KR20080014789A - High temperature biobased lubricant compositions comprising boron nitride - Google Patents

Abstract

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 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 oil, petroleum oil group I, group II, group III, a polyalphaolefin (PAO), and mixtures thereof; 4) optionally, providing at least one additive or combination of additives selected from the group consisting of anti-oxidant(s), corrosion inhibitor(s), metal deactivator(s), viscosity modifier(s), anti-wear inhibitor(s), friction modifier(s), and extreme pressure agent(s); 5) blending 1), 2), 3), and 4) in any sequence to form said composition.

Description

High temperature biobased lubricant compositions comprising boron nitride

The present invention claims priority to US Provisional Patent Application No. 60 / 675,126, filed April 26, 2005, entitled High Temperature Biobased Lubricant Composition Including Boron Nitride. The present invention relates to biological lubricant compositions made from natural and / or synthetic vegetable, animal, plant or tree oils and boron nitride. These compositions provide improved lubricity, anti-wear properties and extreme pressure performance at extremely high temperatures up to 1000 ° C. or higher. These compositions are particularly useful for high temperature applications for flammable engines, ovens, chains, cables, gears, hinge pins, bearings and sliding surfaces. The lubricant composition may include hydraulic fluids, turbine oils, compressor oils, penetration lubricants, greases, anti-seize compounds, thread compounds, deep drawing compounds, rolling oils, metal cutting oils ( metal working fluids), release agents, and lubricants that require anti-wear and extreme pressure performance. In addition, these lubricant compositions provide high dielectric strength useful in electrical insulation and compounds.

Biological oils can be obtained in large quantities from renewable resources derived from vegetables, animals, plants, or trees, and are generally characterized as easily biodegradable or "environmentally nontoxic". As a result, these oils are good for a wide range of applications and are biologically defined in 2002 Farm Bill. These biological oils are obtained in natural or synthetic form.

With regard to use for lubrication purposes, biological oils are not sufficiently satisfactory. Many biological oils do not have the desired characteristic spectrum with regard to pour point, oxidative stability and compatibility with other additives. However, biological oils possess many properties that are desirable for use as lubricants. In particular, biological oils have been found to provide very high viscosity indices that typically provide high flash points, good boundary lubrication and fuel economy and exhibit less than 1% volatility in the NOACK test to reduce engine oil emissions. In addition, biological oils are generally nontoxic and readily biodegradable. For example, under standard test conditions (such as the OCED 301D and ASTM D-5864 test methods), typical vegetable oils can be biodegradable with carbon dioxide and water for up to 80% for 28 days, while biodegradation is less than 25% for typical petroleum lubricants. do. The composition is very effective whenever the lubricant is lost directly to the environment. Sensitive areas include hoist cables and chains, drainage, straddle lift lumber in forestry, mining, marine, agriculture, heavy industry, transportation, rail and ship, pulp and paper, sawmills, plywood mills, and marine shipping areas. Driving on a carrier, automobile and ATV chain.

Biological materials and boron nitride in the composition are listed as approved for food use by USDA and NSF and are environmentally nontoxic. The devices used in the food processing industry vary in three main segments, including meat and poultry, beverages, snack foods, vegetables, and dairy. While the apparatus varies from field to field, moving parts such as bearings, gears and slide machines are similar and often require lubrication. Lubricants most commonly used in these applications include oven lubricants, chain lubricants, cable lubricants, penetration lubricants, anti-stick compounds, thread compounds, deep drawing compounds, rolling oils, mold release agents, gear oils as well as multipurpose greases. These food oils must meet more stringent standards than other industrial lubricants.

Due to the importance of ensuring and maintaining the safety and standards of quality for food products, the food industry must meet the rules and regulations by the USDA. USDA's Food Safety Investigation Service (FSIS) is responsible for all programs for the investigation, grading and standardization of meat, poultry, eggs, dairy products, fruits and vegetables. These programs are mandatory and require the investigation of non-food compounds used in federally investigated plants.

FSIS is the manager of the official list of compounds that are recognized for use in federally investigated plants. This official list (see page 11-1, List of Proprietary and Non-Food Compounds by the U.S. Department of Agriculture's Food Safety Investigation Service (FSIS), publication number 1419 (1989)) includes lubricants and other items that may come into contact with food. The substance is described as being an indirect food additive under the USDA rule. Therefore, these lubricants classified as H-1 or H-2 must be approved by the USDA before being used in food processing plants. The most stringent classification, H-1, is the lubricant allowed for accidental food contact. The H-2 classification is intended for use without food contact and guarantees that no known poison or carcinogen has been used in the lubricant. The present invention relates to H-1 and H-2 certified lubricating oils. H-1 and H-2 applied oils and the term "food grade" will be used interchangeably for the purposes of this application.

USDA no longer applies new ingredients and compositions, but the H-1 and H-2 classifications are still recognized by the global food industry. NSF is recognized as a list of food grade classifications.

In addition to meeting the requirements for safety standards by the Federal Regulatory Authority, the product must be an effective lubricant. Lubricant oils for food processing plants must lubricate mechanical parts, withstand viscosity changes, withstand oxidation, protect against rust and corrosion, provide abrasion protection and prevent the formation of sediments and sludge during use. The product must be effectively implemented at various lubrication standards, ranging from hydrodynamic thick film standards to boundary thin film standards.

The oxidation and thermal characteristics of the lubricating oil make it possible to anticipate how effectively the oil maintains its lubricating properties over time and prevents sludge and deposit formation. Hydrocarbon oils can be partially oxidized upon contact with oxygen for extended periods at elevated temperatures to form hard carbon deposits, which leads to sticking in the proximity resistance of the metal to the metal contact region.

While these lubricants are designed to be non-toxic as food material contaminants, their lubricating properties are less effective compared to conventional lubricants, such as lubricants that do not have ingredients allowed for direct food contact. The lubrication industry has solved this problem to some extent by incorporating certain additives into lubricant compositions. For example, incorporation of performance additives has been used to improve anti-wear properties, oxidation inhibition, rust / corrosion inhibition, metal passivation, extreme pressure, frictional deformation, bubble inhibition, and lubricity. Such chemicals are described in the following patents: US Pat. No. 5,538,6545 (Lawait et al.), US Pat. No. 4,062,785 (Nibert); U.S. 4,828,727 (Macanine); U.S. Patent 5,338,471 and U.S. Patent 5,413,7254 (Lye).

Drawbacks associated with food grade lubricants described in the art relate to oxidation resistance, limited formulation ability to viscosity range, and limited viscosity protection. These lubricants have poor oxidation and flow characteristics when subjected to thermal and mechanical stress.

Accordingly, there is a need for lubricants that exhibit substantial improvements in dielectric strength, oxidation resistance, viscosity index, viscosity width formulation, and viscosity stability when subjected to thermal and mechanical stress with excellent extreme pressure and anti-wear properties. In addition, the composition can provide a dry lubricating film without the formation of hard carbon deposits if the temperature exceeds the autoignition temperature of the biological oil.

U.S. Patent 4,783,274 (Zokkinen et al., November 8, 1988) relates to anhydrous oily lubricants, based on substituted vegetable oils instead of lubricated mineral oils and as saturated and / or unsaturated straight chain C Triglycerides which are esters of ₁₀ to C ₂₂ fatty acids and glycerol. This lubricant is characterized by containing at least 70% by weight of triglycerides, having an iodine number of 50 to 125 and a viscosity index of 190 or more. Instead of or in combination with the triglycerides, the lubricant oil contains polymers prepared by high temperature polymerization of the triglycerides or are made of the corresponding triglycerides. As additives, the lubricant oil may contain customary additives for solvents, fatty acid derivatives, in particular their metal salts, organic or inorganic, natural or synthetic polymers and lubricants.

U.S. Patent 5,538,654 (Lawait et al., July 23, 1996) discloses food grade lubricant compositions useful as working fluids, gear oils and compressor oils for equipment in the food service industry. The composition comprises (A) a large amount of genetically modified vegetable oil and (B) a small amount of performance additive. In another embodiment, the composition contains a compound of (C) phosphorus or (D) vegetable oil that is not genetically modified.

U.S. Pat.No. 5,580,482 (Casan et al., Dec. 3, 1996) discloses an effective amount of N, N-disubstituted aminomethyl-1,2,4- and oils that are triglyceride oils or esters of unsaturated unsaturated alcohol residues or acid residues. A lubricant composition stabilized from the harmful effects of heat and oxygen, comprising triazoles or N, N-disubstituted aminomethylbenzotriazoles and higher alkyl substituted amides of dodecylene succinic acid.

U.S. Patent 5,888,947 (Lambert et al., March 30, 1999) relates to a composition comprising three main components: a base oil, an oil source containing hydroxy fatty acids and an oil source containing vegetable or animal waxes. . Base oils used for reference should consist of primary triglycerols (triglycerides) and mono- and diglycerols (glycerides) and free fatty acids. The composition also includes vegetable oils, wherein the glycerol contains hydroxy fatty acids and constitutes 5% to 20% of the oil. The third component is a wax that constitutes 5% to 10% by volume of the oil additive. Additional synthetic analogues or natural products derived from animal or vegetable compounds may be added up to 5% of the composition volume.

U.S. Patent 6,300,292 (Cornish et al., Oct. 9, 2001) contains vegetable oils having a total unsaturation of 0.3 or less as a base oil and is selected from the group consisting of phenolic antioxidants, amine antioxidants and zinc dithiophosphate antioxidants. A working oil composition comprising at least one antioxidant in an amount of 0.01 to 5% by weight, based on the total amount of the composition.

U. S. Patent No. 6,312, 623 (Ommen et al., Nov. 6, 2001) discloses fatty acid components of at least 75% olefins, less than 10% of diunsaturated fatty acid components; Less than 3% triunsaturated fatty acid component; And less than 8% saturated fatty acid component, the composition comprising a dielectric strength of at least 35 KV / 100 mil gap, a dissipation factor of less than 0.05% at 25 ° C., 0.03 mg KOH / g Having an acidity of less than 1 pS / m at 25 ° C., a flash point of at least 250 ° C. and a pour point of at least −15 ° C., selected from the group consisting of antioxidant additives, pour point depressant additives and copper deactivators At least one additive.

Summary of the Invention

One aspect of the present invention includes various additives and base oils useful for improving the properties of high temperature, environmental and food grade lubricants. Applicants note that when boron nitride is formulated in the compositions of the present invention, the compositions exhibit improved lubricity, anti-wear wear, extreme pressure, and oxidation resistance at extreme temperatures up to or above 1000 ° C. The present invention also provides high dielectric strength useful for insulating solutions and compounds. These compositions can be particularly useful for high temperature applications for flammable engines, ovens, chains, cables, gears, hinge pins, bearings and sliding surfaces. The lubricant composition may be formulated with hydraulic fluid, turbine oil, compressor oil, penetrant, grease, anti-stick compound, thread compound, deep drawing compound, rolling oil, metal cutting oil, mold release agent, and lubricant requiring anti-wear and extreme pressure performance. Can be. Due to the chemical structure of the lubricant base oil with boron nitride, these inventive compositions are burned without relatively abrasive hard carbon deposits, leaving the boron nitride white powder on the surface to be lubricated. The present invention also prevents the continuous formation of hard carbon deposits that cause sticking in the contact zones of the close tolerant area, a known problem with petroleum hydrocarbons.

In addition, the compositions of the present invention exhibit extreme lubricity, anti-wear and extreme pressure performance at temperatures above 500 ° C. where graphite and molybdenum are known to fail.

It has also been found that the compositions of the present invention have an environmental advantage in engine oils by improving fuel economy and reducing emissions.

In addition, the compositions of the present invention can be formulated to food grade and have improved biodegradation, making them environmentally nontoxic.

Another aspect of the invention is selected from the group consisting of a) natural or synthetic vegetable oils, natural or synthetic animal oils, genetically modified vegetable oils, genetically modified synthetic vegetable oils, natural or synthetic wood oils, and mixtures thereof. Biological natural oils and biological synthetic oils above; b) at least one boron nitride and c) optionally other base oils and d) optionally other additives, wherein the components are environmentally non-certified with the H-1 and H-2 approvals required by the US Department of Agriculture. It is toxic and relates to food grade high temperature lubricant compositions. The H-1 and H-2 labels will in most cases ultimately relate to comparable classifications outside of the United States.

In another aspect, the present invention provides a composition comprising: 1) selected from the group consisting of 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. Providing the above biological natural oil or biological synthetic oil; 2) providing at least one boron nitride; And 3) optionally synthetic synthetic esters, solvent refined petroleum oils, hydrocracked petroleum white oils, all hydroprocessed synthetic oils, Fischer Tropsch base oils, petroleum oils group I, group II, group III Providing at least one base oil selected from the group consisting of: polyalphaolefins (PAO), and mixtures thereof; and 4) optionally, antioxidants, corrosion inhibitors, metal deactivators, viscosity modifiers, anti-wear inhibitors, friction Providing at least one additive selected from the group consisting of regulators, extreme pressure agents and emulsifiers; 5) A method for producing an environmentally non-toxic, food grade high temperature lubricant composition comprising the steps of combining 1), 2), 3) and 4) to form the composition.

Another aspect of the invention requires biodegradable liquids, engine oils that reduce fuel emissions and improve fuel economy, and are methods for improving the lubrication of devices used in the field of food use, comprising: 1) a) natural or synthetic At least one biological natural oil and biological synthetic oil selected from the group consisting of vegetable oils, natural or synthetic animal oils, genetically modified vegetable oils, genetically modified synthetic vegetable oils, natural or synthetic tree oils and mixtures thereof; b) providing at least one environmentally non-toxic and food grade hot lubricant composition comprising at least one boron nitride and c) optionally other base oils and d) optionally other additives, and 2) an effective amount of said composition. A method of improving the lubrication of an apparatus for use in the field of food use, which requires biodegradable liquids, engine oil, which reduces the environmental emissions and improves fuel economy, comprising the step of adding to the apparatus.

According to another aspect of the invention, the lubricant is selected from the group consisting of 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 At least one biological natural oil and at least one biological synthetic oil and at least one boron nitride.

According to another aspect of the present invention, lubricants are synthetic esters, solvent refined petroleum oils, hydrocracked petroleum white oils, fully hydroprocessed synthetic oils, Fischer Tropsch base oils, Group I petroleum oils. And at least one base oil selected from the group consisting of oils, Group II petroleum oils, Group III petroleum oils, polyalphaolefins (PAO), and mixtures thereof.

According to another aspect of the present invention, the lubricant comprises one or more additives or combinations of additives selected from the group consisting of antioxidants, corrosion inhibitors, metal deactivators, viscosity modifiers, anti-wear inhibitors, friction modifiers, extreme pressure agents and emulsifiers. Also includes.

According to another aspect of the invention, the oil is a triglyceride having the formula:

In the formula,

R ¹ , R ² and R ³ are aliphatic hydrocarbyl groups containing from about 7 to about 23 carbon atoms.

According to another aspect of the invention, aliphatic hydrocarbyl groups are selected from the group comprising aliphatic hydrocarbon groups, substituted aliphatic hydrocarbon groups and hetero groups.

According to another aspect of the invention, triglycerides have an oleic acid profile of at least about 60%. In another embodiment, the oleic acid profile is 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%.

According to another aspect of the present invention, triglycerides have at least about 60% monounsaturation characteristics. In another embodiment, the monosaturated feature is 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%.

According to another aspect of the present invention, triglycerides have at least about 70% mono-saturation characteristics. In another embodiment, the monosaturation feature is 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%.

According to another aspect of the present invention, triglycerides have at least about 80% mono-saturation characteristics. In another embodiment, the monosaturated feature is 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99 and 100 May be%.

According to another aspect of the invention, the oil is from about 5% to about 99.9% by weight of the lubricant and boron nitride is from about 0.002% to about 50% by weight of the lubricant. In another embodiment, the oil is 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 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 and 99% have.

According to another aspect of the invention, the oil is from about 65% to about 99.9% by weight of the lubricant and the boron nitride is from about 0.002% to about 35% by weight of the lubricant. In another embodiment, the boron nitride is 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 , 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34 and 35%.

According to another aspect of the invention, the oil is from about 95% to about 99.998% by weight of the lubricant and the boron nitride is from about 0.002% to about 5% by weight of the lubricant.

According to another aspect of the invention, the biological oil is from about 5% to about 90% by weight of the lubricant, boron nitride is from about 0.002% to about 80% by weight of the lubricant, and the base oil is from about 20% by weight to about 80% by weight and the additive is from about 0.001% to about 80% by weight of the lubricant.

According to another aspect of the invention, the biological oil is from about 40% to about 80% by weight of the lubricant, boron nitride is from about 0.002% to about 35% by weight of the lubricant, and the base oil is from about 10% by weight to about 20 wt% and the additive is about 0.001 wt% to about 40 wt% of the lubricant.

According to another aspect of the invention, the biological oil is from about 60% to about 90% by weight of the lubricant, boron nitride is from about 0.002% to about 5% by weight of the lubricant, and the base oil is from about 1% by weight to about 10 weight percent and the additive is from about 0.001 weight percent to about 20 weight percent of the lubricant.

According to another aspect of the invention, the base oil is about 50% by weight or less of the lubricant and boron nitride is about 50% or more by weight of the lubricant.

According to another aspect of the present invention, the biological oil is about 50% by weight or less of the lubricant and the base oil, boron nitride and additives are combined to about 50% by weight or more of the lubricant.

According to another aspect of the invention, the biological oil, boron nitride and additives are combined up to about 50% by weight of the lubricant and the base oil is at least about 50% by weight of the lubricant.

According to another aspect of the present invention, a method for improving the lubrication of a device may comprise one or more boron nitrides of natural or synthetic vegetable oils, natural or synthetic animal oils, genetically modified vegetable oils, genetically modified synthetic vegetable oils, natural or synthetic Combining with at least one biological oil selected from the group consisting of wood oil and mixtures thereof and adding an effective amount of said oil and boron nitride to the device.

According to another aspect of the present invention, the process also prior to addition to the apparatus, synthetic esters, solvent refined petroleum oil, hydrocracked petroleum white oil, all hydroprocessed synthetic oils, Fischer Tropsch ) Combining at least one base oil selected from the group consisting of base oil, Group I petroleum oil, Group II petroleum oil, Group III petroleum oil, polyalphaolefin (PAO), and mixtures thereof with biological oil and boron nitride do.

According to another aspect of the invention, the method is selected from the group consisting of antioxidants, corrosion inhibitors, metal deactivators, viscosity modifiers, anti-wear inhibitors, friction modifiers, extreme pressure agents and emulsifiers prior to addition to the apparatus. Comprising the above additive or a composition of the additive with the biological oil, base oil and boron nitride.

Detailed description of the invention

(A) triglyceride oil

In practicing the present invention, the base oil is a synthetic triglyceride or natural oil of the formula:

In the formula,

R ¹ , R ² and R ³ are aliphatic hydrocarbyl groups containing from about 7 to about 23 carbon atoms. The term "hydrocarbyl group" as used herein means a radical having carbon atoms attached directly to the rest of the molecule. Aliphatic hydrocarbyl groups include: (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, henicosenyl; Alkenyl groups containing two or three double bonds, such as 8,11-heptadecadienyl and 8,11,14-heptacatrienyl. All of these isomers are also included, but straight chain groups are used in this embodiment. (2) substituted aliphatic hydrocarbon groups; Ie groups containing non-hydrocarbon substituents which do not alter hydrocarbon characteristics in connection with the present invention. Those skilled in the art will be familiar with suitable substituents: examples are hydroxy, carbalkoxy, (especially lower carbalkoxy) and alkoxy (especially lower alkoxy), and the term "lower" means groups containing up to seven carbon atoms. it means. (3) hetero groups; That is, groups with predominantly aliphatic hydrocarbon characteristics in connection with the present invention contain atoms other than carbon present in the chain or ring composed of aliphatic carbon atoms. Suitable heteroatoms will be apparent to those skilled in the art and include, for example, oxygen, nitrogen and sulfur.

Triglyceride oils suitable for use in the present invention are vegetable oils and animal oils and modified vegetable oils and animal oils. Biological oils Triglycerides are naturally occurring oils. "Natural yield" means that the oiled seeds are not subjected to any genetic modification. The term "natural yield" also means that the oil obtained is not subjected to esterification hydrogenation or any chemical treatment that alters the di- and tri-unsaturated characteristics. Naturally produced biological oils having utility in the present invention are at least one soybean oil, rapeseed oil, sunflower oil, coconut oil, resquelar oil, canola oil, peanut oil, corn oil, cottonseed oil, palm oil, safflower seed oil, meadowfoam oil, animal oil Or castor oil.

Triglyceride oils can be modified vegetable oils and animal oils. Triglyceride oils can be modified chemically or genetically. Hydrogenation of naturally occurring triglycerides is the primary means of chemical modification. Naturally produced triglyceride oils have a variety of fatty acid profiles. The fatty acid profile for naturally produced sunflower oil is as follows:

Palmitic acid 70%

Stearic acid 4.5%

Oleic acid 18.7%

Linoleic acid 67.5%

Linolenic acid 0.8%

Other acid 1.5%

Chemically denaturing sunflower oil by hydrogenation means reacting hydrogen with an unsaturated fatty acid profile such as oleic acid, linoleic acid and linolenic acid. In addition, the purpose is not to hydrogenate such that the oleic acid profile is reduced to the stearic acid profile. The purpose of chemical denaturation through hydrogenation is to participate in the linoleic acid profile to reduce or convert its actual portion to the oleic acid profile. The linoleic acid profile of naturally produced sunflower oil is 67.5%. The purpose of chemical denaturation is to hydrogenate linoleic acid to about 25% reduction. This means that the oleic acid profile increased from 18.7% to about 61% (18.7% original oleic acid profile + 42.5% oleic acid produced from linoleic acid).

Hydrogenation is the reaction of biological oil with hydrogen gas in the presence of a catalyst. The most commonly used catalyst is a nickel catalyst. This treatment is to add hydrogen to the oil to reduce the linoleic acid profile and the linolenic acid profile. Only unsaturated fatty acid profiles participate in the hydrogenation reaction. During hydrogenation, other reactions may also occur, such as the reaction of moving the double bond to a new position and the twisting of the cis form to another high melting point trans form.

Table I shows the oleic acid (18: 1), linoleic acid (18: 2) and linolenic acid (18: 3) profiles of selected natural output vegetable oils. Hydrogenation allows chemical modification of the actual portion of the linoleic acid profile of triglycerides to increase the oleic acid profile to over 60%.

Table I

Genetic modifications can occur in seed stocks through laboratory or natural hybridization controlled under more direct genetic modifications. Collected crops contain triglyceride oils having a higher oleic acid profile and a much lower linoleic acid profile when extracted. Referring to Table I above, the naturally occurring sunflower oil has an oleic acid profile of 18.7%. Genetically modified sunflower oil has an oleic acid profile of 81.3% and a linoleic acid profile of 9.0%. Various vegetable oils from Table I can be genetically modified to obtain at least 90% oleic acid profile. Chemically modified vegetable oils include one or more 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 Canola oil, chemically modified rapeseed oil, chemically modified safflower seed oil, chemically modified soybean oil, chemically modified animal oil, and chemically modified sunflower oil.

In one embodiment, aliphatic hydrocarbyl groups of R ¹ , R ^2, and R ³ are those having triglycerides of at least 60%, in other embodiments at least 70%, in other embodiments at least 80% monounsaturated characteristics. Triglycerides having utility in the present invention can illustrate genetically modified vegetable oils containing higher than normal oleic acid content. Normal sunflower oil has an oleic acid content of 25-30%. By genetic modification of sunflower seeds, sunflower oil can be obtained with an oleic acid content of about 60% to about 90%. That is, R ¹ , R ² and R ³ The group is a heptadecenyl group and the R ¹ COO-, R ² COO- and R ³ COO- to 1,2,3-propanetriyl groups CH ₂ CHCH are residues of the oleic acid molecule. US Pat. No. 4,627,192 and US Pat. No. 4,746,402, incorporated herein by reference, disclose the preparation of high ole sunflower oil.

For example, triglycerides consisting solely of oleic acid residues have an oleic acid content of 100% and thus a monounsaturated content of 100%. When triglycerides are prepared with acid residues that are 70% oleic acid, 10% stearic acid, 13% palmitic acid and 7% linoleic acid, the monounsaturated content is 70%. In one embodiment, the triglyceride oil is high oleic acid, ie, genetically modified vegetable oil (above 605) triglyceride oil. Typical high oleic vegetable oils used in the present invention are high oleic safflower seed oil, high oleic canola oil, high oleic peanut oil, high oleic corn oil, high oleic rape oil, high oleic sunflower oil, high oleic cottonseed oil, high oleic resquelar Oil, high oleic palm oil, high oleic castor oil, high oleic acid meadowfoam and high oleic soybean oil. Canola oil is a variety of rapeseed oils containing less than 1% erucic acid. High oleic vegetable oil is a high oleic sunflower oil available from Helenus S. This product is available as TriSun ^TM high oleic sunflower oil from AC Humko, Cordova, TN, 38018. TriSun 80 is a high oleic acid triglyceride whose acid residue comprises 80% oleic acid. Other high oleic vegetable oils are Brassica Campestris. high oleic acid canola oil available from campestris ) or Brassica napus , and is available as RS high oleic acid oil from AC Humko. RS80 oil defines canola oil, wherein the acid residue comprises 80% oleic acid.

It has been found that genetically modified vegetable oils have a high oleic acid content at the expense of di- and tri-unsaturated acids. Normal sunflower oil has 20-40% oleic acid residues and 50-70% linoleic acid residues. This represents 90% content of mono- and di-unsaturated acid residues (20 + 70) or (40 + 50). Genetically modified vegetable oils produce low di- or triunsaturated residue vegetable rates. Genetically modified oils of the invention have an oleic acid residue: linoleic acid residue ratio of about 2 to about 90. The 60% oleic acid residue content and the 30% linoleic acid residue content of triglyceride oil represent ratio 2. Triglyceride oils consisting of 80% oleic acid residues and 10% linoleic acid residues exhibit ratio 8. Triglyceride oils consisting of 90% oleic acid residues and 1% linoleic acid residues exhibit a ratio of 90. The ratio for normal sunflower oil is 0.5 (30% oleic acid residues and 60% linoleic acid residues).

Triglycerides are processed to biologically synthetic esters and to the natural, chemically modified and genetically modified as described above, vegetable oils, wood oils, vegetable oils, and animal oils can be made into synthetic esters via the ester method described in the patent. Synthetic esters include polyesters, diesters, complex esters and simple esters including ethyl and ethyl esters. Additional patents describing esterifications are described in US Pat. No. 6,051,539; 6,018,063; 5,885,946; 5,427,704; 5,338,471; 6,018,063; 5,994,278; 5,773,391; 6,583,302B1; 6,774,091 and US 2003/0069146.

(B) boron nitride

Advanced Ceramics Corporation is the world's largest manufacturer of boron nitride powders, shapes and coatings as well as other specialty ceramics.

Boron nitride powder is a soft, white lubricious (slidable) powder that makes it an attractive performance enhancer instead of commonly used in graphite, molybdenum disulfide and other inorganic solid lubricants. In addition to good adhesion and thermochemical stability, boron nitride offers opportunities for applications where conventional solid lubricants fail or cannot deliver the desired performance.

These inorganic solid powders are suitable for extreme pressure (EP) applications because they possess lubricity at extreme cooling or high temperatures. It is environmentally friendly and inert to most chemicals. It exhibits excellent electrical insulation properties and, unlike graphite, retains these properties in vacuum.

Current lubrication applications include solid polymer composite shapes, petroleum solvents, additives dispersed in oils and greases, metal-ceramic electrode-position coatings, aqueous and oil dispersions used as release agents, and epoxy coatings, thermal spray coatings and plasma spray coatings. Contains ingredients.

Boron nitride is a material having high fire resistance (heat resistance, stability) with physical and chemical properties comparable to graphite. But unlike graphite, it does not occur naturally. It is typically synthesized from boron oxide or boric acid at temperatures ranging from 800 ° C. to 2000 ° C. in the presence of urea or urea derivatives and ammonia.

Two common crystal structures of BN are cubic and hexagonal. Cubic boron nitride, (c) BN is as hard as diamond and wearable; Hexagonal boron nitride, (h) BN, is soft and lubricity like graphite.

The following discusses the main material properties of (h) BN, which makes it an ideal solid lubricant for high temperature applications.

Hexagonal boron nitride powders exhibit the same characteristics as the solid lubricants found in graphite and molybdenum disulfide. These include the crystal structure, low shear strength, adhesion, low wear, and thermochemical stability of solid lubricating films. In many cases, (h) BN exceeds the performance levels of these conventional solid lubricant characteristics, in particular adhesion and thermochemical stability.

Until recently, how to measure the coefficient of friction or "slip" characteristics of powders is not well known. For example, the INSTRON method commonly used to measure the coefficient of friction is a discernible difference by touch, but cannot distinguish between the various grades of (h) BN powder. (h) In order to compare the slip of BN with other solid lubricants, a new test apparatus was developed in combination with Pallex Corporation.

The test results as shown in FIG. 1 clearly show that (h) BN obtains the lowest coefficient of friction for all other materials measured by the method.

In order to compare the extreme pressure (EP) characteristics of (h) BN for graphite, molybdenum disulfide and other lubricants, a Palex 4-ball EP test was run on Fomblin® oil samples containing 5% by weight of each material.

Two grades of (h) BN, two grades of graphite, molybdenum disulfide (MoS ₂ ), antimony oxide (SbO ₂ ) and teflon (PTFE) were tested. Table 2 shows the results of these tests. (h) BN samples showed higher welding points than others. (The welding point is the weight-kilogram [kgf] of applied force that the lubricant breaks down to allow welding or metal-to-metal transfer). The scar data (s pattern of metal removal before reaching the welding point) shows that at base loading, grade 1 (h) BN has a slightly higher value than other solid lubricants; However, at 400 kgf, both grades of (h) BN are compared group friendly. (Basic loading is defined in this figure as the weld point of pure test fluid at 315 kgf).

Advanced Ceramics produces several grades of boron nitride for lubricants. The new boron nitride powder NX grades are listed as lubricants and include NX1, NX5, NX9 and NX10. In one embodiment, the grade for filtration and solubility has a particle size of 1 micron or less as NX1.

TABLE 2

1

(C) other oil

Compositions (A) and (B) of the present invention comprise (C) (1) synthetic ester base oils, (C) (2) polyalphaolefins or (C) (3) unrefined, refined or refined oils, (C) (4) mixtures of two or more of (C) (1), (C) (2), (C) (3) and (C) (4), as well as all synthetic hydrogenated oils and Fischer Troche base oils It may further comprise other additives and oils, including. Synthetic ester base oil (C) (1) is a monocarboxylic acid of the formula R ⁸ COOH,

의 디카르복시산 또는 Chemical formula

Dicarboxylic acid or

의 아릴 카르복시산과 화학식 Chemical formula

Formula of Aryl Carboxylic Acid

의 알코올과의 반응을 포함하며, 식중에서 R⁸은 약 4 내지 약 24개 탄소원자를 함유하는 히드로카르빌 기이고, R⁹는 수소 또는 약 4 내지 약 50개 탄소원자를 함유하는 히드로카르빌 기이며, R¹⁰은 수소 또는 약 1 내지 약 24개 탄소원자를 함유하는 히드로카르빌 기이고, m은 0 내지 약 6의 정수이며, p는 1 내지 4의 정수이고; R¹¹은 1 내지 약 24개 탄소원자를 함유하는 지방족 기 또는 6 내지 약 18개 탄소원자를 함유하는 방향족 기이고, R¹²는 수소 또는 1 또는 2개 탄소원자를 함유하는 알킬기이며, t는 0 내지 약 40이고 또 n은 1 내지 약 6이다.

Among the comprises the reaction of the alcohol, formula R ⁸ is a hydrocarbyl group containing from about 4 to about 24 carbon atoms, R ⁹ is a hydrocarbyl group containing from hydrogen or from about 4 to about 50 carbon atoms R ¹⁰ is hydrogen or a hydrocarbyl group containing from about 1 to about 24 carbon atoms, m is an integer from 0 to about 6, p is an integer from 1 to 4; R ¹¹ is an aliphatic group containing 1 to about 24 carbon atoms or an aromatic group containing 6 to about 18 carbon atoms, R ¹² is hydrogen or an alkyl group containing 1 or 2 carbon atoms, t is 0 to about 40 And n is from 1 to about 6.

In monocarboxylic acids, in one embodiment, R ⁸ contains about 6 to about 18 carbon atoms. Exemplary but non-limiting monocarboxylic acids are butanoic acid, hexanoic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, carboxylic acids of dodecanoic acid, palmitic acid, stearic acid and oleic acid, as well as isomers of these acids and mixtures thereof. .

In monocarboxylic acids, in one embodiment, R ⁹ contains about 4 to about 24 carbon atoms and m is an integer from 1 to about 3. A list of exemplary and non-limiting dicarboxylic acids is succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, maleic acid and fumaric acid.

In one embodiment, as aryl carboxylic acid, R ¹⁰ contains about 6 to about 18 carbon atoms and p is 2. Useful aryl carboxylic acids are benzoic acid, toluic acid, ethylbenzoic acid, phthalic acid, isophthalic acid, terephthalic acid, hemitic acid, trimellitic acid, trimeric acid and pyromellitic acid.

In one embodiment, in the alcohol, R ¹¹ contains about 3 to about 18 carbon atoms and t is 0 to about 20. The alcohol may be a monohydric alcohol, a polyhydric alcohol or an alkoxylated mono and polyhydric alcohol. Monohydric alcohols may include, for example, primary and secondary alcohols. In one embodiment, however, monohydric alcohols are primary aliphatic alcohols, in particular aliphatic hydrocarbon alcohols such as alkenol and alkanols. Examples of monohydric alcohols from which R ¹¹ is derived are 1-octanol, 1-decanol, 1-dodecanol, 1-tetradecanol, 1-hexadecanol, 1-octadecane, oleyl alcohol, linoleyl alcohol Linoleyl alcohol, phytol, myristyl alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol and behenyl alcohol.

Examples of polyhydric alcohols are alcohols containing from 2 to about 6 hydroxy groups. These are exemplified by alkylene glycols such as ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, dibutylene glycol, tributylene glycol and other alkylene glycols, for example. One example of an alcohol suitable for use in the present invention is a polyhydric alcohol containing up to about 12 carbon atoms. Alcohols of this type are 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-tetrakis (hydroxymethyl) cyclohexanol, 1,10-decanediol, digitalal and the like.

Polyhydric alcohols for use in the present invention are polyhydric alcohols containing 3 to 10 carbon atoms, in particular polyhydric alcohols having 3 to 6 carbon atoms and at least 3 hydroxyl groups. Such alcohols include glycerol, erythritol, pentaerythritol, mannitol, sorbitol, 2-hydroxymethyl-2-methyl-1,3-propanediol (trimethylolpropane), bis-trimethylolpropane, 1,2,4- Hexane triol and the like.

The alkoxylated alcohol may be an alkoxylated monohydric alcohol or an alkoxylated polyhydric alcohol. Alkoxy alcohols are generally produced by reacting an alcohol with an excess of alkylene oxide, such as ethylene oxide or propylene oxide. For example, about 6 to about 40 moles of ethylene oxide or propylene oxide may be condensed with aliphatic alcohols.

In one embodiment, the fatty alcohol contains about 14 to about 24 carbon atoms and may be derived from long chain fatty alcohols such as stearyl alcohol or oleyl alcohol.

Alkoxy alcohols useful for the reaction with carboxylic acids to prepare synthetic esters can be purchased under trade names such as TRITON ^® , TERGITOL ^® (from Union Carbide), ALFONIC ^® (from Vista Chemical) and NEODOL ^® (from Shell Chemical Company). TRITON ^® materials are identified as polyethoxylated alkyl phenols, which can be derived from straight or branched chain alkyl phenols. TERGITOLS ^® are identified as polyethylene glycol ethers of primary or secondary alcohols; ALFONIC ^® materials are identified as ethoxylated straight alcohols and can be represented by the following formula:

Wherein x is 4 to 16; And n is a number from about 3 to 11. ^® ALFONIC ethoxylates characterized by the above formula is ALFONIC ^® 1012-60 (wherein, x is 8 to 10 and being again n is about 5.7 average); ALFONIC ^® 1214-70, where x is about 10-12 and n is about 10.6 on average; ALFONIC ^® 1412-60, where x is 10-12 and n is about 7 on average; And ALFONIC 1218-70 ^® (wherein, x is from about 10 to 16 also being the average n is about 10.7) a.

NEODOL ^® ethoxylates are ethoxylated alcohols in which the alcohol is a mixture of straight and branched chain alcohols containing from 9 to about 15 carbon atoms. Ethoxylates are obtained by reacting alcohols with excess ethylene oxide, such as about 3 to about 12 or more ethylene oxides per mole of alcohol. For example, NEODOL ^® ethoxylates 23-6.5 are mixed straight and branched chain alcoholates of 12 to 13 carbon atoms with an average of about 6.5 ethoxy units.

As mentioned above, synthetic ester base oils comprise reacting the above-described acids or mixtures thereof with the above-described alcohols or mixtures thereof at a rate of at least 1 COOH per 1 OH group, using esterification processes, conditions and catalysts known in the art. do.

As an example, not all OH groups react with COOH groups. Examples of these synthetic ester base oils are glycerol mono-oleate and glycerol di-oleate as the reaction is shown below:

When glycerol mono-oleate and glycerol di-oleate are used as (C) (1), it is common that a mixture of isomers of glycerol mono-oleate and a mixture of isomers of glycerol di-oleate are present.

Additional information on biologically synthetic esters and esterification processes was recently published to the US Soybean Commission under the name "Recent Developments in Soybean Oil-Based Biolubricants" by Dr. Herman Benneck, researcher at the Battle Memorial Institute in Columbus, Ohio. Included in the published paper. Dr. Benek reported the process carried out by Renewable Lubricants, Inc. to evaluate and determine the use contract signed by Batel using the biologically synthetic ester invented by Batel.

A non-limiting list of companies that produce synthetic esters and their trade names are BASF (as Glissofluid), Ciba-Geigi (as Reolube), JCI (as Emkarote), Olefina (as Radialube) and Emery Group of Henkel Corporation (as Emery). )to be.

Polyalphaolefins (C) (2) such as alkylene oxide polymers and interpolymers and derivatives thereof in which terminal hydroxy groups have been modified by esterification, etherification and the like constitute other types of oils that can be used. Examples thereof include oils prepared through the polymerization of ethylene oxide or propylene oxide, alkyl and aryl ethers of polyoxyalkylene polymers (e.g., methylpolyisopropylene glycol ethers having an average molecular weight of about 1000, polyethylene glycols having a molecular weight of about 500-1000 Diphenyl ether, diethyl ether of polypropylene glycol of molecular weight about 1000-1500) or mono- and polycarboxylic acid esters thereof such as acetic acid ester, mixed C ₃ -C ₈ fatty acid ester or C ₁₃ oxo acid of tetraethylene glycol Diester is mentioned.

Unrefined, refined and refined oils, (C) (3) as well as mixtures of two or more thereof may be used in the lubricant composition of the present invention. Unrefined oils are obtained directly from natural or synthetic sources without further purification. For example, shale oil obtained directly from the retort operation, petroleum oil obtained directly from distillation or ester oil obtained directly from the esterification process may be crude oil since it is used without further treatment. In the sense of the present invention, mineral oil is in the range of petroleum oil. Refined oils are similar to unrefined oils except that they have been processed in one or more purification steps to improve one or more properties. Many such purification techniques, such as distillation, solvent extraction, acid or base extraction, filtration and percolation, are known in the art. The refined oil is obtained in a similar manner to the method used to obtain the refined oil applied to the refined oil already used. Such refined oils are known as regenerated oils or reprocessed oils and are further processed by techniques for removing spent additives and oil decomposition products.

All-hydrogenated base oil (C) (4) is considered a synthetic base oil and is commercially available from lubricant manufacturers. Recent refining processes have formed a new class of synthetic oils. For example, a technical paper by Chevron Products Company entitled "The Synthetic Nature Of Group III Base Oils", Presented at the 1999 Lubricants & Waxes Meeting, November 11-12, Houston TX (National Petrochemical & Refines Association), improves lubrication properties. To that end, a whole-hydrogen production route is disclosed that combines three catalytic reactions that selectively or significantly change the size, shape, and heteroatom content of a molecule. Hydrogen is added at high temperature and high pressure in all three stages to produce exceptionally stable oils. In group III preparations, the feedstock is saturated to enrich for isoparaffins. Reactive species such as aromatic, sulfur, and nitrogen containing species are substantially eliminated and species that create problems with low temperature performance such as normal paraffin are also removed. Finally, the paper concludes that analysis of feedstocks and products obtained from industrial Group III preparation has shown that the majority of the source molecules are synthesized by three catalytic methods used to produce modern whole-hydrogenated Group III base oils. Conclude that it shows transformation. These results support the claim that modern Group III base oils made using all-hydrogen treatment routes are necessarily artificial or synthetic and have advantages over hydrocracked base oils according to the prior art. High performance in their lubricant applications also makes them available for high performance products formulated with traditional synthetics such as polyalphaolefins (PAO). The reference does not disclose the use of whole-hydrogenated Group III base oils as raw materials for the preparation of biodegradable vegetable oil based lubricants.

Patents that generally disclose lubricants that can be formed using vegetable oils and group III oils are described in US Pat. No. 6,103,673; US Patent 6,251,840; US Pat. No. 6,451,745 and US Pat. No. 6,528,458, which can be obtained from Lubrizol Corporation, Wycliffe, Ohio. Additional patents include US Pat. No. 6,303,547 and US Pat. No. 6,444,622, which are available from Ethyl Corporation, Richmond, Virginia.

U. S. Patent No. 6,528, 458 discloses (a) oils of lubricating viscosity; (b) 2,5-dimercapto-1,3,4-thiadiazole (DMTD), derivatives of DMTD, or mixtures thereof; (c) friction modifiers; And (d) a composition comprising a dispersant is useful for lubricating a transmission having a plurality of wet clutches and a plurality of partial power transmission shafts, the movement of the gears being synchronized with the fastening of fastened and unfastened partial transmission shafts and wet clutches. It is disclosed that it occurs by the process comprising.

U. S. Patent No. 6,451, 745 discloses that continuously variable transmissions are characterized by (a) oils of lubricating viscosity; (b) dispersants; And (c) can be lubricated by supplying a composition comprising a detergent. At least one of the dispersant (b) and the detergent (c) is a borated paper, and the amount of boron present in the composition should be sufficient to impart improved friction and anti-stick properties to the composition when applied to the transmission.

U.S. Pat.No. 6,444,622 discloses that mixtures of at least one C ₅ -C ₆₀ carboxylic acid and at least one amine selected from the group consisting of guanidines, aminoguanidines, ureas, thioureas and salts thereof and phosphorus containing dispersants are useful as gear oil additives. It starts.

US Pat. No. 6,303,547 discloses that the reaction product of at least one C ₅ -C ₆₀ carboxylic acid and at least one amine selected from the group consisting of guanidine, aminoguanidine, urea, thiourea and salts thereof is useful as gear oil additive.

U. S. Patent No. 6,251, 840 discloses lubricating / working liquid compositions which exhibit improved anti-wear and anti-foam properties in use. This improvement results from the use of silicone and / or fluorosilicone defoamers with 2,5-dimercapto-1,3,4-thiadiazole and derivatives thereof.

U. S. Patent No. 6,103, 673 discloses oils of lubricating viscosity; Shear stability viscosity modifiers; At least 0.1% by weight of overbased metal salts; 0.1 wt% or more of at least one phosphorus compound; And from 0.1 to 0.25% by weight of a combination of two or more friction modifiers provide improved fluids for continuously variable transmissions. The at least one friction modifier is selected from the group comprising zinc salts of fatty acids of at least 10 carbon atoms, hydrocarbyl imidazolines of at least 12 carbon atoms in hydrocarbyl groups and borated epoxides. The total amount of friction modifier is limited to an amount that provides a metal-to-metal friction coefficient of at least about 0.120 as measured at 110 ° C. by ASTM G-77.

The reference does not disclose lubricant formulations containing a combination of vegetable oils and hydrogenated base oils (Group III) and therefore do not suggest or suggest any benefits associated with such formulations. Since all-hydrogenated Group III raw materials are prepared without a solvent purification step, when it comes to purity, they are far superior to Group II or III base oils produced in “hybrid” plants that maintain some solvent processing. In fact, they contain the lowest levels of impurities currently available as mineral base oils, which provide significant performance advantages.

Whole-hydroprocessing involves three steps: hydrocracking, hydroisomerization and hydrofinishing. In the first stage, hydrocracking, most of the sulfur, nitrogen and almost all other non-hydrocarbon impurities are removed and most of the aromatics are saturated by hydrogenation. Molecular remodeling of the remaining saturated species occurs as the ring is opened and the paraffin isomers are redistributed and driven thermodynamically by the reaction rate promoted by the catalyst. Clean fuel is a byproduct of this step and subsequent processes. In the second step, hydrogenation isomerization, n-paraffins and other molecules with waxy side chains are isomerized into branched molecules with many low pour points. Most of the remaining aromatics are saturated and most of the remaining sulfur and nitrogen species are removed. In the final step, hydrogenation, any remaining non-isoparaffin impurities (sulfur species, nitrogen species, aromatics, and olefins) are removed to a trace level.

All-hydrogenated composites are classified as former Group III base oils, but due to the synthesis process they are improved and structured (chemically and physically) to implement the Group III range.

Another paper, "Base Oil Supply / Demand And Quality Issues" by Dave Kramer, Chevron Texco Global Lubricants, Presented at the 8th Annual Fuels & Lubes Asia Conference and Exhibition at the Shangri-La Hotel, Singapore from January 29 through February 1, 2002 Discusses other processes as follows: "Until 2007, Fischer Troche Base Oils (FTBOs) will emerge as the next quantitative leap in base oil quality. These oils should have a higher VI than PAO and in most respects PAO. And better than the existing Group III The Fischer Troche project has a stimulation of environmental and crude oil production, so the volume of FTBO produced can significantly exceed the requirements of Group III and PAO.Kline & Company has a 10 MM supply. Increase to MT, or by 2015, will be 30% of the total base oil market. "

These oils in (C) are discussed in the literature and in the following patents: US Pat. Nos. 5,990,055, 5,863, 872, 5,736,493, 6,534,454B1, 6,774,091.

(D) other additives:

Antioxidants useful in the present invention, including but not limited to, butyrateated hydroxytoluene (BHT), phenol-a-naphthylamine (PANA), other information about antioxidants are listed and described in the following patents : U.S. Patents 5,536,493, 5,863,872, 5,990,055, 6,534,454B1, 6,774,091.

A corrosion inhibitor comprising a non-limiting, the dispersant inhibitor was recorded prior These are: surface-active organic acid, hydroxy acid, hydroxy acid, keto acid, borated amines, paraffin wax, Imada sleepy derivatives, alkenyl succinic acid Half esters, organic polycarboxylic acids, paraffin waxes, nonyl phenoxy acetic acid, phenates, phenolic and amine antioxidants, n-oleyl sarcosine, phosphorus, carboxylic acid derivatives, zinc naphthenates, Ca sulfonates, Ba sulfonates, Ca dialkylbenzene sulfonate, Mg sulfonate, calcium dialkabenzene sulfonate, sodium oxydate, calcium oxydate, barium oxydate, fatty acid amines, sulfated fatty acids, amine nitrite salts, calcium nitrite, calcium acetate, Calcium dichromate, calcium hypophosphite, disodium sebacate, sodium sulfonate, sodium mercaptobenzothiazole, na Cerium nitrite, sodium salt of sodium hydroxide, succinic acid / sulfonate, barium nitrite, barium bromate, monoethanolamine borate, dimmer mercapto, diethoxy dia Paul, amine phosphate, potassium hydroxide, potassium phosphate esters; Amine salts of carboxylic acids, monocarboxylic acids, dicarboxylic acids; Tall oil imidazolines, oleyl imidazolines, vegetable waxes, alkyl zinc dithiophosphates, succinimides, esters or Mannich dispersants; other information on corrosion inhibitors and dispersant inhibitors is disclosed in US Pat. Nos. 5,536,493, 5,863,872 , 5,990,055, 6,534,454 B1, 6,774,091 and described.

Metal deactivators, including but not limited to, tolutriazole, tolyltriazole, triazole, benzotriazole, benzothiazole, benzoimidazole, and derivatives thereof. These metal deactivators and others are further discussed in the references and patents of the following patents: US Pat. Nos. 5,990,055, 5,863,872, 5,736,493, 6,774,091.

Viscosity modifiers alone or in combination, including, but not limited to , pour point inhibitors are ethylene vinyl acetate copolymers, polyisobutylene, polybutene, polymethacrylates, olefin copolymers, esters of styrene maleic anhydride copolymers, hydrogenated Styrene-diene copolymers, styrene isoprene compounds, alkylated polystyrenes, hydrogenated radial polyisoprene, polyacrylate acid esters, fumed silica, food grade adhesive-like natural rubbers, and the like. These viscosity modifiers and pour point inhibitors and others are discussed in the references and patents of the following patents: US Pat. Nos. 5,990,055, 5,863,872, 5,736,493, 6,534,454B1, 6,774,091.

Anti-wear inhibitors, friction modifiers , extreme pressure additives are not limited to these and used alone or in combination: synthetic esters, sulfided synthetic esters, synthetic ester polymers, phosphorus sulfur, fatty phosphites, phosphites, phosphate esters, borate esters Boron oxide, calcium sulfonate, sodium sulfonate, polysulfide, sulfided fats, sulfided olefins, sulfided vegetable oils, antimony, zinc (ZDP), copper, polytetrafluoroethylene, molybdenum and graphite compounds. Some of these additives act as multifunctional additives including antioxidants, for example zinc dithiophosphate is a multifunctional additive in that it acts as a corrosion inhibitor, an antiwear agent and an antioxidant added to the organic material to delay oxidation. . These additives and others are discussed in the references of this patent and in the following patents: US Pat. Nos. 5,990,055, 5,863,872, 5,736,493, 6,534,454B1, 6,774,091.

Emulsifiers including, but not limited to, anions and nonions may be added to the present invention to improve water emulsification or solubility of the formulation.

The present invention contemplates using other effective amounts of additives in the lubricating and working fluid compositions of the present invention. Such additives include, for example, detergents and re-produced or ashless types of dispersants, corrosion and oxidation inhibitors, pour point inhibitors, extreme pressure aids and / or antiwear agents, color stabilizers and antifoams.

Complete additive packages incorporating dispersant inhibitors in combination with conventional detergents and / or corrosion inhibitors may be purchased commercially or obtained in place of dispersion inhibitors. Lubrizol's LZ8955 and / or LZ9802 or a combination of each and / or other dispersing inhibitor may be used. The most recent additive packages produced by Lubrizol include Core API SL LZ 20001, Anti Oxidant Booster LZ 8676, and Friction Modifier Booster LZ 8650 for ILSAC GF3 / GF4.

These additives and others are discussed in Lubrizol's data and MSDS sheets, references in this patent and the following patents: US Pat. Nos. 5,990,055, 5,863,872, 5,736,493, 6,534,454B1 and 6,774,091.

Compositions of the present invention comprising components (A) and (B) or (A), (B), and (C), or (A), (B), (C) and (D) are high temperature biodegradable lubricants. It is useful as food grade lubricant and engine oil.

When the composition comprises components (A) and (B), the following shows the ranges by weight of these components in parts by weight:

ingredient First Embodiment 2nd Embodiment The third Embodiment

(A) 5-99.9 65-99.9 95-99.998

(B) 0.002-50 0.002-35 0.002-5

If the composition comprises components (A), (B), (C) and (D), the following shows the ranges of these components by weight:

ingredient First Embodiment 2nd Embodiment The third Embodiment

(A) 5-90 40-80 60-90

(B) 0.002-80 0.002-35 0.002-5

(C) 20-80 10-20 1-10

(D) 0.001-80 0.001-40 0.001-20

It can be seen that the concentrate of the invention can be formed. The concentrate may contain a small amount of (A) and a large amount of (B), a small amount of (A) and a combination of (B), (C) and (D) or a combination of (A), (B) and (D) Contains traces of water and large amounts of (B).

As used in the description of the invention and the appended claims, the term "trace" refers to when the composition contains "trace" of a particular substance, the amount being less than 50% by weight of the composition.

As used in the description of the present invention and the appended claims, the term "large amount" when the composition contains "large amounts" of a particular substance, is that amount is at least 50% by weight of the composition.

It can be seen that other components other than (A), (B), (C) and (D) may be present in the compositions of the present invention.

The components of the present invention are blended together in accordance with the above-described ranges to effect the solution. Typically (B), (C) and (D) are added to (A), but the order of addition does not affect the results.

The following is a formulated example.

NP 343 is a polyol ester manufactured by ExxonMobil, biologically identified by USDA, Indopol H 1500 is a food grade polybutene made by British phytlium (BP), and PD23 is a white food grade manufactured by Witco Corporation It is mineral oil and boron nitride is food grade.

Formulation # 883 Bio High Temperature (HT) Oven Chain and Cable Lubricant

Formulation # 883A Bio HT Lubricant ISO 100 for Multifunctional Uses

Formulation # 883B Bio HT Oven Chain Lubricant USDA H-2

Formulation # 883C Bio HT Grease Base Oil

Formulation # 883D Bio HT Oven Chain Lubricant USDA H-1

Another aspect of the present invention is directed to a method for improving lubrication of an engine that improves fuel economy by improving oxidation, stability, reducing emission volatility, and reducing friction. Reference patents suggesting high temperature oxidative stability, reduced sediment and volatility and reduced friction include: US Pat. Nos. 5,990,055, 5,863,872, 5,736,493, 6,534,454B1, 6,774,091.

These patents disclose the use of the benefits of combining these components to reduce the synergy and oxidation of two or more antioxidants and / or anti-wear extremes and to significantly lower the coefficient of friction.

Most of the informational reference patents are owned by Applicant and / or Renewal Lubricant Inc., with the exception of US Pat. No. 6,774,091, owned by Ashland Inc. (Balboline).

Applicants have found that boron nitride can be used in combination with a molybdenum compound and / or polytetrafluoroethylene to substitute one of the additives.

The present invention provides a composition comprising: 1) one or more biological natural oils selected from the group consisting of 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 Or providing a biological synthetic oil; 2) providing at least one boron nitride; And 3) optionally synthetic synthetic esters, solvent refined petroleum oils, hydrocracked petroleum white oils, whole-hydrogenated synthetic oils, Fischer Tropsch base oils, petroleum oil groups I, group II, groups Providing one or more base oils selected from the group consisting of III, polyalphaolefins (PAO), and mixtures thereof, and 4) optionally US Pat. Nos. 5,990,055, 5,863,872, 5,736,493, 6,534,454 B1, 6,774,091, Antioxidants, corrosion inhibitors, metal deactivators, viscosity modifiers, anti-wear, selected from Provisional Application Nos. 60 / 474,572 and 60 / 502,669, filed by 6,620,772, 6,624,124, 6,383,992 and Renewable Lubricants Inc. Providing at least one additive selected from the group consisting of inhibitors, friction modifiers, extreme pressure agents and emulsifiers; 5) A method of making an improved high temperature engine lubricant composition comprising the steps of combining 1), 2), 3) and 4) in any order to form the composition.

The combination of the chemistry of the present invention reduces friction between moving parts of the engine such that in operation a very fine film of the chemical component is formed on the metal surface.

At high temperatures and pressures in the engine, the surface active component reacts with the film to continuously form a very thin lubrication layer that has an extremely low coefficient of friction and withstands extreme temperatures and pressures to provide excellent lubricity during initiation of the reaction and during the running phase of the engine. do.

The following shows some formulated examples that were formulated at 10.5-10.7 cSt (SAE 30) using 5 W satisfying cold pumping performance for mini rotor viscometer:

Passenger Car Motor Oil (PCMO) Synthesis SAE 5W30

Passenger Car Motor Oil Synthesis SAE 5W30

Passenger Car Motor Oil Synthesis SAE 5W30

Passenger Car Motor Oil Synthesis SAE 5W30

Passenger Car Motor Oil Synthesis SAE 5W30

Passenger Car Motor Oil Synthesis SAE 5W30

Boron nitride particle additives sometimes disperse better when formulated with base oil carriers and / or biological oils prior to formulation. One embodiment will be one part boron nitride dispersed in 3-10 parts NP343, but is not limited thereto.

Passenger Car Motor Oil Concentrated Additive Formulation As Biological Booster Package (Bio-Booster Pack) for Top Treat Conventional Motor Oils

The 8 oz bottle is treated with 4-5 quarts of motor oil to formulate the concentrated additive. Bio-booster packs can be added to gasoline to extend oil life and increase engine life by reducing wear and improving fuel economy. This package has a high percentage of extreme pressure friction modifiers and anti-wear agents (LZ8650, as identified by Lubrizol as an antioxidant additive to Crankcase engine oil to meet the new API SL / SM and ILSAC GF3 / GF). The concentrated balance of these additives does not exceed the treatment rate when added as a concentrate to the motor oil. Engine additive package LZ20001, Pour Point Inhibitor LZ6662, and Viscosity Modifier LZ7070D are added at appropriate percentages to balance the additives in fully formulated engine oils and not to dilute the additives. Molyvan 855, NX1 boron nitride and Teflon increased to a percentage in the formulation when formulated sufficiently. When adding about 5% (8 ounces to 5 quarters) of additives at a viscosity of SAE 20, SAE 30, SAE 40 or SAE 50, the bio-booster pack is formulated to a viscosity of 12 cSt, so do not choose a formulation outside the SAE engine oil viscosity. Will not.

The bio-booster pack is similar to the method described above that meets the Heavy Duty Diesel Motor (HDMO) specification by replacing the LZ20001 with the LZ4998 diesel engine additive package with the booster additives LZ8790, LZ8791 and LZ8791Z, which are commercially available from Lubrizol Corporation. Can be formulated. Bio-booster packs can vary in viscosity, such as older excipients using standard factory fill 10.5 cSt. You will benefit from boosting the oil to a high slide with a SAE rating of 12 cSt. This can be done by increasing the polymer or adding high viscosity biological oils. The polymer can be enhanced by adding more shear stable polymers as in LZ7075F replacing LZ7070D. A suitable procedure would be to formulate a booster pack for PCMO as well as a booster pack for HDMO.

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The particular compositions, methods or embodiments discussed are for illustration of the invention described herein. Variations to these compositions, methods or embodiments are included as part of the present invention as will be apparent to those skilled in the art in view of what is described herein.

The foregoing detailed description has been given for clarity of understanding and does not imply any limitation therefrom, and upon reading the disclosure, modifications are apparent to those skilled in the art and may be made without departing from the spirit of the invention and the appended claims. Accordingly, the invention is not limited to any specific embodiment described above. Rather, the protection is intended to be within the spirit and scope of the appended claims.

The numerical values and variables setting forth the broad scope of the invention are approximations, but the numerical values set forth in the specific examples are reported as precisely as possible. However, some values will inherently contain certain errors due to standard deviations in each test measurement.

The invention has been described with some embodiments. Obviously, reading and understanding the specification will enable variations and variations. Applicants deem all such modifications and variations as fall within the scope of the appended claims or their equivalents. Therefore, the present invention described so far is claimed as follows.

Claims (21)

At least one biological oil selected from the group consisting of natural or synthetic vegetable oils, natural or synthetic animal oils, genetically modified vegetable oils, genetically modified synthetic vegetable oils, natural or synthetic wood oils, and mixtures thereof; And A lubricant comprising at least one boron nitride. 2. The lubricant of claim 1 wherein the lubricant is a synthetic ester, solvent refined petroleum oil, hydrocracked petroleum white oil, all-hydrogenated synthetic oil, Fischer Tropsch base oil, Group I petroleum oil, group At least one base oil selected from the group consisting of II petroleum oils, Group III petroleum oils, polyalphaolefins (PAO), and mixtures thereof. 3. The lubricant of claim 2 wherein the lubricant is at least one additive or combination of additives selected from the group consisting of antioxidants, corrosion inhibitors, metal deactivators, viscosity modifiers, anti-wear inhibitors, friction modifiers and extreme pressure agents. slush. The lubricant of claim 1 wherein the oil is triglycerides having the formula:

In the formula, R ¹ , R ² and R ³ are aliphatic hydrocarbyl groups containing from about 7 to about 23 carbon atoms. The lubricant of claim 4 wherein the aliphatic hydrocarbyl group is selected from the group comprising aliphatic hydrocarbon groups, substituted aliphatic hydrocarbon groups and hetero groups. 6. The lubricant of claim 5, wherein the triglyceride has an oleic acid profile of at least about 60%. The lubricant of claim 4 wherein the triglyceride has at least about 60% mono-saturation characteristics. 8. The lubricant of claim 7, wherein the triglycerides have a monosaturation characteristic of at least 70%. 9. The lubricant of claim 8 wherein triglycerides have at least about 80% mono-saturation characteristics. The lubricant of claim 1 wherein the oil is from about 5% to about 99.9% by weight of the lubricant and boron nitride is from about 0.002% to about 50% by weight of the lubricant. The lubricant of claim 10 wherein the oil is from about 65% to about 99.9% by weight of the lubricant and boron nitride is from about 0.002% to about 35% by weight of the lubricant. The lubricant of claim 11 wherein the oil is from about 95% to about 99.998% by weight of the lubricant and boron nitride is from about 0.002% to about 5% by weight of the lubricant. The method of claim 3 wherein the biological oil is from about 5% to about 90% by weight of the lubricant, boron nitride is from about 0.002% to about 80% by weight of the lubricant, the base oil is from about 20% to about 80% by weight of the lubricant %, And the additive is about 0.001% to about 80% by weight of the lubricant. The method of claim 13, wherein the biological oil is from about 40% to about 80% by weight of the lubricant, boron nitride is from about 0.002% to about 35% by weight of the lubricant, and the base oil is from about 10% to about 20% by weight of the lubricant. %, And the additive is from about 0.001% to about 40% by weight of the lubricant. 15. The method of claim 14 wherein the biological oil is from about 60% to about 90% by weight of the lubricant, boron nitride is from about 0.002% to about 5% by weight of the lubricant, and base oil is from about 1% to about 10% by weight of the lubricant. %, And the additive is from about 0.001% to about 20% by weight of the lubricant. The lubricant of claim 1 wherein the oil is at most about 50% by weight of the lubricant and boron nitride is at least about 50% by weight of the lubricant. 4. The lubricant of claim 3 wherein the biological oil is up to about 50% by weight of the lubricant and the base oil, boron nitride and additives together are at least about 50% by weight of the lubricant. 4. The lubricant of claim 3 wherein the biological oil, boron nitride and additives are in total up to about 50% by weight of the lubricant and the base oil is at least about 50% by weight of the lubricant. At least one boron nitride is selected from the group consisting of 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; Compounding; And Adding an effective amount of said oil and boron nitride to the device. 20. The synthetic ester, solvent refined petroleum oil, hydrocracked petroleum white oil, all-hydrogenated synthetic oil, Fischer Tropsch base oil, Group I prior to addition to the apparatus. Further comprising combining at least one base oil selected from the group consisting of petroleum oil, Group II petroleum oil, Group III petroleum oil, polyalphaolefin (PAO), and mixtures thereof with biological oil and boron nitride. The combination of at least one additive or additive of claim 20 selected from the group consisting of antioxidants, corrosion inhibitors, metal deactivators, viscosity modifiers, anti-wear inhibitors, friction modifiers and extreme pressure agents prior to addition to the device. Further comprising combining the biological oil with the base oil and boron nitride.