WO2014179726A1 - Préparations d'huile moteur à base de diester ayant des propriétés améliorées de faible noack et d'écoulement à froid - Google Patents
Préparations d'huile moteur à base de diester ayant des propriétés améliorées de faible noack et d'écoulement à froid Download PDFInfo
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- WO2014179726A1 WO2014179726A1 PCT/US2014/036633 US2014036633W WO2014179726A1 WO 2014179726 A1 WO2014179726 A1 WO 2014179726A1 US 2014036633 W US2014036633 W US 2014036633W WO 2014179726 A1 WO2014179726 A1 WO 2014179726A1
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M111/00—Lubrication compositions characterised by the base-material being a mixture of two or more compounds covered by more than one of the main groups C10M101/00 - C10M109/00, each of these compounds being essential
- C10M111/02—Lubrication compositions characterised by the base-material being a mixture of two or more compounds covered by more than one of the main groups C10M101/00 - C10M109/00, each of these compounds being essential at least one of them being a non-macromolecular organic compound
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
- C10M105/08—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen
- C10M105/32—Esters
- C10M105/38—Esters of polyhydroxy compounds
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- 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
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- 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
- C10M2203/102—Aliphatic fractions
- C10M2203/1025—Aliphatic fractions used as base material
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/28—Esters
- C10M2207/283—Esters of polyhydroxy compounds
- C10M2207/2835—Esters of polyhydroxy compounds used as base material
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- 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
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/02—Pour-point; Viscosity index
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- 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
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/04—Detergent property or dispersant property
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- 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
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/08—Resistance to extreme temperature
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- 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
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/10—Inhibition of oxidation, e.g. anti-oxidants
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- 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
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/64—Environmental friendly compositions
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- 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
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/74—Noack Volatility
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/25—Internal-combustion engines
Definitions
- the present invention relates to a multi-grade engine oils formulated to meet the specifications for SAE viscosity grade OW-XX or 5W-XX engine oil, wherein XX represents the integer 16, 20, 30, or 40.
- Formulations meeting the specifications for SAE viscosity grade OW-20 and 5W-20 have been successfully prepared using the present invention. This desired properties achieved include multi-grade OW-20 and 5W-20 SAE motor oils with low Noack and excellent cold flow properties.
- Esters have been used as lubricating oils for over 50 years. They are used in a variety of applications ranging from jet engines, refrigeration and motor oils. In fact, esters were the first synthetic crankcase motor oils in automotive applications. However, esters gave way to polyalphaolefins (PAOs) due to the lower cost of PAOs and their formulation similarities to mineral oils. In full synthetic motor oils, however, esters are almost always used in combination with PAOs to balance the effect on seals, additives solubility, volatility reduction, and energy efficiency improvement by enhanced lubricity. In this aspect, novel diester-based multi-grade engine oil compositions comprising PAOs have been described in commonly-assigned United States Patent Application Serial No. 12/548,191; filed August 26, 2009.
- Ester-based lubricants in general, have excellent lubrication properties due to the polarity of the ester molecules of which they are comprised.
- the polar ester groups of such molecules adhere to positively-charged metal surfaces creating protective films which slow down the wear and tear of the metal surfaces.
- Such lubricants are less volatile than the traditional lubricants and tend to have much higher flash points and much lower vapor pressures.
- Ester lubricants are excellent solvents and dispersants, and can readily solvate and disperse the degradation by-products of oils. Therefore, they greatly reduce sludge buildup.
- ester lubricants are stable to thermal and oxidative processes, the ester functionalities give microbes a handle to do their biodegrading more efficiently and more effectively than their mineral oil-based analogues. Therefore, there exists an opportunity to employ an alternative blending component that reduces volatility at a reduced cost and with other advantages not afforded with PAO.
- FT Fischer-Tropsch
- Novel diester-based lubricant compositions and their corresponding syntheses have been described in commonly-assigned United States Patent No. US 7,871,967 B2; issued January 18, 2011.
- the synthetic routes described in this patent application comprise and/or generally proceed through the following sequence of reaction steps: (1) epoxidation of an olefin to form an epoxide; (2) conversion of the epoxide to form a diol; and (3) esterification of the diol to form a diester.
- novel diester-based lubricant compositions and their corresponding syntheses have been described in commonly-assigned United States Patent No. US 7,867,959 B2; issued January 1 1, 201 1.
- the synthetic routes described in this patent application comprise and/or generally proceed through the following sequence of reaction steps: (1) epoxidation of an olefin to form an epoxide; (2) directly esterifying the epoxide with a carboxylic acid to form a diester species.
- OEM Original Equipment Manufacturers
- API American Petroleum Institute
- ASTM Association des Consructeurs d' Automobiles
- ASAM American Society of Testing and Materials
- IVSAC International Lubricant Standardization and Approval Committee
- SAE Society of Automotive Engineers
- Engine oils are finished crankcase lubricants intended for use in automobile engines and diesel engines and consist of two general components (i.e., a lubricating base oil and additives).
- Lubricating base oil is the major constituent in these finished lubricants and contributes significantly to the properties of the engine oil. Accordingly, there is need for Multi-grade engine oils formulated lubricating oils, which have improved low volatility, excellent cold flow properties and improved fuel economy to meet today's stringent performance requirements.
- the minimum specifications for the various viscosity grades of engine oils is established by SAE J300 standards as revised in January 2009. SUMMARY OF THE INVENTION
- the present invention is directed to a multi-grade engine oil comprising: a) a diester component, comprising a quantity of at least one diester species having the following Formula I:
- Ri, R 2 , R 3 and R4 are the same or independently selected from C 2 to C17 hydrocarbon groups;
- the second base is selected from the group consisting of Group I base oil,
- Group II base oil or Group III base oil are Group II base oil or Group III base oil.
- Figure 1 is a chart illustrates the Noack and CCS Viscosity of the diesters of the present invention as compared to the current commercial esters as presented in Table 6 and other Group II and III bases oils.
- the present invention is directed to a multi-grade engine oil comprising: a) a diester component, comprising a quantity of at least one diester species of Formula I, wherein Ri, R 2 , R 3 and R4 are the same or independently selected from C 2 to C17 hydrocarbon groups; b) a second base oil; and c) an additive package, wherein the second base is selected from the group consisting of Group I base oil, Group II base oil or Group III base oil.
- the present invention is directed to a multi-grade engine oil, wherein a quantity of at least one diester species comprises a mixture of isomers where Ri and R2 are different for each isomer.
- the present invention is directed to a multi-grade engine oil, further comprising, a third base oil.
- the present invention is directed to a multi-grade engine oil, wherein the diester has a Noack Volatility between about 6 and 10 wt%, a CCS Viscosity at -30°C between about 700 and 2000 cP, a pour point less than about -10°C, a cloud point less than about -10°C, a kinematic viscosity at 100°C between about 2.5 to 6.5 centistokes, a VI greater than about 110 and a BN Oxidator greater than about 20 hours.
- the diester has a Noack Volatility between about 6 and 10 wt%, a CCS Viscosity at -30°C between about 700 and 2000 cP, a pour point less than about -10°C, a cloud point less than about -10°C, a kinematic viscosity at 100°C between about 2.5 to 6.5 centistokes, a VI greater than about 110 and a BN Oxidator greater than about 20 hours.
- the present invention is directed to a multi-grade engine oil, wherein the diester has a Noack Volatility between about 6 and 9 wt%, and a CCS Viscosity at -30°C between about 800 and 1900 cP.
- the present invention is directed to a multi-grade engine oil, wherein the diester has a Noack Volatility between about 6 and 9 wt%, and a CCS Viscosity at -25°C between about 400 and 1250 cP.
- the present invention is directed to a multi-grade engine oil, wherein the second base and third base oil are independently selected from the group consisting of light neutral base oil, medium neutral base oil, Yubase 4, Yubase 6, 150R, 600R, 1 lORLV, 220R and 100R.
- the present invention is directed to a multi-grade engine oil, meeting the specifications for SAE viscosity grade 0W-XX or 5W-XX, wherein XX represents the integer 16, 20, 30, or 40.
- the present invention is directed to a multi-grade engine oil, wherein the multi-grade engine oil meets the SAE J300 standards as revised in January 2009.
- the present invention is directed to a multi-grade engine oil, having: a) a viscosity index between about 140-200; b) a kinematic viscosity at 100°C between about 6-10 cSt; c) a Pour Point less than about -30° C; and d) a Noack volatility of less than about 15 wt %, wherein the multi-grade engine oil is a 0W- SAE grade with a CCS Viscosity at -35°C less than about 6200 cP or the multi-grade engine oil is a 5W- SAE grade with a CCS Viscosity at -30°C less than about 6600 cP.
- the present invention is directed to a multi-grade engine oil, wherein the kinematic viscosity of the multi-grade engine oil at a temperature of 100°C is between about 3 to 10 centistokes. In some embodiments, the present invention is directed to a multi-grade engine oil, wherein the CCS Viscosity at -30°C less than about 6,600 cP.
- the present invention is directed to a multi-grade engine oil, wherein the CCS Viscosity at -35°C less than about 6,200 cP.
- the present invention is directed to a multi-grade engine oil, wherein the Noack Volatility less than about 15 wt%.
- the present invention is directed to a multi-grade engine oil, wherein Ri and R2 are selected to have a combined carbon number of from 6 to 16 and R 3 and R4 are selected to have a combined carbon number of from 10 to 34.
- the present invention is directed to a multi-grade engine oil, wherein Ri and R2 of Formula I are selected to have a combined carbon number of Ci 6 , C14 or C12 and R3 and R4 are independently selected from the group consisting of C12 and a mixture of Ce-Cio.
- the present invention is directed to a multi-grade engine oil, wherein the at least one diester species is derived from a Cs to C 18 olefin and a Ce to C 14 carboxylic acid.
- the present invention is directed to a multi-grade engine oil, wherein said composition comprises quantities of at least two different diester isomers.
- the present invention is directed to a multi-grade engine oil, wherein the at least one diester species has a molecular mass that is from at least about 340 a.m.u. to at most about 780 a.m.u.
- the present invention is directed to a multi-grade engine oil, wherein the at least one diester species is selected from the group consisting of decanoic acid 2-decanoyloxy- l-hexyl-octyl ester and its isomers, tetradecanoic acid-l -hexyl-2- tetradecanoyloxy-octyl esters and its isomers, dodecanoic acid 2-dodecanoyloxy-l -hexyl- octyl ester and its isomers, hexanoic acid 2-hexanoyloxy-l -hexy-octyl ester and its isomers, octanoic acid 2-octanoyloxy- l-hexyl-octyl ester and its isomers, hexanoic acid 2- hexanoyloxy- l-hexyl-octyl ester and its is
- the present invention is directed to a multi-grade engine oil, wherein the multi-grade engine oil is formulated as a OW-20 SAE OW-16 or 5W-20 SAE engine oil.
- Base oils are the most important component of lubricant compositions, generally comprising greater than 70% of the lubricant compositions.
- Lubricant compositions comprise a base oil and at least one additive.
- Lubricant compositions can be used in automobiles, diesel engines, axles, transmissions, and industrial applications.
- Lubricant compositions must meet the specifications for their intended application as defined by the concerned governing organization.
- Additives which can be blended with the base oil, to provide a lubricant composition include those which are intended to improve select properties of the lubricant composition.
- Typical additives include, for example, anti-wear additives, extreme pressure agents, detergents (e.g., metal-containing detergents), dispersants (e.g., ashless dispersants), antioxidants, pour point depressants, VI Improvers (VII), viscosity modifiers, friction modifiers, demulsifiers, antifoaming agents, inhibitors (e.g., corrosion inhibitors, rust inhibitors, etc.), seal swell agents, emulsifiers, wetting agents, lubricity improvers, metal deactivators, gelling agents, tackiness agents, bactericides, fluid-loss additives, colorants, and the like.
- Additives can be added in the form of an additive package, containing various additives.
- Dispersants are generally used to maintain in suspension insoluble materials resulting from oxidation during use, thus preventing sludge flocculation and precipitation or deposition on engine parts.
- examples of dispersants include nitrogen- containing ashless (metal-free) dispersants.
- An ashless dispersant generally comprises an oil soluble polymeric hydrocarbon backbone having functional groups that are capable of associating with particles to be dispersed.
- Other examples of dispersants include, but are not limited to, amines, alcohols, amides, or ester polar moieties attached to the polymer backbones via bridging groups.
- An ashless dispersant may be selected from oil soluble salts, esters, amino-esters, amides, imides, and oxazolines of long chain hydrocarbon substituted mono and dicarboxylic acids or their anhydrides; thiocarboxylate derivatives of long chain hydrocarbons, long chain aliphatic hydrocarbons having a polyamine attached directly thereto; and Mannich condensation products formed by condensing a long chain substituted phenol with formaldehyde and polyalkylene polyamine.
- Carboxylic dispersants are reaction products of carboxylic acylating agents (acids, anhydrides, esters, etc.) comprising at least 34 and preferably at least 54 carbon atoms with nitrogen containing compounds (such as amines), organic hydroxy compounds (such as aliphatic compounds including monohydric and polyhydric alcohols, or aromatic compounds including phenols and naphthols), and/or basic inorganic materials.
- carboxylic acylating agents as acids, anhydrides, esters, etc.
- nitrogen containing compounds such as amines
- organic hydroxy compounds such as aliphatic compounds including monohydric and polyhydric alcohols, or aromatic compounds including phenols and naphthols
- basic inorganic materials include imides, amides, and esters, e.g., succinimide dispersants.
- Suitable ashless dispersants may also include amine dispersants, which are reaction products of relatively high molecular weight aliphatic halides and amines, preferably polyalkylene polyamines.
- amine dispersants which are reaction products of relatively high molecular weight aliphatic halides and amines, preferably polyalkylene polyamines.
- Other examples may further include "Mannich dispersants," which are reaction products of alkyl phenols in which the alkyl group contains at least 30 carbon atoms with aldehydes (especially formaldehyde) and amines (especially polyalkylene polyamines).
- ashless dispersants may even include post-treated dispersants, which are obtained by reacting carboxylic, amine or Mannich dispersants with reagents such as dimercaptothiazoles, urea, thiourea, carbon disulfide, aldehydes, ketones, carboxylic acids, hydrocarbon-substituted succinic anhydrides, nitrile epoxides, boron compounds and the like.
- Suitable ashless dispersants may be polymeric, which are interpolymers of oil-solubilizing monomers such as decyl methacrylate, vinyl decyl ether and high molecular weight olefins with monomers containing polar substitutes.
- Other suitable ashless dispersants may also include an ethylene carbonate-treated bissuccinimide derived from a polyisobutylene having a number average molecular weight of about 2300 Daltons (“PIBSA 2300").
- Viscosity Index Improvers The viscosity index of an engine oil base stock can be increased, or improved, by incorporating therein certain polymeric materials that function as viscosity modifiers (VM) or viscosity index improvers (VII) in an amount of 0.3 to 25 wt %. of the final weight of the engine oil.
- VM viscosity modifiers
- VI viscosity index improvers
- Examples include but are not limited to olefin copolymers, such as ethylene-propylene copolymers, styrene-isoprene copolymers, hydrated styrene-isoprene copolymers, polybutene, polyisobutylene, polymethacrylates, vinylpyrrolidone and methacrylate copolymers and dispersant type viscosity index improvers.
- olefin copolymers such as ethylene-propylene copolymers, styrene-isoprene copolymers, hydrated styrene-isoprene copolymers, polybutene, polyisobutylene, polymethacrylates, vinylpyrrolidone and methacrylate copolymers and dispersant type viscosity index improvers.
- viscosity modifiers can optionally be grafted with grafting materials such as, for example, maleic anhydride, and the grafted material can be reacted with, for example, amines, amides, nitrogen-containing heterocyclic compounds or alcohol, to form multifunctional viscosity modifiers (dispersant-viscosity modifiers).
- grafting materials such as, for example, maleic anhydride
- the grafted material can be reacted with, for example, amines, amides, nitrogen-containing heterocyclic compounds or alcohol, to form multifunctional viscosity modifiers (dispersant-viscosity modifiers).
- viscosity modifiers include star polymers (e.g., a star polymer comprising isoprene/styrene/isoprene triblock).
- star polymers e.g., a star polymer comprising isoprene/styrene/isoprene triblock.
- examples of viscosity modifiers include poly alkyl(meth)acrylates of low Brookfield viscosity and high shear stability, functionalized poly alkyl(meth)acrylates with dispersant properties of high Brookfield viscosity and high shear stability, polyisobutylene having a weight average molecular weight ranging from 700 to 2,500 Daltons and mixtures thereof.
- the lubricating oil composition may comprise at least a friction modifier (e.g., a sulfur-containing molybdenum compound).
- a friction modifier e.g., a sulfur-containing molybdenum compound.
- Certain sulfur-containing organo-molybdenum compounds are known to modify friction in lubricating oil compositions, while also offering antioxidant and antiwear credits.
- oil soluble organo-molybdenum compounds include molybdenum succinimide complex, dithiocarbamates, dithiophosphates, dithiophosphinates, xanthates, thioxanthates, sulfides, and the like, and mixtures thereof.
- Other examples include at least a mono-, di- or triester of a tertiary hydroxyl amine and a fatty acid as a friction modifying fuel economy additive.
- Other examples are selected from the group of succinamic acid, succinimide, and mixtures thereof.
- aliphatic fatty amine an ether amine, an alkoxylated aliphatic fatty amine, an alkoxylated ether amine, an oil-soluble aliphatic carboxylic acid, a polyol ester, a fatty acid amide, an imidazoline, a tertiary amine, a hydrocarbyl succinic anhydride or acid reacted with an ammonia or a primary amine, and mixtures thereof.
- Seal fixes are also termed seal swelling agents or seal pacifiers. They are often employed in lubricant or additive compositions to insure proper elastomer sealing, and prevent premature seal failures and leakages.
- Seal swell agents may be selected from oil-soluble, saturated, aliphatic, or aromatic hydrocarbon esters such as di-2- ethylhexylphthalate, mineral oils with aliphatic alcohols such as tridecyl alcohol, triphosphite ester in combination with a hydrocarbonyl-substituted phenol, and di-2-ethylhexylsebacate.
- Corrosion inhibitors are typically added to reduce the degradation of the metallic parts contained in the engine oil in amounts from about 0.02 to 1 wt %.
- Examples include zinc dialkyldithiophosphate, phosphosulfurized hydrocarbons and the products obtained by reaction of a phosphosulfurized hydrocarbon with an alkaline earth metal oxide or hydroxide, preferably in the presence of an alkylated phenol or of an alkylphenol thioester.
- the rust inhibitor or anticorrosion agents may be a nonionic polyoxyethylene surface active agent.
- Nonionic polyoxyethylene surface active agents include, but are not limited to, polyoxyethylene lauryl ether, polyoxyethylene higher alcohol ether, polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene octyl stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene sorbitol monostearate, polyoxyethylene sorbitol mono-oleate, and polyethylene glycol monooleate.
- Rust inhibitors or anticorrosion agents may also be other compounds, which include, for example, stearic acid and other fatty acids, dicarboxylic acids, metal soaps, fatty acid amine salts, metal salts of heavy sulfonic acid, partial carboxylic acid ester of polyhydric alcohols, and phosphoric esters.
- the rust inhibitor may be a calcium stearate salt.
- Detergents In engine oil compositions, metal-containing or ash-forming detergents function both as detergents to reduce or remove deposits and as acid neutralizers or rust inhibitors, thereby reducing wear and corrosion and extending engine life.
- Detergents generally comprise a polar head with long hydrophobic tail, with the polar head comprising a metal salt of an acid organic compound.
- the engine oil composition may contain one or more detergents, which are normally salts (e.g., overbased salts. Overbased salts, or overbased materials), are single phase, homogeneous Newtonian systems characterized by a metal content in excess of that which would be present according to the stoichiometry of the metal and the particular acidic organic compound reacted with the metal.
- the engine oil composition may comprise at least a carboxylate detergent.
- Carboxylate detergents e.g., salicylates, can be prepared by reacting an aromatic carboxylic acid with an appropriate metal compound such as an oxide or hydroxide.
- the engine oil composition may comprise at least an overbased detergent.
- overbased detergents examples include, but are not limited to calcium sulfonates, calcium phenates, calcium salicylates, calcium stearates and mixtures thereof.
- Overbased detergents may be low overbased (e.g., Total Base Number (TBN) below about 50).
- Suitable overbased detergents may alternatively be high overbased (e.g., TBN above about 150) or medium overbased (e.g., TBN between 50 and 150).
- TBN Total Base Number
- the lubricating oil compositions may comprise more than one overbased detergents, which may be all low-TBN detergents, all high-TBN detergents, or a mix of those two types.
- Suitable detergents for the lubricating oil compositions include "hybrid" detergents such as, for example, phenate/s alkylates, sulfonate/phenates, sulfonate/salicylates, sulfonates/phenates/salicylates, and the like.
- the composition may comprise detergents made from alkyl benzene and fuming sulfonic acid, phenates (high overbased, medium overbased, or low overbased), high overbased phenate stearates, phenolates, salicylates, phosphonates, thiophosphonates, sulfonates, carboxylates, ionic surfactants and sulfonates and the like.
- Oxidation Inhibitors/Antioxidants reduce the tendency of mineral oils to deteriorate in service, which deterioration is evidenced by the products of oxidation such as sludge, lacquer, and varnish-like deposits on metal surfaces.
- the engine oil composition may contain from about 50 ppm to about 5.00 wt % of at least an antioxidant selected from the group of phenolic antioxidants, aminic antioxidants, or a combination thereof.
- the amount of antioxidants may be between 0.10 to 3.00 wt %.
- the amount of antioxidants may be between about 0.20 to 0.80 wt %.
- An example of an antioxidant used is di-C8-diphenylamine, in an amount of about 0.05 to 2.00 wt % of the total weight of the oil composition.
- Other examples of antioxidants include MoS and Mo oxide compounds.
- antioxidants include hindered phenols; alkaline earth metal salts of alkylphenolthioesters having C5 to C12 alkyl side chains; calcium nonylphenol sulphide; oil soluble phenates and sulfurized phenates; phosphosulfurized or sulfurized hydrocarbons or esters; phosphorous esters; metal thiocarbamates; oil soluble copper compounds known in the art; phenyl naphthyl amines such as phenylene diamine, phenothiazine, diphenyl amine, diarylamine; phenyl-alphanaphthylamine, 2,2'-diethyl-4,4'-dioctyl diphenylamine, 2,2'diethyl-4-t-octyldiphenylamine; alkaline earth metal salts of alkylphenol thioesters, having C5 to C12 alkyl side chains, e.g., calcium nonylphenol sulfide, bar
- the engine oil may comprise an anti-foamant (foam inhibitor) in amounts ranging from about 5 to about 50 ppm.
- anti-foamant fluorosilicone
- examples include alkyl methacrylate polymers, dimethyl silicone polymers, and foam inhibitors of the polysiloxane type, e.g., silicone oil and polydimethyl siloxane, for foam control.
- the anti-foamant may be a mixture of polydimethyl siloxane and fluorosilicone.
- Another example of an anti-foamant may be an acrylate polymer anti-foamant, with a weight ratio of the fluorosilicone antifoamant to the acrylate anti-foamant ranging from about 3: 1 to about 1 :4.
- an anti- foamant may be an anti-foam-effective amount of a silicon-containing anti-foamant such that the total amount of silicon in the engine oil is at least 30 ppm.
- the silicon-containing antifoam agent may be selected from the group consisting of fluorosilicones, polydimethylsiloxane, phenyl-methyl polysiloxane, linear siloxanes, cyclic siloxanes, branched siloxanes, silicone polymers and copolymers, organo-silicone copolymers, and mixtures thereof.
- Anti-wear agents can also be added to the engine oil composition.
- the composition may comprise at least an anti-wear agent selected from phosphates, phosphites, carbamates, esters, sulfur containing compounds, and molybdenum complexes.
- Other representative of suitable antiwear agents are zinc dialkyldithiophosphate, zinc diaryldilhiophosphate, Zn or Mo dithiocarbamates, phosphites, amine phosphates, borated succinimide, magnesium sulfonate, and mixtures thereof.
- the composition may comprise at least a dihydrocarbyl dithiophosphate metal as antiwear and antioxidant agent in amounts of about 0.1 to about 10 wt %.
- the metal may be an alkali or alkaline earth metal, or aluminum, lead, tin, molybdenum, manganese, nickel or copper.
- the engine oil composition may comprise an extreme pressure agent.
- extreme pressure agents include alkaline earth metal borated extreme pressure agents and alkali metal borated extreme pressure agents.
- Other examples include sulfurized olefins, zinc dialky-1 -dithiophosphate (primary alkyl, secondary alkyl, and aryl type), di-phenyl sulfide, methyl tri-chlorostearate, chlorinated naphthalene, fluoroalkylpolysiloxane, lead naphthenate, neutralized or partially neutralized phosphates, di-thiophosphates, and sulfur- free phosphates.
- additives can provide a multiplicity of effects; thus for example, a single additive may act as a dispersant as well as an oxidation inhibitor. These multifunctional additives are well known.
- each additive is typically blended into the base oil in an amount that enables the additive to provide its desired function. It may be desirable, although not essential to prepare one or more additive concentrates comprising additives (concentrates sometimes being referred to as "additive packages") whereby several additives can be added simultaneously to the oil to form the end oil composition.
- the final composition may employ from about 0.5 to about 30 wt % of the concentrate, the remainder being the oil of lubricating viscosity.
- the components can be blended in any order and can be blended as combinations of components.
- Group I Base Oil contain less than 90 percent saturates and/or greater than 0.03 percent sulfur and have a viscosity index greater than or equal to 80 and less than 120 using the ASTM methods specified in Table E-l of American Petroleum Institute Publication 1509.
- Group II Base Oil refers to a base oil which contains greater than or equal to 90% saturates and less than or equal to 0.03% sulfur and has a viscosity index greater than or equal to 80 and less than 120 using the ASTM methods specified in Table E-l of American Petroleum Institute Publication 1509.
- Group 11+ Base Oil refers to a Group II base oil having a viscosity index greater than or equal to 1 10 and less than 120.
- Group III Base Oil refers to a base oil which contains greater than or equal to 90% saturates and less than or equal to 0.03% sulfur and has a viscosity index greater than or equal to 120 using the ASTM methods specified in Table E-l of American Petroleum Institute Publication 1509.
- Fischer-Tropsch derived means that the product, fraction, or feed originates from or is produced at some stage by a Fischer-Tropsch process.
- petroleum derived means that the product, fraction, or feed originates from the vapor overhead streams from distilling petroleum crude and the residual fuels that are the non-vaporizable remaining portion.
- a source of the petroleum derived product, fraction, or feed can be from a gas field condensate.
- multi-grade engine oil refers to an engine oil that has viscosity/temperature characteristics which fall within the limits of two different SAE numbers in SAE J300.
- the present invention is directed to the discovery that multi-grade engine oils meeting the specifications under SAE J300 as revised 2009, including the MRV viscosity specifications, may be prepared from Fischer-Tropsch base oils having a defined cycloparaffin functionality when they are blended with a pour point depressing base oil blending component and an additive package.
- light neutral base oil refers to a base oil with a boiling range from about 700°F to about 800°F, a kinematic viscosity at 100°C from 4 cSt to about 5 cSt.
- intermediate neutral base oil refers to a base oil with a boiling range from about 800°F to about 900°F, a kinematic viscosity at 100°C from 5 cSt to about 8 cSt.
- Highly paraffinic wax means a wax having a high content of n-paraffins, generally greater than 40 wt %, but can be greater than 50 wt %, or even greater than 75 wt %, and less than 100 wt % or 99 wt %.
- highly paraffinic waxes include slack waxes, deoiled slack waxes, refined foots oils, waxy lubricant raffinates, n-paraffin waxes, NAO waxes, waxes produced in chemical plant processes, deoiled petroleum derived waxes, microcrystalline waxes, Fischer-Tropsch waxes, and mixtures thereof.
- derived from highly paraffinic wax means that the product, fraction, or feed originates from or is produced at some stage by from a highly paraffinic wax.
- Representative examples include, but are not limited to, benzene, biphenyl, naphthalene, and the like.
- Molecules with cycloparaffinic functionality mean any molecule that is, or contains as one or more substituents, a monocyclic or a fused multicyclic saturated hydrocarbon group.
- the cycloparaffinic group can be optionally substituted with one or more, such as one to three, substituents.
- Representative examples include, but are not limited to, cyclopropyl, cyclobutyl, cyclohexyl, cyclopentyl, cycloheptyl, decahydronaphthalene, octahydropentalene, (pentadecan-6-yl)cyclohexane, 3,7, 10-tricyclohexylpentadecane, decahydro-l-(pentadecan-6- yl)naphthalene, and the like.
- Molecules with monocycloparaffinic functionality mean any molecule that is a monocyclic saturated hydrocarbon group of three to seven ring carbons or any molecule that is substituted with a single monocyclic saturated hydrocarbon group of three to seven ring carbons.
- the cycloparaffinic group can be optionally substituted with one or more, such as one to three, substituents. Representative examples include, but are not limited to, cyclopropyl, cyclobutyl, cyclohexyl, cyclopentyl, cycloheptyl, (pentadecan-6-yl)cyclohexane, and the like.
- Molecules with multicycloparaffinic functionality mean any molecule that is a fused multicyclic saturated hydrocarbon ring group of two or more fused rings, any molecule that is substituted with one or more fused multicyclic saturated hydrocarbon ring groups of two or more fused rings, or any molecule that is substituted with more than one monocyclic saturated hydrocarbon group of three to seven ring carbons.
- the fused multicyclic saturated hydrocarbon ring group often is of two fused rings.
- the cycloparaffinic group can be optionally substituted with one or more, such as one to three, substituents.
- Brookfield Viscosity ASTM D2983-04a is used to determine the low-shear-rate viscosity of automotive fluid lubricants at low temperatures. The low-temperature, low-shear- rate viscosity of automatic transmission fluids, gear oils, torque and tractor fluids, and industrial and automotive hydraulic oils are frequently specified by Brookfield viscosities.
- Kinematic viscosity is a measurement of the resistance to flow of a fluid under gravity. Many base oils, lubricant compositions made from them, and the correct operation of equipment depends upon the appropriate viscosity of the fluid being used. Kinematic viscosity is determined by ASTM D445-06. The results are reported in mm 2 /s.
- Viscosity index (VI) is an empirical, unitless number indicating the effect of temperature change on the kinematic viscosity of the oil. Viscosity index is determined by ASTM D2270-04.
- Pour point is a measurement of the temperature at which a sample of base oil will begin to flow under carefully controlled conditions. Pour point can be determined as described in ASTM D5950-02. The results are reported in degrees Celsius. Many commercial base oils have specifications for pour point. When base oils have low pour points, the base oils are also likely to have other good low temperature properties, such as low cloud point, low cold filter plugging point, and low temperature cranking viscosity.
- Noack volatility is usually tested according to ASTM D5800-05 Procedure B.
- a more convenient method for calculating Noack volatility and one which correlates well with ASTM D5800-05 is by using a thermogravimetric analyzer (TGA) test by ASTM D6375-05.
- TGA Noack volatility is used throughout the present disclosure unless otherwise stated.
- the base oils of the lubricant composition as disclosed herein also have excellent viscometric properties under low temperature (i.e., cold flow properties) and high shear, making them very useful in multi-grade engine oils.
- the cold-cranking simulator apparent viscosity (CCS VIS) is a test used to measure the viscometric properties of base oils under low temperature and high shear.
- the test method to determine CCS VIS is ASTM D5293-02. Results are reported in mPa-s.
- CCS VIS has been found to correlate with low temperature engine cranking. Specifications for maximum CCS VIS are defined for automotive engine oils by SAE J300, revised in 2009. The maximum CCS VIS for a 0W SAE Viscosity Grade engine oil is 6200 mPa-s at -35°C.
- the phrase "improving cold flow properties" refers to one or more of lowering CCS VIS (cold-cranking simulator apparent viscosity) at -25° C, -30°C or -35° C, lowering pour point and lowering Noack.
- the Mini-Rotary Viscometer (MRV) test ASTM D4684-07, which is related to the mechanism of pumpability, is a low shear rate measurement.
- Slow sample cooling rate is the method's key feature.
- a sample is pretreated to have a specified thermal history which includes warming, slow cooling, and soaking cycles.
- the MRV measures an apparent yield stress, which, if greater than a threshold value, indicates a potential air-binding pumping failure problem.
- the oil may be subject to pumpability failure by a mechanism called "flow limited" behavior.
- An SAE 0W oil for example, is required to have a maximum viscosity of 60,000 mPa-s at -40°C with no yield stress. This method also measures an apparent viscosity under shear rates of 1 to 50 s "1 .
- High temperature high shear rate viscosity is a measure of a fluid's resistance to flow under conditions resembling highly-loaded journal bearings in fired internal combustion engines, typically 1 million s "1 at 150°C.
- HTHS is a better indication of how an engine operates at high temperature with a given lubricant than the kinematic low shear rate viscosities at 100°C.
- the HTHS value directly correlates to the oil film thickness in a bearing.
- SAE J300 2009 contains the current specifications for HTHS measured by ASTM D4683, ASTM D4741, or ASTM D5481.
- An SAE 20 viscosity grade engine oil for example, is required to have a minimum HTHS of 2.6 mPa-s.
- ASTM D5133-05 is used to measure the low temperature, low shear rate, viscosity/temperature dependence of engine oils.
- the low temperature, low shear viscometric behavior of an engine oil determines whether the oil will flow to the sump inlet screen, then to the oil pump, then to the sites in the engine requiring lubrication in sufficient quantity to prevent engine damage immediately or ultimately after cold temperature starting.
- ASTM D5133-05 the Scanning Brookfield Viscosity technique, measures the Brookfield viscosity of a sample as it is cooled at a constant rate of l°C/hour.
- ASTM D5133-05 is intended to relate to the pumpability of an oil at low temperatures.
- the test reports the gelation point, defined as the temperature at which the sample reaches 30,000 mPa-s.
- the gelation index is also reported, and is defined as the largest rate of change of viscosity increase from -5°C to the lowest test temperature.
- the latest API SM/ILSAC GF-4 specifications for passenger car engine oils require a maximum gelation index of 12.
- “Lubricants,” as defined herein, are substances (usually a fluid under operating conditions) introduced between two moving surfaces so to reduce the friction and wear between them.
- Base oils used as motor oils are generally classified by the American Petroleum Institute as being mineral oils (Group I, II, and III) or synthetic oils (Group IV and V). See American Petroleum Institute (API) Publication Number 1509.
- Pul point represents the lowest temperature at which a fluid will pour or flow. See, e.g., ASTM International Standard Test Methods D 5950-96, D 6892- 03, and D 97.
- Cloud point represents the temperature at which a fluid begins to phase separate due to crystal formation. See, e.g., ASTM Standard Test Methods D 5773-95, D 2500, D 5551, and D 5771.
- R n refers to a hydrocarbon group, wherein the molecules and/or molecular fragments can be linear and/or branched.
- C n As defined herein, "C n ,” where “n” is an integer, describes a hydrocarbon molecule or fragment (e.g., an alkyl group) wherein “n” denotes the number of carbon atoms in the fragment or molecule.
- bio refers to an association with a renewable resource of biological origin, such as resource generally being exclusive of fossil fuels.
- Yubase 4 and Yubase 6 are base oils defined as presented in Table 1 shown below.
- the diester- free base oil blend was prepared by mixing 82.67 wt% Yubase 4 and 17.33 wt% Yubase 6.
- the base oil component with diester was prepared by mixing 69.7 wt% Yubase 4, 13.8 wt% Yubase 6, and 16.5 wt% diester of Formula I wherein Ri and R2 are combined to have a carbon number of C12 and R 3 and R4 are both C12. Both samples were submitted for standard base oil testing, including API gravity, viscosity at 40°C and 100°C, Viscosity Index, pour point, cloud point, Noack volatility, cold cranking viscosity, and Bromine number.
- This example serves to illustrate the base oil blends with the diesters of the present invention, a single comparative without diester and a second comparative with a commercially available ester (i.e., Esterex A51) with the analytics presented in Table 4 below.
- Diester A is a diester of Formula I, wherein Ri and R2 are combined to have a carbon number of C12 and R 3 and R4 are both C12.
- Diester B2 is a diester of Formula I, wherein Ri and R2 are combined to have a carbon number of C12 and R 3 and R4 are both independently C6-C1 0 .
- Table 3 were prepared in a similar manner as those of Example 1 herein. Table 4
- This example serves to illustrate the diesters prepared and their respective properties as presented in Table 5.
- This example serves to illustrate the Noack and CCS Viscosity of the diesters of the present invention as compared to the current commercial esters and other Group II and III bases oils as presented in Table 6 and Figure 1.
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Abstract
La présente invention concerne généralement des préparations d'huile moteur multigrade, à base de diester. Les diesters employés présentent un certain nombre d'avantages en termes d'efficacité dans des applications de lubrifiant - parmi ceux-ci : la biodégradabilité, l'efficacité aux températures extrêmes, la stabilité à l'oxydation, la solubilité pour des additifs et des précurseurs de dépôt et de boue, les points éclair et de feu. Cependant, l'utilisation d'ester dans des lubrifiants a été plutôt limitée due à leur coût élevé. Nous utilisons des nouveaux diesters brevetés, qui sont différents de façon structurale des diesters classiques et qui sont fabriqués à partir d'acides gras et d'alpha oléfines dans des étapes de traitement simples, présentant cependant une efficacité similaire à des esters lubrifiants plus classiques.
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Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
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US20080194444A1 (en) * | 2007-02-12 | 2008-08-14 | Chevron U.S.A. Inc. | Diester-Based Lubricants and Methods of Making Same |
US7867959B2 (en) | 2008-01-31 | 2011-01-11 | Chevron U.S.A. Inc. | Synthesis of diester-based biolubricants from epoxides |
US20110053817A1 (en) * | 2007-02-12 | 2011-03-03 | Chevron U.S.A. Inc. | Multi-grade engine oil formulations comprising a bio-derived ester component |
US20130029893A1 (en) * | 2011-07-27 | 2013-01-31 | Chevron U.S.A. | Process for Preparing a Turbine Oil Comprising an Ester Component |
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2014
- 2014-05-02 WO PCT/US2014/036633 patent/WO2014179726A1/fr active Application Filing
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
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US20080194444A1 (en) * | 2007-02-12 | 2008-08-14 | Chevron U.S.A. Inc. | Diester-Based Lubricants and Methods of Making Same |
US7871967B2 (en) | 2007-02-12 | 2011-01-18 | Chevron U.S.A. Inc. | Diester-based lubricants and methods of making same |
US20110053817A1 (en) * | 2007-02-12 | 2011-03-03 | Chevron U.S.A. Inc. | Multi-grade engine oil formulations comprising a bio-derived ester component |
US7867959B2 (en) | 2008-01-31 | 2011-01-11 | Chevron U.S.A. Inc. | Synthesis of diester-based biolubricants from epoxides |
US20130029893A1 (en) * | 2011-07-27 | 2013-01-31 | Chevron U.S.A. | Process for Preparing a Turbine Oil Comprising an Ester Component |
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