EP1877528A1 - High temperature biobased lubricant compositions comprising boron nitride - Google Patents
High temperature biobased lubricant compositions comprising boron nitrideInfo
- Publication number
- EP1877528A1 EP1877528A1 EP06751491A EP06751491A EP1877528A1 EP 1877528 A1 EP1877528 A1 EP 1877528A1 EP 06751491 A EP06751491 A EP 06751491A EP 06751491 A EP06751491 A EP 06751491A EP 1877528 A1 EP1877528 A1 EP 1877528A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- lubricant
- approximately
- oil
- oils
- weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Ceased
Links
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- 229910052582 BN Inorganic materials 0.000 title claims abstract description 68
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- 125000002960 margaryl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 231100000647 material safety data sheet Toxicity 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 235000013372 meat Nutrition 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 239000005078 molybdenum compound Substances 0.000 description 1
- 150000002752 molybdenum compounds Chemical class 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N n-hexanoic acid Natural products CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 1
- 125000005187 nonenyl group Chemical group C(=CCCCCCCC)* 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 150000002924 oxiranes Chemical class 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 238000005325 percolation Methods 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- RAFRTSDUWORDLA-UHFFFAOYSA-N phenyl 3-chloropropanoate Chemical compound ClCCC(=O)OC1=CC=CC=C1 RAFRTSDUWORDLA-UHFFFAOYSA-N 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 150000003047 pimelic acids Chemical class 0.000 description 1
- 239000010773 plant oil Substances 0.000 description 1
- 239000011120 plywood Substances 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical compound CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
- 150000004671 saturated fatty acids Chemical class 0.000 description 1
- 231100000241 scar Toxicity 0.000 description 1
- 150000003330 sebacic acids Chemical class 0.000 description 1
- 239000003079 shale oil Substances 0.000 description 1
- 235000011888 snacks Nutrition 0.000 description 1
- 235000010288 sodium nitrite Nutrition 0.000 description 1
- FVEFRICMTUKAML-UHFFFAOYSA-M sodium tetradecyl sulfate Chemical compound [Na+].CCCCC(CC)CCC(CC(C)C)OS([O-])(=O)=O FVEFRICMTUKAML-UHFFFAOYSA-M 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 229940012831 stearyl alcohol Drugs 0.000 description 1
- 150000003442 suberic acids Chemical class 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000003444 succinic acids Chemical class 0.000 description 1
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical class O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 239000003784 tall oil Substances 0.000 description 1
- CNALVHVMBXLLIY-IUCAKERBSA-N tert-butyl n-[(3s,5s)-5-methylpiperidin-3-yl]carbamate Chemical compound C[C@@H]1CNC[C@@H](NC(=O)OC(C)(C)C)C1 CNALVHVMBXLLIY-IUCAKERBSA-N 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- 125000005040 tridecenyl group Chemical group C(=CCCCCCCCCCCC)* 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 125000005065 undecenyl group Chemical group C(=CCCCCCCCCC)* 0.000 description 1
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- 239000003981 vehicle Substances 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
- C10M169/04—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
- C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
- C10M2201/06—Metal compounds
- C10M2201/061—Carbides; Hydrides; Nitrides
-
- 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
- C10M2205/0206—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers used as base material
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
- C10M2205/17—Fisher Tropsch reaction products
- C10M2205/173—Fisher Tropsch reaction products 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
- C10M2207/2805—Esters 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
- 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
- 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
- C10M2207/404—Fatty vegetable or animal oils obtained from genetically modified species
- C10M2207/4045—Fatty vegetable or animal oils obtained from genetically modified species 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
- C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
- C10N2020/01—Physico-chemical properties
- C10N2020/065—Saturated Compounds
-
- 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
- C10N2020/067—Unsaturated Compounds
Definitions
- This application claims priority to a provisional patent application, Serial No. 60/675,126, filed April 26, 2005, entitled HIGH TEMPERATURE BIOBASED LUBRICANT COMPOSITIONS FROM BORON NITRIDE.
- This invention relates to biobased lubricant compositions made from nalural and/or synthetic vegetable, animal, plant or tree oil and boron nitride, These compositions provide improved lubricity, anti-wear, and extreme pressure performance at extreme high temperatures up to and over 1000 0 C, These compositions can be particularly useful in high temperature applications for lubricating corrs ⁇ b ⁇ "ngines, ovens, chains, cables, gears, hinge pins, bearings, and sliding surfaces
- the lubricant composition can also be formulated into hydraulic fluids, turbine oils, compressor oils, penetrating lubricants, greases, anti-seize compounds, thread compounds, deep drawing compounds, rolling oils, metal working fluids, release agents, and any lubricant that requires antiwear and extreme pressure performance.
- Biobased oils are obtainable in large volumes from renewable resources derived from vegetables, animals, plants, or trees and in general are characterized as readily biodegradable or "environmentally non-toxic”. As a result, such oils are potentially attractive for use in a wide variety of applications and are defined in the 2002 Farm Bill as biobased. These biobased oils are obtained in natural and synthetic form.
- biobased oils With respect to use for lubrication purposes, biobased oils have not been fully desirable. Many biobased oils do not possess the desired spectrum of characteristics relating to: pour point; oxidative stability; and compatibility with additives among others. Biobased oils do however possess many desirable properties for use as a lubricant. In particular, biobased oils typically provide high flash point, good boundary lubrication, and very high viscosity index that can provide fuel economy, and are less than 1% volatility in the NOACK test which has shown to reduce engine oil emissions.
- biobased oils are generally nontoxic and readily biodegradable,
- a typical vegetable oil can biodegrade up to 80% into carbon dioxide and water in 28 days, as compared to 25% or less for typical petroleum-based lubricating fluids.
- the composition has exceptional benefits whenever there is direct loss of the lubricant into the environment.
- Sensitive areas include forestry, mining, marine, agriculture, heavy industry, transportation, rail and shipping, pulp and paper mills, saw mills, plywood mills, hoist cables and chains in marine shipping areas, draglines, drives on straddle lift lumber carriers, motorcycle and ATV chains, etc.
- the biobased materials and the boron nitride in this composition are listed by the USDA and NSF as food grade approved and are environmentally non-toxic.
- the equipment used in the food processing industry varies by segment with the three leading segments C-UTvpijs ⁇ -.. ,cat and poultry, beverages, snack foods, vegetables, and dairy. While the equipment varies from segment to segment, the moving parts such as bearing, gears and slide mechanisms are similar and often require lubrication.
- the lubricants most often used in these applications include oven lubricants, chain lubricants, cable lubricants, penetrating lubricants, anti-seize compound, thread compound, deep drawing compound, rolling oils, mold release agents, gear oils as well as all-purpose greases. These food industry oils must meet more stringent standards than other industry lubricants.
- the FSIS is custodian of the official list of authorized compounds for use in federally inspected plants.
- the official list (see page 11-1, List of Proprietary Substances and Nonfood Compounds, Miscellaneous Publication Number 1419 (1989) by the Food Safety and Inspection Service, United States Department of Agriculture) states that lubricants and other substances that are susceptible to incidental food contact are considered indirect food additives under USDA regulations. Therefore, these lubricants, classified as either H-I or H- 2, are required to be approved by the USDA before being used in food processing plants. The most stringent classification, H-I is for lubricants approved for incidental food contact.
- the H-2 classification is for uses where there is no possibility of food contact and assures that no known poisons or carcinogens are used in the lubricant.
- the instant invention pertains to H-I and H-2 approved lubricating oil.
- H-I and H-2 approved oil and the terms "food grade” will be used interchangeably for the purpose of this application.
- Lubricating oils for food processing plants should ivH-'nf :-' ⁇ Jiine parts, resist viscosity change, resist oxidation, protect against rusting and corrosion, provide wear protection, and resist the formation of deposits and sludge in service.
- the product should also perform effectively at various lubrications regimes ranging from hydrodynamic thick film regimes to boundary thin film regimes.
- the oxidation, and thermal characteristics of a lubricating oil helps predict how effectively an oil will maintain its lubricating properties over time and resist sludge and deposit formation.
- Hydrocarbon oils are partially oxidized when contacted with oxygen at elevated temperatures for prolonged periods of time and can develop hard carbon deposits that cause seizer in close tolerant metal to metal contact areas,
- a drawback with the food-grade-lubricants described in the related art relates to oxidation resistance, limited formulating capability for viscosity breadth, and limited viscosity protection.
- the lubricants often have poor oxidation and rheology characteristics when subjected to prolonged heat and mechanical stress.
- this composition can provide a dry lubricating film when temperatures exceed the auto-ignition temperatures of the biobase oils without developing hard carbon deposits.
- U.S. Patent No. 4,783,274 (Jokinen et al., November 8, 1988) is concerned with an cTib ⁇ ' ⁇ : ⁇ • AIy lubricant, which; is based on vegetable oils, which is substituted for mineral lubricant oils, and which, as its main component, contains triglycerides that are esters of saturated and/or unsaturated straight-chained Cio to C 22 fatty acids and glycerol.
- the lubricant is characterized in that it contains at least 70 percent by weight of a triglyceride whose iodine number is at least 50 and no more than 125 and whose viscosity index is at least 190.
- the lubricant oil may also contain a polymer prepared by hot-polymerization out of the said triglyceride or out of a corresponding triglyceride.
- the lubricant oil may contain solvents, fatty acid derivatives, in particular their metal salts, organic or inorganic, natural or synthetic polymers, and customary additives for lubricants.
- U. S. Patent No. 5,538,654 (Lawate et al., July 23, 1996) describes a food grade lubricant composition which is useful as hydraulic oil, gear oil, and compressor oil for equipment in the food service industry.
- This composition comprises (A) a major amount of a genetically modified vegetable oil and (B) a minor amount of a performance additive.
- the composition contains either (C) a phosphorus compound or (D) a non- genetically modified vegetable oil.
- U. S. Patent No. 5,580,482 (Chassan et al., December 3, 1996) relates to a lubricant composition stabilized against the deleterious effects of heat and oxygen said composition comprising a triglyceride oil or an oil which is an ester wherein unsaturation is present in either the alcohol moiety or the acid moiety and an effective stabilizing amount of either an N,N-disubstituted aminomelhyl-l,2,4-triazole or an N,N-di substituted aminomethyl- benzotriazole and a higher alkyl substituted amide of dodecylene succinic acid.
- U. S. Patent No. 580,482 Chossan et al., December 3, 1996) relates to a lubricant composition stabilized against the deleterious effects of heat and oxygen said composition comprising a triglyceride oil or an oil which is an ester wherein unsaturation is present in either the alcohol moiety or the acid moiety and
- 5,888,947 (Lambert et al., March 30, 1999 relates to a composition that has three main components: a base oil, an oil source containing hydroxy fatty acids and an oil source containing vegetable or animal waxes,
- the base oil used in the reference needs to consist of primarily triglycerols (triglycerides) and mono- and diglycerols (glycerides) and free fatty acids.
- the composition further consists of vegetable oils where the glycerols contain hydroxy fatty acids, making up 5% to 20% of the oil.
- a third component is waxes composing 5% to 10% of the oil additives by volume. Additional synthetic mimics or natural products derived from animal or vegetable compounds may be added up to 5% of the compositional volume.
- Patent No. 6,300,292 (Konishi et al., October 9, 2001 relates to a hydraulic oil composition comprising vegetable oil with a total degree of unsaturation of 0.3 or less as base oil, and comprising at least one antioxidant selected from the group consisting of a phenol antioxidant, an amine antioxidant and a zinc dithiophosphate antioxidant in an amount of 0.01 to 5% by mass based on the total amount of the composition.
- U. S. Patent No. 6,312,623 (Oommen et al., November 6, 2001) is directed to an electrical insulation fluid comprising at least 75% of a high oleic acid triglyceride composition that comprises fatty acid components of at least 75% oleic acid, less than 10% diunsaturated fatty acid component; less than 3% tri unsaturated fatty acid component; and less than 8% saturated fatty acid component; and wherein said composition is further characterized by the properties of a dielectric strength of at least 35 KWl 00 mil gap, a dissipation factor of less than 0.05% at 25 0 C, acidity of less than 0.03 mg KOH/g, electrical conductivity of less than 1 pS/m at 25°C, a flash point of at least 250 0 C 1 and a pour point of at least -15 0 C, and one or more additives selected from the group of an antioxidant additive, a pour point depressant additive and a copper deactivator.
- One aspect of the present invention is to extend the variety and compass of additives and base oils useful for improving the properties of high temperature, environmental, and food- grade-lubricants.
- the applicant has now discovered that when boron nitrides are formulated into the inventive compositions, the compositions show enhanced lubricity, anti- wear, extreme pressure, and oxidation resistance in extreme high temperatures up to and above 1000 0 C,
- the present invention provides a high dielectric strength that is beneficial in insulating fluids and compounds, These compositions can be particularly useful in high temperature applications for lubricating combustible engines, ovens, chains, cables, gears, hinge pins, bearings, and sliding surfaces.
- the lubricant composition can also be formulated into hydraulic fluids, turbine oils, compressor oils, penetrants, greases, anti-seize compounds, thread compounds, deep drawing compounds, rolling oils, metal working fluids, release agents, and any lubricant that requires anti-wear and extreme pressure performance. Because of the chemical structure of the lubricant base oil(s) with the boron nitrides these inventive compositions burns relatively free from abrasive hard carbon deposits allowing the boron nitride white powder to remain on the surface to be lubricated. This inventive cy, iii ⁇ ii also helps prevent the continuous build up of hard carbon deposits that cause seizing in the contact zone of close tolerant areas, which is a known problem with petroleum hydrocarbons.
- inventive compositions have shown to have improved lubricity, anti- wear, and extreme pressure performance at temperatures above 500 0 C where graphite and molybdenum are known to fail.
- inventive compositions have shown to have environmental benefits in engine oils by improving fuel economy and reducing emissions.
- inventive compositions can be formulated to be food grade and have shown to have improved biodegradability making them environmentally non-toxic.
- Another aspect of the present invention relates to an environmentally non-toxic and food-grade high temperature lubricant comprising: a) at least one biobased natural oil and biobased synthetic oil selected from the group consisting of natural or synthetic vegetable oil, natural or synthetic animal oil ⁇ genetically modified vegetable oil, genetically modified synthetic vegetable oil, natural or synthetic tree oil, and mixtures thereof; b) providing at lease one boron nitride and c) optionally, other base oils and d) optionally, other additives wherein said composition ingredients have H-I and H-2 approval as required by the United States Department of Agriculture. It is understood that the H-I and H-2 designation will ultimately relate to a comparable classification in countries outside the United States in most cases.
- the present invention discloses a method for the preparation of an environmentally non-toxic and food grade high temperature lubricant composition
- a method for the preparation of an environmentally non-toxic and food grade high temperature lubricant composition comprising the steps of 1) providing at least one biobased natural oil or biobased synthetic oil selected from the group consisting of natural or synthetic vegetable oil, natural or synthetic animal oil, genetically modified vegetable oil, genetically modified synthetic vegetable oil, natural or synthetic tree oil, and mixtures thereof; 2) providing at least one boron nitride; and 3) optionally, providing at least one base oil selected from the group consisting of a synthetic ester, solvent refined petroleum oil, a hydrocracked petroleum white oil, an all hydroprocessed synthetic oil, Fischer Tropsch base oil, petroleum oil group I, group II, group PL i pol/ ⁇ l ⁇ hciolcfi ⁇ (? ⁇ C), and mixtures thereof; 4) optionally, providing at least one additive selected from the group consisting of anti-oxidant(s), corrosion inhibitor(s), metal deactivator(
- Another aspect of the invention relates to a method of enhancing the lubrication of equipment that require biodegradable fluids, engine oils that reduce environmental emissions and improve fuel economy, and equipment used in the food service industry, comprising the steps of: 1) providing at least one environmentally non-toxic and food-grade high temperature lubricant composition comprising; a) at least one biobased natural oil or biobased synthetic oil selected from the group consisting of natural or synthetic vegetable oil, natural or synthetic animal oil, genetically modified vegetable oil, genetically modified synthetic vegetable oil, natural or synthetic tree oil, and mixtures thereof; b) at least one boron nitride; and c) optionally, other base oils and; d) optionally, other additives 2) adding an effective amount of said composition into said equipment.
- a lubricant includes at least one biobased oil selected from the group comprising: natural or synthetic vegetable oils, natural or synthetic animal oils, genetically modified vegetable oils, genetically modified synthetic vegetable oils, natural or synthetic tree oils, and mixtures thereof and at least one boron nitride.
- the lubricant further comprises at least one base oil selected from the group comprising: synthetic esters, solvent refined petroleum oils, hydrocracked petroleum white oils, all hydroprocessed synthetic oils,
- Fischer Tropsch oils group I petroleum oils, group II petroleum oils, group III petroleum oils, polyalphaolefins (PAOs), and mixtures thereof.
- the lubricant further includes at least one additive or combination of additives selected from the group comprising: anti-oxidants, corrosion inhibitors, metal deactivators, viscosity modifiers, anti-wear inhibitors, friction modifiers, and extreme pressure.
- the oil is a triglyceride having the formula
- R , R 2 , and R 3 are aliphatic hydrocarbyl groups that contain from about 7 to about 23 carbon atoms.
- the aliphatic hydrocarbyl groups are chosen from the group comprising: aliphatic hydrocarbon groups, substituted aliphatic hydrocarbon groups, and hetero groups.
- the triglyceride has an oleic acid profile of approximately 60% or above.
- the oleic acid profile can be any of the following percentages: 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, and 100.
- the triglyceride has a monosaturated character of approximately 60% or greater.
- the monosaturated character can be any of the following percentages: 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, and 100.
- the triglyceride has a monosaturated character of approximately 70% or greater.
- the monosaturated character can be any of the following percentages: 70, 71, 72, 73, 74, 75, 76,
- the triglyceride has a monosaturated character of approximately 80% or greater.
- the monosaturated character can be any of the following percentages: 80, 81, 82, 83, 84, 85, 86,
- the oil is approximately
- O ooo o / ⁇ c approximately 50% by weight of the lubricant.
- the oil cm be any of the following percentages: 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21,
- the oil is approximately
- the boron nitride can be any of the following percentages: 1, 2, 3, 4, 5, 6, 7, 8, 9,
- the oil is approximately
- the biobased oil is approximately 5% to approximately 90%> by weight of the lubricant
- the boron nitride is approximately 0.002% to approximately 80% by weight of the lubricant
- the base oil is approximately 20% to approximately 80% by weight of the lubricant
- the additive is approximately 0.001% to approximately 80% by weight of the lubricant.
- the biobased oil is approximately 40% to approximately 80% by weight of the lubricant
- the boron nitride is approximately 0.002% to approximately 35% by weight of the lubricant
- the base oil is approximately 10% to approximately 20% by weight of the lubricant
- the additive is approximately 0.001% to approximately 40% by weight of the lubricant.
- the biobased oil is approximately 60% to approximately 90% by weight of the lubricant
- the boron nitride is approximately 0.002% to approximately 5% by weight of the lubricant
- the base oil is approximately 1% to approximately 10% by weight of the lubricant
- the additive is approximately 0.001% to approximately 20% by weight of the lubricant.
- the oil is approximately coo/ I) v,d)-,hi- rr lc?s s of the lubricant and the boron nitride is approximately ⁇ 0 o/ " by weight, or greater, of the lubricant.
- the biobased oil is approximately 50% by weight, or less, of the lubricant
- the base oil, boron nitride, and additives together are approximately 50% by weight, or greater, of the lubricant.
- the biobased oil, boron nitride, and additives together are approximately 50% by weight, or less, of the lubricant, and the base oil is approximately 50% by weight, or greater, of the lubricant.
- a method for enhancing lubrication of equipment includes the steps of blending at least one boron nitride with at least one biobased oil selected from the group comprising: natural or synthetic vegetable oils, natural or synthetic animal oils, genetically modified vegetable oils, genetically modified synthetic vegetable oils, natural or synthetic tree oils, and mixtures thereof and adding an effective amount of the oil and boron nitride to the equipment.
- the method further comprises the step of prior to adding to the equipment, blending at least one base oil selected from the group comprising: synthetic esters, solvent refined petroleum oils, hydrocracked petroleum white oils, all hydroprocessed synthetic oils, Fischer Tropsch oils, group I petroleum oils, group II petroleum oils, group III petroleum oils, polyalphaolefms (PAOs), and mixtures thereof with the biobased oil and boron nitride.
- at least one base oil selected from the group comprising: synthetic esters, solvent refined petroleum oils, hydrocracked petroleum white oils, all hydroprocessed synthetic oils, Fischer Tropsch oils, group I petroleum oils, group II petroleum oils, group III petroleum oils, polyalphaolefms (PAOs), and mixtures thereof with the biobased oil and boron nitride.
- the method further comprises the step of prior to adding to the equipment, blending at least one additive or combination of additives selected from the group comprising: anti-oxidants, corrosion inhibitors, metal deactivators, viscosity modifiers, anti-wear inhibitors, friction modifiers, and extreme pressure with the biobased oil, the base oil, and the boron nitride.
- additives selected from the group comprising: anti-oxidants, corrosion inhibitors, metal deactivators, viscosity modifiers, anti-wear inhibitors, friction modifiers, and extreme pressure with the biobased oil, the base oil, and the boron nitride.
- the base oil is a synthetic triglyceride or a natural oil of the formula
- R 1 , R 2 and R 3 are aliphatic hydrocarbyl groups that contain from about 7 to about 23 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: (1) 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 used in this embodiment.
- Substituted aliphatic hydrocarbon groups that is groups containing non-hydrocarbon substituents which, in the context of this invention, do not alter the predominantly hydrocarbon character of the group.
- substituents examples are hydroxy, carbalkoxy, (especially lower carbalkoxy) and alkoxy (especially lower alkoxy), the term, "lower” denoting groups containing not more than 7 carbon atoms.
- Hetero groups that is, groups which, while having predominantly aliphatic hydrocarbon character within the context of this invention, contain atoms other than carbon present in a chain or ring otherwise composed of aliphatic carbon atoms. Suitable hetero atoms will be apparent Io those skilled in the art and include, for example, oxygen, nitrogen and sulfur.
- the triglyceride oils suitable for use in this invention are the vegetable and animal oils and modified vegetable and animal oils.
- the biobased oil triglycerides are naturally occurring oils.
- naturally occurring it is meant that the seeds from which the oils are obtained have not been subjected to any genetic altering.
- naturally occurring it is meant that the oils obtained are not subjected to esterification hydrogenation or any chemical treatment that alters the di- and tri-unsaturation character.
- the naturally occurring biobased oils having utility in this invention comprise at least one of soybean oil, rapeseed oil, sunflower oil, coconut oil, lesquerella oil, canola oil, peanut oil, corn oil, cottonseed oil, palm oil, safflower oil, meadowfoam oil, animal oil, or castor oil.
- J(N>49) TIK trigly ceride oils may also be modified vegetable and animal oils. Tri g lyceride oils are modified either chemically or genetically. Hydrogenation of naturally occurring triglycerides is the primary means of chemical modification. Naturally occurring triglyceride oils have varying fatty acid profiles. The fatty acid profile for naturally occurring sunflower oil is palmitic acid 70 percent stearic acid 4.5 percent oleic acid 18.7 percent linoleic acid 67.5 percent linolenic acid 0.8 percent other acids 1.5 percent
- chemically modifying sunflower oil by hydrogenation it is meant that hydrogen is permitted to react with the unsaturated fatty acid profile present such as oleic acid, linoleic acid and linolenic acid.
- the object is not to remove all the unsaturation. Further, the object is not to hydrogenate such that the oleic acid profile is reduced to a stearic acid profile.
- the object of chemical modification via hydrogenation is to engage the linoleic acid profile and reduce or convert a substantial portion of it to an oleic acid profile.
- the linoleic acid profile of naturally occurring sunflower oil is 67.5 percent. It is a goal of chemical modification to hydrogenate such that the linoleic acid is reduced to about 25 percent.
- oleic acid profile is increased from 18.7 percent to about 61 percent (18.7 percent original oleic acid profile plus 42.5 percent generated oleic acid from linoleic acid).
- Hydrogenation is the reaction of a biobased oil with hydrogen gas in the presence of a catalyst.
- the most commonly used catalyst is a nickel catalyst. This treatment results in the addition of hydrogen to the oil, thus reducing the linoleic acid profile and linolenic acid profile.
- Only the unsaturated fatty acid profiles participate in the hydrogenation reaction.
- other reactions also occur, such as shifting of the double bonds to a new position and also twisting from the cis form to the higher melting trans form.
- Table I shows the oleic acid (18:1), linoleic acid (18:2) and linolenic acid (18:3) profiles of selected naturally occurring vegetable oils. It is possible to chemically modify, via hydrogenation, a substantial portion of the linoleic acid profile of the triglyceride to increase th oleic acid piofilc to above 60 percent.
- Genetic modification occurs in the seed stock through natural field hybridization or in a controlled laboratory under more direct genetic modification.
- the harvested crop then contains a triglyceride oil that when extracted has a much higher oleic acid profile and a much lower linoleic acid profile.
- a naturally occurring sunflower oil has an oleic acid profile of 18.7 percent.
- a genetically modified sunflower oil has an oleic acid profile of 81.3 percent and linoleic acid profile of 9.0 percent.
- the chemically modified vegetable oils comprise at least one of a chemically modified corn oil, chemically modified cottonseed oil, chemically modified peanut oil, chemically modified palm oil, chemically modified coconut oil, chemically modified castor oil, chemically modified canola oil, chemically modified rapeseed oil, chemically modified safflower oil, chemically modified soybean oil, chemically modified animal oil, and chemically modified sunflower oil.
- the aliphatic hydrocarbyl groups of R 1 , R 2 , and R 3 are such that the triglyceride has a monounsaturated character of at least 60 percent, in another embodiment, at least 70 percent, and in another embodiment, at least 80 percent.
- Triglycerides having utility in this invention are exemplified by vegetable oils that are genetically modified such that they contain a higher than normal oleic acid content. 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 content is from about 60 percent up to about 90 percent.
- the R 1 , R 2 , and R 3 groups are heptadecenyl groups and the R 1 COO-, R 2 COO- and R 3 COO- to the 1,2,3-propanetriyl group CH 2 CHCH 2 are the u Mciue ⁇ l uu uLk, duid molecule.
- U.S. Pat. No. 4,627,192 and U.S, Pat No. 1,7"° 1C? arc herein incorporated by reference for their disclosure of the preparation of high oleic sunflower oil.
- a triglyceride comprised exclusively of an oleic acid moiety has an oleic acid content of 100% and consequently a monounsaturated content of 100%.
- the triglyceride is made up of acid moieties that are 70% oleic acid, 10% stearic acid, 13% palmitic acid, and 7% linoleic acid, the monounsaturated content is 70%.
- the triglyceride oils are high oleic acid, that is, genetically modified vegetable oils (at least 60 percent) triglyceride oils.
- Typical high oleic vegetable oils employed within the instant invention are high oleic safflower oil, high oleic canola oil, high oleic peanut oil, high oleic corn oil, high oleic rapeseed oil, high oleic sunflower oil, high oleic cottonseed, high oleic lesquerella oil, high oleic palm oil, high oleic castor oil, high oleic meadowfoam oil and high oleic soybean oil.
- Canola oil is a variety of rapeseed oil containing less than 1 percent erucic acid.
- One high oleic vegetable oil is high oleic sunflower oil obtained from Helianthus sp.
- TriSun 80 is a high oleic triglyceride wherein the acid moieties comprise 80 percent oleic acid.
- Another high oleic vegetable oil is high oleic canola oil obtained from Brassica campestris or Brassica napus, also available from AC Humko as RS high oleic oil.
- RS80 oil signifies a canola oil wherein the acid moieties comprise 80 percent oleic acid.
- genetically modified vegetable oils have high oleic acid contents at the expense of the di-and tri- unsaturated acids.
- a normal sunflower oil has from 20-40 percent oleic acid moieties and from 50-70 percent linoleic acid moieties. This gives a 90 percent content of mono- and di- unsaturated acid moieties (20+70) or (40+50).
- Genetically modifying vegetable oils generate a low di- or tri- unsaturated moiety vegetable oil.
- the genetically modified oils of this invention have an oleic acid moiety:linoleic acid moiety ratio of from about 2 up to about 90.
- a 60 percent oleic acid moiety content and 30 percent linoleic acid moiety content of a triglyceride oil gives a ratio of 2.
- the ratio for normal sunflower oil is 0.5 (30 percent oleic acid .uoiciv and 50 percent Ku oleic acid moiety).
- a triglyceride can be processed into a biobased synthetic ester and any of the above natural, chemically modified, and genetically modified, vegetable oils, tree oils, plant oils, and animal oils can be made into synthetic esters through an esterification process described further in this patent.
- Synthetic esters include polyesters, diesters, complex esters, and simple esters including methyl and ethyl esters. Additional patents that describe esterification include 6,051,539; 6,018,063; 5,885,946; 5,427,704; 5,338,471; 6,018,063; 5,994,278; 5,773,391; 6,583,302Bl; 6,774,091; and US 2003/0069146.
- B Boron Nitrides
- Advanced Ceramics Corporation is the world's largest producer of boron nitride powders, shapes and coatings, as well as other specialty ceramics.
- Boron nitride powder is a soft, white lubricious (slippery) powder with unique characteristics that make it an attractive, performance-enhancing alternative to graphite, molybdenum disulfide and other frequently used inorganic solid lubricants. With its superior adherence and thermochemical stability, boron nitride presents an opportunity for applications where conventional solid lubricants break down or fail to deliver the desired performance.
- This inorganic solid powder retains its ability to lubricate in extreme cold or heat and is well suited to extreme pressure (EP) applications.
- Boron nitride is a highly refractory (heat-resistant, stable) material with physical and chemical properties comparable to graphite. But, unlike graphite, it does not occur naturally in nature. It is typically synthesized from boric oxide or boric acid in the presence of urea or urea derivatives and ammonia, at temperatures ranging from 800°C to 2000 0 C.
- BN The two common crystalline structures of BN are cubic and hexagonal.
- Cubic boron nitride, (c)BN is like diamond, being hard and abrasive; and hexagonal boron nitride, (h)BN, is like graphite, being soft and lubricious.
- Hexagonal boron nitride powder exhibits the same characteristics of solid lubricants found in graphite and molybdenum disulfide. These include crystalline structure, low shear strength, adherence of the solid lubricant film, low abrasivity, and thermochemical stability.
- (h)BN exceeds the performance levels of these conventional solid lubricant characteristics, particularly adherence and thermochemical stability.
- Fomblin® oil samples containing 5 wt % of each material Fomblin® oil samples containing 5 wt % of each material.
- Advanced Ceramics produces several grades of boron nitrides for lubricants.
- the New Boron Nitride Powder NX Grades are listed for lubricants and include NXl, NX5, NX9, and NXlO.
- the grade for filtration and solubility is NXl which has a particle size of 1 micron or smaller.
- jCOTl [ Table 2
- composition of this invention may further comprise other additives and oils comprising (C) (1) a synthetic ester base oil, (C) (2) a polyalphaolefm or (C) (3) unrefined, refined or rerefined oils, (C) (4) a synthetic all hydroprocessed oil and Fischer Tropsch base oils, as well as mixtures of two or more of any of (C) (1), (C) (2), (C) (3), and (C) (4).
- the synthetic ester base oil (C) (1) comprises the reaction of a monocarboxylic acid of the formula
- R 10 -Ar(COOH) p wherein R is a hydrocarbyl group containing from about 4 to about 24 carbon atoms, R is hydrogen or a hydrocarbyl group containing from about 4 to about 50 carbon atoms, R 10 is hydrogen or a hydrocarbyl group containing from 1 up to about 24 carbon atoms, m is an integer of from zero to about 6 and p is an integer of from 1 to about 4; with an alcohol of the formula
- R 1 ' [0(CH 2 CHO) 1 H] n wherein R 1 ' is an aliphatic group containing from 1 to about 24 carbon atoms or an aromatic group containing from 6 to about 18 carbon atoms, R 12 is hydrogen or an alkyl group containing 1 or 2 carbon atoms, t is from O to about 40 and n is from 1 to about 6. [0073] Within the monocarboxylic acid, R 8 , in this embodiment, contains from about 6 to about 18 carbon atoms.
- monocarboxylic acids are the carboxylic acids of butanoic acid, hexanoic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid,-dddecanoic acid, palmitic acid, stearic acid and oleic acid, as well as isomers of these acids and mixtures thereof.
- R 9 contains from about 4 to about 24 carbon atoms and m is an integer of from 1 to about 3.
- An illustrative, but non-exhaustive, list of dicarboxylic acids are succinic, glutaric, adipic, pimelic, suberic, azelaic, sebacic, maleic, and fumaric acids.
- R 10 in this embodiment, contains from about 6 to about 18 carbon atoms and p is 2.
- Aryl carboxylic acids having utility are benzoic, toluic, ethylbenzoic, phthalic, isophthalic, terephthalic, hemimellitic, trimellitic, trimeric, and pyromellitic acids.
- R 11 contains from about 3 to about 18 carbon atoms and t is from 0 to about 20.
- the alcohols may be monohydric, polyhydric or alkoxylated monohydric and polyhydric.
- Monohydric alcohols can comprise, for example, primary and secondary alcohols.
- the monohydric alcohols are primary aliphatic alcohols, especially aliphatic hydrocarbon alcohols such as alkenols and ciikfcinois.
- polyhydric alcohols are those containing from 2 to about 6 hydroxy groups. They are illustrated, for example, by the alkylene glycols such as ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, dibutylene glycol, tributylene glycol, and other alkylene glycols.
- alkylene glycols such as ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, dibutylene glycol, tributylene glycol, and other alkylene glycols.
- One class of alcohols suitable for use in this invention are those polyhydric alcohols containing up to about 12 carbon atoms.
- This class of alcohols includes glycerol, erythritol, pentaerythritol, dipentaerythritol, gluconic acid, glyceraldehyde, glucose, arabinose, 1 ,7-heptanediol, 2,4- heptanediol, 1,2,3-hexanetriol, 1,2,4-hexanetriol, 1,2,5-hexanetriol, 2,3,4-hexanetriol, 1,2,3- butanetriol, 1,2,4-butanetriol, quinic acid, 2,2,6,6-tetralds (hydroxymethyl) cyclohexanol, 1- 10-decanediol, digitaloal, and the like.
- polyhydric alcohols for use in this invention are the polyhydric alcohols containing 3 to 10 carbon atoms and particularly those containing 3 to 6 carbon atoms and having at least three hydroxyl groups.
- Such alcohols are exemplified by a glycerol, erythritol, pentaerythritol, mannitol, sorbitol, 2-hydroxymethyl-2-methyl- 1,3, propanediol (trimethylolpropane), bis-trimethylolpropane. 1 ,2,4-hexanetriol and the like.
- the alkoxylated alcohols may be alkoxylated monohydric alcohols or alkoxylated polyhydric alcohols.
- the alkoxy alcohols are generally produced by treating an alcohol with an excess of an alkylene oxide such as ethylene oxide or propylene oxide.
- an alkylene oxide such as ethylene oxide or propylene oxide.
- an alkylene oxide such as ethylene oxide or propylene oxide.
- ethylene oxide or propylene oxide may be condensed with an aliphatic alcohol.
- the aliphatic alcohol contains from about 14 to about 24 carbon atoms and may be derived from long chain fatty alcohols such as stearyl alcohol or oleyl alcohol.
- the alkoxy alcohols useful in the reaction with the carboxylic acids to prepare synthetic esters are available commercially under such trade names as TRITON ' , TERGITOL ® from Union Carbide, ALFONIC ® from Vista Chemical, and NEODOL ® from Shell Chunked Company.
- the TRITON ® materials are idcn+ificd generally as polyethoxylated alkyl phenols which may be derived from straight chain or branched chain alkyl phenols.
- the TERGITOLS ® are identified as polyethylene glycol ethers of primary or secondary alcohols; the ALFONIC ® materials are identified as ethyoxylated linear alcohols which may be represented by the general structure formula
- ALFONIC ® ethoxylates characterized by the above formula include ALFONIC ® 1012-60 wherein x is about 8 to 10 and n is an average of about 5.7; ALFONIC ® 1214-70 wherein x is about 10-12 and n is an average of about 10.6; ALFONIC ® 1412-60 wherein x is from 10-12 and n is an average of about 7; and ALFONIC ® 1218-70 wherein x is about 10-16 and n is an average of about 10,7.
- the NEODOL ® ethoxylates are ethoxylated alcohols wherein the alcohols are a mixture of linear and branched alcohols containing from 9 to about 15 carbon atoms.
- the ethoxylates are obtained by reacting the alcohols with an excess of ethylene oxide such as from about 3 to about 12 or more moles of ethylene oxide per mole of alcohol.
- NEODOL ® ethoxylate 23-6.5 is a mixed linear and branched chain alcoholate of 12 to 13 carbon atoms with an average of about 6.5 ethoxy units.
- the synthetic ester base oil comprises reacting any above-identified acid or mixtures thereof with any above-identified alcohol or mixtures thereof at a ratio of not more than 1 COOH per 1 OH group using eslerif ⁇ cation procedures, conditions and catalysts known in the art.
- a non-exhaustive list of companies that produce synthetic esters and their trade names are BASF as Glissofluid, Ciba-Geigy as Reolube, JCI as Emkarote, Oleofina as Radialube and the Emery Group of Henkel Corporation as Emery.
- the polyalphaolefms (C) (2) such as alkylene oxide polymers and interpolymers ana derivative thereof where the terminal hydroxyl groups have been modified by esterification, etherification, etc., constitute another class of oils that can be used.
- oils prepared through polymerization of ethylene oxide or propylene oxide the alkyl and aryl ethers of these polyoxyalkylene polymers (e.g., methylpolyisopropylene glycolether having an average molecule weight of about 1000, diphenyl ether of polyethylene glycol having a molecular weight of about 500-1000, diethyl ether of polypropylene glycol having a molecular weight of about 1000-1500, etc.) or mono- and polycarboxylic esters thereof, for example, the acetic acid esters, mixed C 3 -Cs fatty acid esters, or the Ci 3 Oxo acid diester of tetraethyleneglycol.
- these polyoxyalkylene polymers e.g., methylpolyisopropylene glycolether having an average molecule weight of about 1000, diphenyl ether of polyethylene glycol having a molecular weight of about 500-1000, diethyl ether of polypropylene glycol having a molecular weight
- Unrefined oils are those obtained directly from a natural or synthetic source without further purification treatment.
- a shale oil obtained directly from retorting operations a petroleum oil obtained directly from distillation or ester oil obtained directly from an esterification process and used without further treatment would be an unrefined oil.
- mineral oils are under the purview of petroleum oils.
- Refined oils are similar to the unrefined oils except they have been further treated in one or more purification steps to improve one or more properties.
- Patents that generally disclose lubricants that can be formed using vegetable oil and group III oils include U.S. Pat. No. 6,103,673; U.S. Pat. No. 6,251,840; U.S. Pat. No. 6,451,745; and U.S. Pat. No. 6,528,458 all of which are from the Lubrizol Corporation (Wicldiffe, OH). Additional patents include U.S. Pat. No. 6,303,547 and U.S. Pat. No. 6,444,622 both from the Ethyl Corporation (Richmond, VA).
- U.S. Patent No, 6,528,458 discloses that compositions comprising (a) an oil of lubricating viscosity; (b) 2,5-dimercapto-l,3,4-thiadiazole (DMTD), a derivative of DMTD, or mixtures thereof; (c) a friction modifier; and (d) a dispersant, are useful for lubricating a transmission having a plurality of wet clutches and a plurality of partial power transmission shafts, wherein shifting of gears occurs by a process comprising synchronization of an engaged and a non-engaged partial transmission shaft and engagement of a wet clutch.
- DMTD 2,5-dimercapto-l,3,4-thiadiazole
- a dispersant are useful for lubricating a transmission having a plurality of wet clutches and a plurality of partial power transmission shafts, wherein shifting of gears occurs by a process comprising synchronization of an engaged and a non-engaged partial transmission shaft and
- 6,451,745 discloses that a continuously variable transmission can be lubricated by supplying to them a composition of (a) an oil of lubricating viscosity; (b) a dispersant; and (c) a detergent. At least one of the dispersant (b) and the detergent (c) is a borated species, and the amount of boron present in the composition is sufficient to impart improved friction and anti-seizure properties to the composition when employed in said transmission.
- U.S. Patent No. 6,444,622 discloses mixtures of the reaction product of at least one C 5 -C 6O carboxylic acid and at least one amine selected from the group comprising: guanidine, aminoguanidine, urea, thioruea and salts thereof and a phosphorus-containing dispersant are useful as gear oil additives.
- U.S. Patent No. 6,303,547 discloses that the reaction product of at least one C 5 -C 6O carboxylic acid and at least one amine selected from the group comprising: guanidine, aminoguanidine, urea, thioruea, and salts thereof is useful as a gear oil additive.
- U.S. Patent No. 6,251 ,840 discloses a lubricating/functional fluid composition which exhibits in use improved antiwear and anti foaming properties. The improvements result from uct of 2,5 diid/ur fiuorosilicone antifoam agents.
- U.S. Patent No. 6,103,673 discloses a composition comprising of an oil of lubricating viscosity; a shear stable viscosity modifier; at least 0.1 percent by weight of an overbased metal salt; at least 0.1 percent by weight of at least one phosphorus compound; and 0.1 to 0.25 percent by weight of a combination of at least two friction modifiers provides an improved fluid for continuously variable transmissions.
- At least one of the friction modifiers is selected from the group comprising: zinc salts of fatty acids having at least 10 carbon atoms, hydrocarbyl imidazolines containing at least 12 carbon atoms in the hydrocarbyl group, and borated epoxides.
- the total amount of the friction modifiers is limited to those amounts which provide a metal-to-metal coefficient of friction of at least about 0.120 as measured at 110°C by ASTM G-77.
- the first step hydrocracking, the majority of sulfur, nitrogen, and essentially all other non-hydrocarbon impurities are removed and most aromatics are saturated via hydrogen addition, Molecular reshaping of remaining saturated species occurs as rings are opened and paraffin isomers are redistributed, driven by thermodynamics with reaction rates facilitated by catalysts.
- Clean fuels are by-products of this and subsequent steps of the process.
- hydroisomerization n-paraffms and other molecules with waxy side chains are isomerized into branched molecules with much lower pour points, The majority of remaining aromatics are saturated and the majority of remaining sulfur and nitrogen species are removed.
- hydrofmishing any remaining non-isoparaffin impurities (sulfur species, nitrogen species, aromatics, and olefins) ⁇ i ⁇ /uiio ⁇ c J iu trace levels.
- Anti-oxidant(s) useful in this inventions including, but not limited to, are butyrated hydroxytoluene (BHT), phenl-a-naphthylamine (PANA), and further information on anti- oxidants are listed and explained in the following patents: 5,536,493, 5,863,872, 5,yyu,U55, 6,534,454 Bl, 6,774,091.
- BHT butyrated hydroxytoluene
- PANA phenl-a-naphthylamine
- Corrosion Inhibitor(s), Dispersant Inhibitor(s) including, but not limited to, those previously listed and also the following: surface-active organic acids, oxyacids, hydroxy acids, keto acids, borated amine, paraffin wax, imadazoline derivative, alkenyl succinic acid half ester, organic polycarboxylic acid, paraffin wax, nonyl phenoxy acetic acid, phenates, phenolic and amine anitoxidants, n-oleyl sarcosine, phosphorus, carboxylic acid derivatives, zincnapthenates, Ca sulphonate(s), Ba sulphonate(s), Ca dialkylbenzene sulphonate(s), Mg sulfonate(s), calcium dialkabezene sulphonate, sodium oxidate, calcium oxidate, barium oxidate, fatty acid amines, sulfurized fatty acids, amine nitrite salts, calcium nitrite,
- Metal Deactivator(s) including, but not limited to, tolutriazole, tolytriazole, triazole, benzotriazole, benzothiazole, benzoimidazole, and their derivatives. These metal deactivators and others are discussed further in this patent's references and the following patents: 5,990,055, 5,863,872, 5,736,493, 6,774,091.
- Viscosity modifier(s), Pour Point Depressants including, but not limited to, alone or in combination with, ethylene vinyl acetate copolymer, polyisobutylenes, polybutenes, polymethacrylates, olefin copolymers, esters of styrene maleic anyhdride copolymers, hydro genated styrerie-diene copolymers, styrene isoprene compounds, alkylated polystyrene, hydro genated radial polyisoprene, polyacrylate acid esters, fumed silicas, food grade tackifiers like natural rubber, etc.
- Anti-wear inhibitor(s), friction modifier(s), extreme pressure additive(s) are, but not limited to, alone or in combination with, as follows: synthetic ester, sulfurized synthetic esters, synthetic ester polymers, phosphorous sulfurs, fatty phosphites, phosphites, phosphate esters, borate ester, boron oxide, calcium sulfonates, sodium sulfonates, polysulfides, sulfurized fats, sulferized olefin, sulferized vegetable oils, antimony, zinc (ZDP), copper, polytetrafluoroethylene, molybdenum, and graphite compounds.
- synthetic ester synthetic ester, sulfurized synthetic esters, synthetic ester polymers, phosphorous sulfurs, fatty phosphites, phosphites, phosphate esters, borate ester, boron oxide, calcium sulfonates, sodium sulfonates, polysulfides, sulfurized fats, sulferized o
- antioxidants for example zinc dithiophosphate is a multi-function additive in that it functions as a corrosion inhibitor, anitwear agent, and antioxidants added to organic materials to retard oxidation.
- antioxidants for example zinc dithiophosphate is a multi-function additive in that it functions as a corrosion inhibitor, anitwear agent, and antioxidants added to organic materials to retard oxidation.
- E ⁇ i ⁇ Isifier(s) including, but not limited to, anionic and non-ionic con ils ⁇ be added to the invention to improve water emulsification or solubility of the formulas.
- the invention also contemplates the use of an effective amount of other additives in the lubricating and functional fluid compositions of this invention.
- additives include, for example, detergents and dispersants of the ash-producing or ashless type, corrosion and oxidation-inhibiting agents, pour point depressing agents, auxiliary extreme pressure and/or anitwear agents, color stabilizers and anti-foam agents.
- Lubrizol's LZ8955 and/or LZ9802 or combinations thereof with each other and/or other dispersion inhibitors may be used.
- the newest additive packages produced by Lubrizol include the Core API SL LZ 20001, Anti Oxidant booster LZ 8676, and Friction Modifier booster LZ 8650 for ILSAC GF3/GF4.
- compositions of the present invention comprising components (A) and (B) or (A), (B), and (C), or (A), (B), (C), and (D) are useful as high temperature biodegradable lubricants, food grade lubricants, and engine oils.
- the composition comprises components (A) and (B)
- composition comprises components (A), (B), (C) and (D), the following states the ranges of these components in parts by weight.
- concentrates of the invention can be formed.
- the concentrates comprise a minor amount of (A) with a major amount of (B), a minor amount of
- minor amount as used in the description and appended claims is intended to mean that when a composition contains a “minor amount” of a specific material that amount is less than 50 percent by weight of the composition.
- NP 343 is a polyol ester from ExxonMobil that has been identified as biobased by the
- Another aspect of the invention relates to a method of enhancing the lubrication of an engine by improving oxidation, stability, reducing emission volatility, and reducing friction that improves fuel economy.
- Reference patents that teach high temperature oxidation stability, reducing deposits and volatility, and friction reduction include the following: 5,990,055, 5,863,872, 5,736,493, 6,534,454 Bl, 6,774,091.
- These patents also teach the utilization of a synergy of two or more antioxidants and/or antiwear extreme pressure agents and the benefits of combining these components to reduce oxidation and greatly lower the coefficient of friction.
- This present invention discloses a method for the preparation of an improved high temperature engine lubricant composition comprising the steps of: 1) providing at least one biobased natural oil or biobased synthetic oil selected from the group consisting of natural or "y-ithctic vegetable oil, natural or synthetic animal oil, gene+ically rn ⁇ difcd vegetable oil, genetically modified synthetic vegetable oil, natural or synthetic tree oil, and mixtures thereof; 2) providing at least one boron nitride; and 3) optionally, providing at least one base oil selected from the group consisting of a synthetic ester, solvent refined petroleum oil, a hydrocracked petroleum white oil, an all hydroprocessed synthetic oil, Fischer Tropsch oil, petroleum oil group I, group II, group III, a polyalphaolefin (PAO), and mixtures thereof; 4) optionally, providing at least one base oil selected from the group consisting of a synthetic ester, solvent refined petroleum oil, a hydrocracked petroleum white oil, an all hydroprocessed synthetic oil, Fischer Tropsch oil, petroleum oil group I,
- the boron nitride particle additives sometimes disperse better when formulated into the base oil carrier and/or biobased oil prior to formulating.
- An example would be, but does not limit to, 1 part boron nitride dispersed in 3-10 parts NP343.
- Teflon 8.00 2.00 [0143] This concentrated additive is formulated where an 8 ounce bottle will treat 4-5 quarts of motor oil.
- Bio-Booster Pak can be added to gasoline engines to extend the oil life and increase the life of the engines by reducing wear and improving fuel economy.
- the package has a higher percentage of extreme pressure friction modifiers and antiwear (LZ8650 identified by Lubrizol as a friction modifier supplement for crank case engine oils) and antioxidant (LZ8676 identified by Lubrizol as an antioxidant supplement for crank case engine oils to meet the new API SL/SM and ILSAC GF3/GF4).
- LZ8650 identified by Lubrizol as a friction modifier supplement for crank case engine oils
- antioxidant LZ8676 identified by Lubrizol as an antioxidant supplement for crank case engine oils to meet the new API SL/SM and ILSAC GF3/GF4
- the engine additive package LZ20001, the pour point depressant LZ6662, and the viscosity modifier LZ7070D are added at the proper percentages to help balance and not dilute the additives already in the fully formulated engine oils.
- the Molyvan 855, NXl Boron Nitride, and Teflon have also been increased to match the percentages in the above formulas when fully formulated.
- Bio-Booster Pak has been formulated to the viscosity of 12 cSt. so when adding the additive at approximately 5% (8 ounces to 5 c ⁇ rrts) to P ⁇ 9 AR 20, SAE 7 O, SAF 40, or SAE 50 viscosity it will not take the formulation out of the SAE engine oil viscosity specification.
- the Bio-Booster Pak can be formulated in the same method as described above to meet heavy duty diesel motor (HDMO) specifications by replacing LZ20001 with LZ4998 diesel engine additive package with booster additives LZ8790, LZ8791, and LZ8791Z that are commercially available and identified from the Lubrizol Corporation.
- the Bio-Booster Pak can also be varied in viscosity, for example older vehicles will receive benefits by boosting the standard factory fill 10.5 cSt. oil to the high side of the SAE grade of 12 cSt. This can be done by increasing the polymer or adding a heavier viscosity biobased oil.
- the polymer can also be improved by adding a more shear stable polymer as in LZ7075F replacing LZ7070D. A proper procedure would be to formulate a booster pack for HDMO as well as one for PCMO. Modifications
- compositions, methods, or embodiments discussed are intended to be only illustrative of the invention disclosed by this specification. Variation on these compositions, methods, or embodiments are readily apparent to the person of skill in the art based upon the teachings of this specification and are therefore intended to be included as part of the inventions disclosed herein. [0146J
- the foregoing detailed description is given primarily tor clearness of understanding and no unnecessary limitations are to be understood therefrom, for modification will become obvious to those skilled in the art upon reading this disclosure and may be made upon departing from the spirit of the invention and scope of the appended claims. Accordingly, this invention is not intended to be limited by the specific exemplifications presented hereinabove. Rather, what is intended to be covered is within the spirit and scope of the appended claims.
Abstract
Description
Claims
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US67512605P | 2005-04-26 | 2005-04-26 | |
PCT/US2006/015820 WO2006116502A1 (en) | 2005-04-26 | 2006-04-26 | High temperature biobased lubricant compositions comprising boron nitride |
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EP1877528A1 true EP1877528A1 (en) | 2008-01-16 |
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EP06751491A Ceased EP1877528A1 (en) | 2005-04-26 | 2006-04-26 | High temperature biobased lubricant compositions comprising boron nitride |
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US (1) | US20100105583A1 (en) |
EP (1) | EP1877528A1 (en) |
CN (1) | CN101218331B (en) |
AU (1) | AU2006241193B2 (en) |
BR (1) | BRPI0610628A8 (en) |
CA (1) | CA2609652C (en) |
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-
2006
- 2006-04-26 BR BRPI0610628A patent/BRPI0610628A8/en not_active Application Discontinuation
- 2006-04-26 AU AU2006241193A patent/AU2006241193B2/en active Active
- 2006-04-26 CN CN2006800141198A patent/CN101218331B/en active Active
- 2006-04-26 US US11/412,164 patent/US20100105583A1/en not_active Abandoned
- 2006-04-26 CA CA2609652A patent/CA2609652C/en active Active
- 2006-04-26 WO PCT/US2006/015820 patent/WO2006116502A1/en active Application Filing
- 2006-04-26 EP EP06751491A patent/EP1877528A1/en not_active Ceased
-
2007
- 2007-10-25 ZA ZA200709214A patent/ZA200709214B/en unknown
Non-Patent Citations (2)
Title |
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A.F. HOLLEMANN, E. WIBERG: "Lehrbuch der Anorganischen Chemie", 1985, DE GRUYTER, Berlin, New York, ISBN: 3-11-007511-3, pages: 857 - 859 * |
See also references of WO2006116502A1 * |
Also Published As
Publication number | Publication date |
---|---|
ZA200709214B (en) | 2008-10-29 |
AU2006241193A1 (en) | 2006-11-02 |
CA2609652A1 (en) | 2006-11-02 |
US20100105583A1 (en) | 2010-04-29 |
CN101218331A (en) | 2008-07-09 |
WO2006116502A1 (en) | 2006-11-02 |
CA2609652C (en) | 2013-09-10 |
AU2006241193B2 (en) | 2011-04-28 |
CN101218331B (en) | 2013-04-24 |
BRPI0610628A2 (en) | 2010-07-13 |
BRPI0610628A8 (en) | 2016-03-08 |
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