfonates (especially the sulfonates of C 16 -C 50 alkyl substituted benzene or toluene sulfonic acids which have a total base number of about 80 to 300).
  • overbased materials may be used as the sole metal detergent additive or in combination with the same additives in the neutral form; but the overall metal detergent additive should have a basicity as represented by the foregoing total base number.
  • they are present in amounts of from about 3 to about 6 wt % with a mixture of overbased magnesium sulfurized phenate and neutral calcium sulfurized phenate (obtained from C 9 or C 12 alkyl phenols).
  • Suitable anti-wear additives are oil-soluble zinc dihydrocarbyldithiophosphates with a total of at least 5 carbon atoms and are typically used in amounts from about 1 to about 6 wt % by weight.
  • Other anti-wear additives include dithiophosphates and in particular, zinc dialkyl dithiophosphates, metal sulfonates, metal phenate sulfides, fatty acids, acid phosphate esters and alkyl succinic acids.
  • Anti-wear additives adsorb on metal, and provide a film that reduces metal-to-metal contact.
  • anti-wear additives include zinc dialkyldithiophosphates, tricresyl phosphate, didodecyl phosphite, sulfurized sperm oil, sulfurized terpenes and zinc dialkyldithiocarbamate.
  • Rust inhibitors protect surfaces against rust and include alkylsuccinic type organic acids and derivatives thereof, alkylthioacetic acids and derivatives thereof, organic amines, organic phosphates, polyhydric alcohols, and sodium and calcium sulphonates. Rust inhibitors are employed in very small proportions such as from about 0.1 to about 1 wt % with suitable rust inhibitors being exemplified by C 9 -C 30 aliphatic succinic acids or anhydrides such as dodecenyl succinic anhydride.
  • Anti-foam additives reduce or prevent the formation of a stable surface foam and are typically present in amounts from about 0.01 to about 1 wt %.
  • Polymethylsiloxanes, polymethacrylates, salts of alkylene dithiophosphates, amyl acrylate telomer and poly(2-ethylhexylacrylate-co-ethyl acrylate) are non-limiting examples of anti-foam additives.
  • Viscosity of an automotive oil is classified in SAE (Society of Automotive Engineers) viscosity grades represented by numbers such as 30, 40, 50. The higher the number, the thicker the oil and the greater it's effectiveness in high temperature operations. Lower numbered oils that are thinner oils with low viscosity are used in cold climates as they flow more easily and are identified by a “W” mark next to the grade of oil on the package. Multigrade oils 5Wxx, 10Wxx, 20Wxx, etc. are suitable for both low and high temperature conditions. Lubricating oils made specifically for industrial use have their viscosity classified by ISO (international Organization for Standardization) grades.
  • SAE grade motor oils high and low viscosity mineral oils are added to the environmentally friendly lubricant.
  • the SAE grade motor oils that can be achieved include 0W-30, 5W-30, 10W-30, and 10W-40.
  • Mineral oils from Group I to Group V are preferred.
  • Preferred examples useful in the formulation include: TABLE 4 Mineral Oils Kin. Visc. @ Kin. Visc. @ Group Example 40° C. (cSt) 100° C.
  • EXCEL 100-HCTM, 230-HCTM, and 575-HCTM are Group II mineral oils made by PENNZOIL-QUAKER STATE COMPANY (Houston, Tex.). Yubase 150NTM and 240NTM are Group III mineral oils made by Yukong (Seoul, Korea).
  • CHEVRON UCBO7RTM is a Group III mineral oil made by CHEVRON.
  • SHELL XHVI TM is a Group III mineral oil made by Shell Chemical Company. Mineral oils are used generally in amounts of from about 0 to about 40 wt %.
  • Table 5A and Table 5B provide the formulations and physical properties of lubricants using polar ester-type viscosity modifiers.
  • the dispersant/inhibitor package was LUBRIZOL 9850UTM.
  • the pour point depressant was Viscoplex 1-3004TM.
  • the mineral oil was Yubase 150NTM and the synthetic ester was Emkarate 1130TM.
  • the vegetable oil was AGRI-PURE 560TM.
  • the gelation index (Gi) for formulations including LUBRIZOL 7764TM and LUBRIZOL 7785TM were plotted against the weight percent of viscosity modifier (VII) as shown in FIG. 1.
  • This graph indicates that when the amount of viscosity modifier was higher than about 2.2 wt % and about 1.2 wt % of LUBRIZOL 7764TM and LUBRIZOL 7785TM, respectively, formulations failed the GF-3/API SL specification of the gelation index maximum of 12.
  • the formulations passed the gelation index, but the finished oils were limited to the SAE 30 viscosity grade.
  • using lower than 1.2 wt % of LUBRIZOL 7764TM gave formulations that passed the gelation index of 12, but the finished oils were limited to the SAE 20 viscosity grade.
  • Formulation I is an SAE 30 grade lubricant. It is possible to raise the viscosity of Formulation I to SAE 40 grade by increasing the non-biodegradable heavy oil, such as Excel 575-HC, which would decrease the biodegradability of the formulation.
  • Table 7A represents blends using a combination of the ester-type and the olefin copolymer type viscosity modifiers in a base oil comprising Group III mineral oils (Yubase 150NTM and Yubase 240NTM), a dibasic ester, and modified vegetable oil (AGRI-PURE 560TM).
  • Table 7B discloses the physical properties of the oils in Table 7A. These formulations pass the GF-3/API SL gelation index specification of less than about 12 and meet other physical properties of a SAE 5W-30 grade oil.
  • Formulation K was submitted to independent testing laboratories for ASTM D-6335 Thermo-Oxidation Engine Oil Simulation Test (TEOST), and ASTM D-5864-95 Biodegradability tests were performed at BfB Oil Research in Belgium. Results are shown in Table 8.
  • TEOST may be useful in determining the piston deposit control capability of the motor oil. According to the GF-3/API SL specification the total deposit in TEOST is 45 mg maximum.
  • Group III mineral oils in Example 3 can be replaced by Group II mineral oils, such as Excel HC or Exxon HC (hydro-conversion) oils.
  • Table 9A discloses formulations, in which the different viscosity grades of Group II oils were used alone or in combination to make wide viscosity ranges of motor oils.
  • Table 9B shows the properties of the formulations.
  • additional antioxidants i.e. Irganox L-64TM
  • Irganox L-64TM can be added to the formulation as illustrated in the formulation Q.
  • Formulation R replaces the Irganox L-64TM with NAUGALUBE MOLYFM 2543TM (Crompton Corporation, Middlebury, Conn.) which is a multifunctional friction modifier, anti-wear, and antioxidant additive.
  • TABLE 9A Formulations M-R Formulation M N O P Q R SAE Grade Descrip- 0W-30 5W-30 10W-30 10W-40 10W-40 10W-30 Components tion wt % wt % wt % wt % wt % wt % wt % DI, Lz 9850U DI 12 12 12 12 12 12 12 12 12 Viscoplex 1-3004 PPD 0.1 0.1 0.1 0.1 0.1 0.1 Lz 7764 VII 1.7 1.2 1.1 1.7 1.7 0 Lz 7075D VII 3.3 1.5 0 3.3 3.3 3.3 3.3 Excel 100-HC Group II 25 10 0 0 0 25 Oil Excel 575-HC Group II 0 20 30 30 29.5 0 Oil Irganox
  • the formulation Q was submitted to PerkinElmer Automotive Research Laboratory (San Antonio, Tex.) for high temperature TEOST MHT-4 Thermo-Oxidation Engine Oil Simulation test, Homogeneity and Miscibility (H&M) test, Foam sequence I, II, and III test, High Temperature Foam test, EOFT (Engine Oil Filterability test), and EOWTT (Engine Oil Filterability/water tolerance test).
  • H&M Thermo-Oxidation Engine Oil Simulation test
  • H&M Homogeneity and Miscibility
  • Foam sequence I, II, and III test High Temperature Foam test
  • EOFT Engine Oil Filterability test
  • EOWTT Engine Oil Filterability/water tolerance test
  • the aging cycle was designed to mimic that of the sequence VI B aging with the following parameters: 1500 rpm, 71.4 ft. lbs. torque (load) for 7320 seconds, 18.9 ft. lbs. torque for 1920 seconds, 71.4 ft. lbs. torque for 100 seconds (total aging 9340 seconds), 212° F. coolant temperature, and 220° F. oil temperature.
  • the Highway cycle consisted of a 300 second cycle programmed as follows: minimum rpm: 850, maximum rpm 1840, load varied from: 5 to 28 ft. lbs.
  • the Metro cycle consisted of a 504 second, low rpm and load cycle programmed as follows: minimum rpm: 560, maximum rpm: 1320, load varied from: 0 to 40 ft. lbs. Emissions readings were taken beginning at the onset of each programmed test cycle and ran for the entire duration of each.
  • Table 12 represents a range of SAE grade lubricant oils formulated from blends using a combination of the ester-type and the olefin copolymer type viscosity modifiers in a base oil comprising a blend of Group II mineral oils (Excel 100-HCTM and Excel 575-HCTM), a dibasic ester, and CARGILL modified vegetable oil, AGRI-PURE 560TM.
  • the dispersant/inhibitor additive package was Oloa 55007 and the pour point depressant was Viscoplex 1-3004.
  • Table 12 discloses the physical properties of the oils in Table 12. These formulations pass API SL gelation index specification of less than about 12 and meet other physical properties for their appropriate SAE grade.
  • Table 13 represents a range of SAE grade lubricant oils formulated from blends using a combination of the ester-type and the olefin copolymer type viscosity modifiers in a base oil comprising a blend of Group II mineral oils (Excel 100-HCTM and Excel 575-HCTM), a dibasic ester, and modified vegetable oil (AGRI-PURE 560TM).
  • the dispersant/inhibitor additive package was Lubrizol 20000 and the pour point depressant was Viscoplex 1-3004.
  • Table 13B discloses the physical properties of the oils in Table 13A.
  • Table 14 represents a 5W-30 SAE grade lubricant oil formulation using a combination of the ester-type and the olefin copolymer type viscosity modifiers in a base oil comprising a blend of Group II mineral oils (Excel 100-HCTM and Excel 575-HCTM), a dibasic ester, and modified vegetable oil (AGRI-PURE 560TM).
  • the dispersant/inhibitor additive package was Lubrizol 20000 and the pour point depressant was Viscoplex 1-3004. To enhance performance, an extra antioxidant was added. This formulation passed all API SL bench test requirements. Table 14 also discloses the physical properties of the formulation.
  • the formulation AA was submitted to PerkinElmer Automotive Research Laboratory (San Antonio, Tex.) for high temperature TEOST MHT-4 Thermo-Oxidation Engine Oil Simulation test, Homogeneity and Miscibility (H&M) test, Foam sequence I, II, and III test, High Temperature Foam test, EOFT (Engine Oil Filterability test), EOWTT (Engine Oil Filterability/water tolerance test), Gelation Index, NOACK Volatility, Volatility Loss, Phosphorous and Ball Rust Test. In the H&M test, the tested oil shall remain homogeneous and miscible when mixed with SAE reference oils. Table 15 discloses the results.
  • the formulation AA was also submitted for ASTM Sequence IIIF engine tests.
  • the Sequence IIIF Test is a fired-engine, dynamometer lubricant test for evaluating automotive engine oils for certain high-temperature performance characteristics, including oil thickening, sludge and varnish deposition, oil consumption, and engine wear.
  • the Sequence IIIF Test utilizes a 1996 model Buick 3800 Series II, water-cooled, 4-cycle, V-6 engine as the test apparatus.
  • the Sequence IIIF test engine is an overhead valve design (OHV) and uses a single camshaft opeating both intake and exhaust valves via pushrods and hydrualic valve lifters in a sliding-follower arrangement. The engine uses one intake and one exhaust valve per cylinder.
  • the Sequence IIIF Test consists of a 10-minute operational check, followed by 80 hours of engine operaton at moderately high speed, load, and temperature conditions. Following each 10-hour segment, and the 10-minute operational check, oil samples are drawn from the engine. The kinematic viscosities of the 10-hour segment samples are compared to the viscosity of the 10-minute sample to determine the viscosity increase of the test oil.
  • the Sequence IIIF Test is operated at the test states in Table 16 during the 80 hour portion of the test. Table 17 discloses the results. According to ASTM Sequence IIIF engine tests, the oil meets the bench test of the ILSAC GF-3/API SL minimum performance standard and passed all API-SL bench tests requirements. TABLE 16 Test states of Sequence IIIF testing Parameter Set Point Engine Speed 3600 r/min Engine Load 200 N-m Oil Filter Block Temperature 155° C. Coolant Outlet Temperature 122° C. Fuel Pressure 365 kPa Inlet Air Temperature 27° C. Inlet Air Pressure 0.05 kPa Inlet Air Dew Point 16.1° C.
  • embodiments of the invention provide an environmentally friendly lubricant that meets API SL bench test specifications, and is overall at least 60% biodegradable in ASTM D-5864-95 biodegradability testing. Additional characteristics and advantages provided by embodiments of the invention are apparent to those skilled in the art.
  • the compositions may include numerous compounds and/or characteristics not mentioned herein. In other embodiments, the compositions do not include, or are substantially free of, one or more compounds and/or characteristics not enumerated herein. Variations and modifications from the described embodiments exist.
  • the environmentally friendly lubricant need not be a mixture within the compositions given above. It can comprise any amount of components, so long as the properties desired in the environmentally friendly lubricant are met.
  • the application of the environmentally friendly lubricant composition is not limited to lubricants for automobiles; it can be used in any environment which requires an environmentally friendly lubricant, such as a trucks, vans or buses. It is noted that the methods for making and using the environmentally friendly lubricant composition are described with reference to a number of steps. These steps can be practiced in any sequence. One or more steps may be omitted or combined but still achieve substantially the same results. The appended claims intend to cover all such variations and modifications as falling within the scope of the invention.

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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)
US10/253,126 2001-09-25 2002-09-24 Environmentally friendly lubricants Abandoned US20030186824A1 (en)

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US20050059562A1 (en) * 2003-09-12 2005-03-17 Renewable Lubricants Vegetable oil lubricant comprising all-hydroprocessed synthetic oils
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US20050070449A1 (en) * 2003-09-30 2005-03-31 Roby Stephen H. Engine oil compositions
US20050112267A1 (en) * 2003-11-20 2005-05-26 Kian Yeong S. Lubricant base from palm oil and its by-products
US20060035794A1 (en) * 2004-08-11 2006-02-16 Daniel Graiver Triglyceride based lubricant
US20060113512A1 (en) * 2004-12-01 2006-06-01 Chevron U.S.A. Inc. Dielectric fluids and processes for making same
US20060135378A1 (en) * 2003-02-21 2006-06-22 Nippon Oil Corporation Lubricating oil composition for transmissions
US20060172898A1 (en) * 2005-01-31 2006-08-03 Roby Stephen H Lubricating base oil compositions and methods for improving fuel economy in an internal combustion engine using same
US20060211585A1 (en) * 2003-09-12 2006-09-21 Renewable Lubricants, Inc. Vegetable oil lubricant comprising Fischer Tropsch synthetic oils
WO2008013698A1 (fr) * 2006-07-21 2008-01-31 Exxonmobil Research And Engineering Company Procédé pour lubrifier un appareil à engrenage renforcé
US20080300157A1 (en) * 2007-03-30 2008-12-04 Wu Margaret M Lubricating oil compositions having improved low temperature properties
US20090031614A1 (en) * 2007-08-01 2009-02-05 Ian Macpherson Environmentally-Friendly Fuel Compositions
US20090156442A1 (en) * 2007-12-17 2009-06-18 Laurent Chambard Lubricant Compositions With Low HTHS for a Given SAE Viscosity Grade
US20090163393A1 (en) * 2007-12-21 2009-06-25 Boffa Alexander B Lubricating oil compositions for internal combustion engines
WO2010043371A1 (fr) * 2008-10-14 2010-04-22 Natoil Ag Liquide hydraulique et huile à engrenages à base d'huile végétale
US20100152078A1 (en) * 2007-05-04 2010-06-17 Ian Macpherson Environmentally-friendly lubricant compositions
US20100212624A1 (en) * 2004-12-22 2010-08-26 Breon Lewis D Method of Viscosity Control
US20100216678A1 (en) * 2009-02-24 2010-08-26 Abhimanyu Onkar Patil Lubricant compositions containing glycerol tri-esters
US20100240567A1 (en) * 2007-07-20 2010-09-23 Jean-Emile Zanetto Treatment/cleaning of textile materials utilizing formulations of carboxylic acid diesters
US20100240564A1 (en) * 2007-07-20 2010-09-23 Jean-Emile Zanetto Formulations of carboxylic acid diesters useful for treating/cleaning textile and other materials
US20120289445A1 (en) * 2011-03-08 2012-11-15 Cognis Ip Management Gmbh High Viscosity Lubricant Compositions Meeting Low Temperature Performance Requirements
US20130017984A1 (en) * 2010-03-31 2013-01-17 Idemitsu Kosan Co., Ltd. Biodegradable lubricating oil composition having flame retardancy
US8586518B2 (en) 2011-08-26 2013-11-19 State Industrial Products Corporation Biobased penetrating oil
EP2853801A1 (fr) * 2013-09-26 2015-04-01 M-I Finland Oy Composition d'agent de réduction de traînée, procédé pour sa préparation et procédé pour réduire la traînée
EP2853802A1 (fr) * 2013-09-26 2015-04-01 M-I Finland Oy Composition d'agent améliorateur d'écoulement, son procédé de préparation et procédés d'utilisation de celui-ci
US9028727B2 (en) 2011-09-23 2015-05-12 E I Du Pont De Nemours And Company Dielectric fluids comprising polyol esters
US9296969B2 (en) 2009-02-16 2016-03-29 Chemtura Corporation Fatty sorbitan ester based friction modifiers
US20160137948A1 (en) * 2013-07-05 2016-05-19 Tsubakimoto Chain Co. Lubricant composition for chains, and chain
WO2016156313A1 (fr) * 2015-03-30 2016-10-06 Basf Se Lubrifiants induisant une meilleure propreté d'équipements
US20180094203A1 (en) * 2016-09-30 2018-04-05 Chevron U.S.A. Inc. Fuel composition
US11525100B2 (en) * 2020-07-01 2022-12-13 Petro-Canada Lubricants Inc. Biodegradable fluids

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US7994107B2 (en) 2008-05-06 2011-08-09 Archer-Daniels-Midland Company Lubricant additives
CN101845354B (zh) * 2010-02-02 2013-06-19 新疆现代石油化工股份有限公司 一种采棉机摘锭油及其制备方法
EP3759200B1 (fr) 2018-03-02 2024-04-03 Chevron Oronite Technology B.V. Composition d'huile lubrifiante assurant une protection contre l'usure à faible viscosité
EP3759201A1 (fr) 2018-03-02 2021-01-06 Chevron Oronite Technology B.V. Composition d'huile lubrifiante assurant une protection contre l'usure à faible viscosité
CN110330430B (zh) * 2019-06-06 2022-04-19 深圳市优宝新材料科技有限公司 一种带有极性酯基支链的聚α烯烃化合物及其制备方法
JP2023049434A (ja) * 2021-09-29 2023-04-10 出光興産株式会社 潤滑油基油

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Cited By (56)

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US20010018484A1 (en) * 1999-09-17 2001-08-30 Bitler Steven P. Polymeric thickeners for oil-containing compositions
US7449511B2 (en) 1999-09-17 2008-11-11 Landec Corp. Polymeric thickeners for oil-containing compositions
US20050272618A1 (en) * 1999-09-17 2005-12-08 Bitler Steven P Polymeric thickeners for oil-containing compositions
US6989417B2 (en) * 1999-09-17 2006-01-24 Landec Corporation Polymeric thickeners for oil-containing compositions
US7101928B1 (en) * 1999-09-17 2006-09-05 Landec Corporation Polymeric thickeners for oil-containing compositions
US20030176301A1 (en) * 2002-03-13 2003-09-18 Barnes John F. Lubricant for two-cycle engines
US20060135378A1 (en) * 2003-02-21 2006-06-22 Nippon Oil Corporation Lubricating oil composition for transmissions
US9102897B2 (en) * 2003-02-21 2015-08-11 Nippon Oil Corporation Lubricating oil composition for transmissions
US20040241309A1 (en) * 2003-05-30 2004-12-02 Renewable Lubricants. Food-grade-lubricant
US20050059562A1 (en) * 2003-09-12 2005-03-17 Renewable Lubricants Vegetable oil lubricant comprising all-hydroprocessed synthetic oils
WO2005026300A1 (fr) * 2003-09-12 2005-03-24 Renewable Lubricants, Inc. Lubrifiant a base d'huile vegetale contenant toutes les huiles synthetiques hydrotraitees
US20060211585A1 (en) * 2003-09-12 2006-09-21 Renewable Lubricants, Inc. Vegetable oil lubricant comprising Fischer Tropsch synthetic oils
US20100132645A1 (en) * 2003-09-30 2010-06-03 Chevron Oronite Company Llc Engine oil compositions
US20050070450A1 (en) * 2003-09-30 2005-03-31 Roby Stephen H. Engine oil compositions
US7926453B2 (en) * 2003-09-30 2011-04-19 Chevron Oronite Company Llc Engine oil compositions
US20050070449A1 (en) * 2003-09-30 2005-03-31 Roby Stephen H. Engine oil compositions
US7678747B2 (en) * 2003-09-30 2010-03-16 Cherron Oronite Company LLC Engine oil compositions
US20090197783A1 (en) * 2003-09-30 2009-08-06 Chevron Oronite Company Llc Engine oil compostions
US7781384B2 (en) * 2003-11-20 2010-08-24 Malaysian Palm Oil Board Lubricant base from palm oil and its by-products
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US7601677B2 (en) * 2004-08-11 2009-10-13 Daniel Graiver Triglyceride based lubricant
US20060035794A1 (en) * 2004-08-11 2006-02-16 Daniel Graiver Triglyceride based lubricant
US20060113512A1 (en) * 2004-12-01 2006-06-01 Chevron U.S.A. Inc. Dielectric fluids and processes for making same
US7510674B2 (en) * 2004-12-01 2009-03-31 Chevron U.S.A. Inc. Dielectric fluids and processes for making same
US20100212624A1 (en) * 2004-12-22 2010-08-26 Breon Lewis D Method of Viscosity Control
US7465696B2 (en) 2005-01-31 2008-12-16 Chevron Oronite Company, Llc Lubricating base oil compositions and methods for improving fuel economy in an internal combustion engine using same
US20060172898A1 (en) * 2005-01-31 2006-08-03 Roby Stephen H Lubricating base oil compositions and methods for improving fuel economy in an internal combustion engine using same
US20080248983A1 (en) * 2006-07-21 2008-10-09 Exxonmobil Research And Engineering Company Method for lubricating heavy duty geared apparatus
WO2008013698A1 (fr) * 2006-07-21 2008-01-31 Exxonmobil Research And Engineering Company Procédé pour lubrifier un appareil à engrenage renforcé
US20080300157A1 (en) * 2007-03-30 2008-12-04 Wu Margaret M Lubricating oil compositions having improved low temperature properties
US20100152078A1 (en) * 2007-05-04 2010-06-17 Ian Macpherson Environmentally-friendly lubricant compositions
US7863232B2 (en) * 2007-07-20 2011-01-04 Rhodia Operations Treatment/cleaning of textile materials utilizing formulations of branched carboxylic acid diesters
US7871970B2 (en) * 2007-07-20 2011-01-18 Rhodia Operations Formulations of carboxylic acid diesters useful for treating/cleaning textile and other materials
US20100240567A1 (en) * 2007-07-20 2010-09-23 Jean-Emile Zanetto Treatment/cleaning of textile materials utilizing formulations of carboxylic acid diesters
US20100240564A1 (en) * 2007-07-20 2010-09-23 Jean-Emile Zanetto Formulations of carboxylic acid diesters useful for treating/cleaning textile and other materials
US20090031614A1 (en) * 2007-08-01 2009-02-05 Ian Macpherson Environmentally-Friendly Fuel Compositions
US20090156442A1 (en) * 2007-12-17 2009-06-18 Laurent Chambard Lubricant Compositions With Low HTHS for a Given SAE Viscosity Grade
US8703677B2 (en) 2007-12-21 2014-04-22 Chevron Japan Ltd Lubricating oil compositions for internal combustion engines
US20090163393A1 (en) * 2007-12-21 2009-06-25 Boffa Alexander B Lubricating oil compositions for internal combustion engines
WO2010043371A1 (fr) * 2008-10-14 2010-04-22 Natoil Ag Liquide hydraulique et huile à engrenages à base d'huile végétale
US9296969B2 (en) 2009-02-16 2016-03-29 Chemtura Corporation Fatty sorbitan ester based friction modifiers
US20100216678A1 (en) * 2009-02-24 2010-08-26 Abhimanyu Onkar Patil Lubricant compositions containing glycerol tri-esters
WO2010098825A1 (fr) * 2009-02-24 2010-09-02 Exxonmobil Research And Engineering Company Compositions lubrifiantes contenant des triesters de glycérol
US20130017984A1 (en) * 2010-03-31 2013-01-17 Idemitsu Kosan Co., Ltd. Biodegradable lubricating oil composition having flame retardancy
US20120289445A1 (en) * 2011-03-08 2012-11-15 Cognis Ip Management Gmbh High Viscosity Lubricant Compositions Meeting Low Temperature Performance Requirements
US9783761B2 (en) * 2011-03-08 2017-10-10 Cognis Ip Management Gmbh High viscosity lubricant compositions meeting low temperature performance requirements
US8586518B2 (en) 2011-08-26 2013-11-19 State Industrial Products Corporation Biobased penetrating oil
US9028727B2 (en) 2011-09-23 2015-05-12 E I Du Pont De Nemours And Company Dielectric fluids comprising polyol esters
US20160137948A1 (en) * 2013-07-05 2016-05-19 Tsubakimoto Chain Co. Lubricant composition for chains, and chain
WO2015048386A1 (fr) * 2013-09-26 2015-04-02 M-I Finland Oy Composition d'adjuvant améliorant l'écoulement, son procédé de préparation et ses procédés d'utilisation
EP2853802A1 (fr) * 2013-09-26 2015-04-01 M-I Finland Oy Composition d'agent améliorateur d'écoulement, son procédé de préparation et procédés d'utilisation de celui-ci
EP2853801A1 (fr) * 2013-09-26 2015-04-01 M-I Finland Oy Composition d'agent de réduction de traînée, procédé pour sa préparation et procédé pour réduire la traînée
WO2016156313A1 (fr) * 2015-03-30 2016-10-06 Basf Se Lubrifiants induisant une meilleure propreté d'équipements
US20180094203A1 (en) * 2016-09-30 2018-04-05 Chevron U.S.A. Inc. Fuel composition
US10301566B2 (en) * 2016-09-30 2019-05-28 Chevron U.S.A. Inc. Fuel composition
US11525100B2 (en) * 2020-07-01 2022-12-13 Petro-Canada Lubricants Inc. Biodegradable fluids

Also Published As

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ATE317889T1 (de) 2006-03-15
AR036616A1 (es) 2004-09-22
KR20040039416A (ko) 2004-05-10
CN1568360A (zh) 2005-01-19
DK1436369T3 (da) 2006-06-19
MY128504A (en) 2007-02-28
CN100384968C (zh) 2008-04-30
TWI258503B (en) 2006-07-21
AU2002334650B2 (en) 2007-09-20
DE60209260D1 (de) 2006-04-20
ES2258172T3 (es) 2006-08-16
CA2461158A1 (fr) 2003-04-03
EP1436369A1 (fr) 2004-07-14
JP2005504141A (ja) 2005-02-10
EP1436369B1 (fr) 2006-02-15
BR0212786A (pt) 2004-10-05
ZA200402221B (en) 2005-04-15
WO2003027212A1 (fr) 2003-04-03
DE60209260T2 (de) 2006-11-23

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