Reaction products of organic amines and glycidol and their use as friction modifiers

Abstract

The present disclosure relates generally to friction modifiers comprising the reaction product of an organic amine and glycidol and their use in non-aqueous lubricant compositions. Also provided are methods for reducing friction between sliding components of an engine by contacting the engine with the non-aqueous lubricant composition.

Description

[0001] Cross-reference to related applications

[0002] This application claims priority to U.S. Provisional Application No. 63 / 126,112, filed December 16, 2020. The referenced application is incorporated herein by reference.

[0003] Statement regarding federally funded research or development

[0004] not applicable. Technical Field

[0005] field

[0006] This disclosure generally relates to friction modifiers comprising reaction products of: (i) organic amines selected from alkylamines, alicyclic amines, aryl amines, alkylalkoxylated monoamines and mixtures thereof; and (ii) glycidyl; and relates to the use of the friction modifier in non-aqueous lubricant compositions for reducing friction between sliding parts of an engine. Background Technology

[0007] background

[0008] Engine oil plays a vital role in lubricating various sliding components in an engine, including, for example, piston rings / cylinder liners, crankshaft and connecting rod bearings, and valve mechanisms such as camshafts and valve tappets. Engine oil also functions to cool the engine interior, disperse combustion products, and inhibit rust and corrosion.

[0009] The primary consideration for engine oil is preventing wear and seizing of engine components. Most lubricated engine components are in a state of fluid lubrication. However, valve systems and the top and bottom dead centers of pistons may be in a state of boundary and / or film lubrication. Friction between these engine components can lead to significant energy loss, thereby reducing fuel efficiency. To improve fuel efficiency, friction between engine components (such as valve systems and piston parts) must be reduced.

[0010] Organic friction modifiers are typically long molecules with straight hydrocarbon chains, consisting of at least 10 carbon atoms and a polar group at one end. The polar end group is one of the controlling factors for the molecule's effectiveness as a friction modifier. Common organic friction modifiers are esters of fatty acids and polyols, fatty acid amides, amines derived from fatty acids, and organic dithiocarbamates or dithiophosphate compounds. For example, EP1367116, EP0799883, EP0747464, US3,933,659, and EP335701 disclose various organic friction modifiers already used in lubricants. Glyceryl monooleate (GMO) is one of the most commonly used organic friction modifiers in engine lubricant compositions, as described, for example, in the following documents: US Patent Nos. 5,885,942; 5,866,520; 5,114,603; 4,957,651; and 4,683,069.

[0011] Given the increasing demands for engine fuel economy, it remains necessary to further improve the friction reduction and fuel economy of internal combustion engines using lubricant compositions. Therefore, it is desirable to improve the friction-reducing properties of known friction modifiers (such as glyceryl monooleate) that are already commonly used in the field. Summary of the Invention

[0012] Overview

[0013] This disclosure relates to a friction modifier comprising a reaction product of the following substances: (i) an amine selected from alkylamines, alicyclic amines, arylamines, alkylalkoxylated monoamines, and mixtures thereof; and (ii) glycidyl ether. This friction modifier can be combined with a base oil to form a non-aqueous lubricant composition for use in lubricating engines.

[0014] A method for reducing friction between sliding parts of an engine is also provided, which is carried out by bringing at least one of the sliding parts into contact with the non-aqueous lubricant composition.

[0015] Finally, a friction-reducing additive package is provided, which comprises the reaction product of this disclosure and one or more additives. Attached Figure Description

[0016] Brief description of the attached figures

[0017] Figure 1 and 2 The coefficient of friction of commercially available oils at 130°C is described for use alone or in combination with the friction modifier of the present invention.

[0018] Detailed instructions

[0019] The following terms will have the following meanings:

[0020] The term “comprising” and its derivatives are not intended to exclude the presence of any additional components, steps, or procedures, whether or not they are disclosed herein. For the avoidance of any doubt, all compositions claimed herein by using the term “comprising” may contain any additional additives or compounds unless otherwise indicated. In contrast, the term “consistently composed of” if it appears herein excludes from the scope of any subsequent statement any other components, steps, or procedures except those not essential for operability, and the term “composed of” if used excludes any components, steps, or procedures not specifically described or listed. Unless otherwise stated, the term “or” refers individually or in any combination to the listed members.

[0021] The articles “a” and “an” used herein refer to one or more (i.e., at least one or more) grammatical objects of that article. For example, “a friction modifier” refers to one or more friction modifiers. Phrases such as “in one embodiment”, “according to one embodiment,” etc., generally refer to a specific feature, structure, or characteristic following the phrase that is included in at least one embodiment of this disclosure and may be included in more than one embodiment of this disclosure. Importantly, such phrases do not necessarily refer to the same aspect. If the specification states that a component or feature “may,” “can,” “could,” or “might” is included or has a certain characteristic, it is not required that the specific component or feature is included or has that characteristic.

[0022] The term “about” as used herein allows for a degree of variability in the value or range, for example, it may be within 10%, 5%, or 1% of the stated value or the stated range limit.

[0023] Values ​​expressed in range format should be interpreted flexibly, including not only the values ​​explicitly listed as the boundaries of the range, but also all individual values ​​or subranges contained within the range, as if each value and subrange were explicitly listed. For example, a range such as 1 to 6 should be considered to have specifically disclosed subranges, such as 1 to 3, 2 to 4, 3 to 6, etc., as well as individual numbers within that range, such as 1, 2, 3, 4, 5, and 6. This applies regardless of the width of the range.

[0024] The terms "preferred" and "ideal" refer to embodiments that provide certain benefits in certain circumstances. However, other embodiments may also be preferred in the same or other circumstances. Furthermore, the statement of one or more preferred embodiments does not imply that other embodiments are useless, nor is it intended to exclude other embodiments from the scope of this disclosure.

[0025] The term "substantially free" refers to a composition in which the presence of a particular compound or structural moiety has no material effect on the composition. In some embodiments, "substantially free" may refer to a composition in which the presence of a particular compound or structural moiety in the composition is less than 2% by weight, or less than 1% by weight, or less than 0.5% by weight, or less than 0.1% by weight, or less than 0.05% by weight, or even less than 0.01% by weight based on the total weight of the composition, or where no amount of the particular compound or structural moiety is present in the respective composition.

[0026] When substituents are specified by their conventional chemical formula written from left to right, they also include chemically identical substituents produced by structures written from right to left; for example, -CH2O- is equivalent to -OCH2-.

[0027] The term "alkyl" refers to a straight-chain or branched saturated hydrocarbon group having 1 to about 100 carbon atoms. In some embodiments, the alkyl substituent may be a lower alkyl group. The term "lower" refers to an alkyl group having 1 to 3 carbon atoms. Examples of "lower alkyl" include, but are not limited to, methyl, ethyl, n-propyl, and isopropyl.

[0028] The term "alicyclic" refers to an alicyclic substituent as known in the art, and may have about 3 to about 12 cyclic carbon atoms or about 3 to 10 cyclic carbon atoms, including but not limited to cyclopentyl and cyclohexyl.

[0029] The term "aryl" refers to an aryl substituent or functional group as known in the art, such as, but not limited to, any substituent or functional group derived from an aromatic ring, including but not limited to phenyl, naphthyl, thiophene, and indole. The aryl group may be substituted with one or more alkyl groups on the ring.

[0030] The terms “optional” or “optionally” mean that the event or situation described below may or may not occur, and the description includes instances where the event or situation occurs and instances where it does not occur.

[0031] This disclosure generally relates to a friction modifier comprising a reaction product of the following substances: (i) an organic amine selected from alkylamines, alicyclic amines, arylamines, alkylalkoxylated monoamines and mixtures thereof, and (ii) glycidyl ether.

[0032] This disclosure also relates to a friction-reducing additive package comprising the friction modifier disclosed herein and one or more additives.

[0033] This disclosure further relates to a non-aqueous lubricant composition comprising a base oil and the friction modifier disclosed herein.

[0034] This disclosure also relates to a method for reducing friction in an engine, which is carried out by bringing the sliding parts of the engine into contact with the non-aqueous lubricant composition.

[0035] It has been surprisingly discovered that when the friction modifier of this disclosure is combined with a base oil to form a non-aqueous lubricant composition, the lubricity of the non-aqueous lubricant composition is increased, thereby greatly reducing wear on engine surfaces, engine parts or components, or engine component parts that come into contact with or have come into contact with the non-aqueous lubricant composition.

[0036] According to one embodiment, the organic amine is an alkylamine having the formula N(R1)3, wherein each R1 is hydrogen or alkyl, provided that at least one R1 is hydrogen. In one embodiment, at least one R1 is C1-C 50 Alkyl or C1-C 30 Alkyl groups. Examples of alkylamines include, but are not limited to, ethylamine, propylamine, isopropylamine, butylamine, ethylenediamine, dipropylamine, octamethylenediamine, octylamine, tetramethylethylenediamine, tridecaneamine, 2-ethylhexylamine, tetraethylenepentaneamine; hexamethylenediamine, dodecaneamine, cocoamine, oleamine, tallow amine, pentadecaneamine, stearamine, and soyamine.

[0037] In another embodiment, the organic amine is an alicyclic amine. Examples of alicyclic amines include, but are not limited to, cyclopentylamine, cyclohexylamine, cycloheptylamine, cyclododecylamine, 4-methylcyclohexylamine, N,N-dimethylcyclohexylamine, hexamethyleneimine, piperidine, and isophorone diamine.

[0038] In another embodiment, the organic amine is an aryl amine. Examples of aryl amines include, but are not limited to, aniline, diaminotoluene, diphenylalanine, N-phenylbenzylamine, and toluidine. In another embodiment, the aryl amine is C1-C 50 Group or C1-C 20 Alkyl substitution.

[0039] In yet another embodiment, the organic amine is an alkylalkoxylated monoamine comprising an amino group attached to the end of a monoether or polyether backbone. As discussed further below, the monoether or polyether backbone is based on (i.e., further defined by) an alkylene oxide group, such as propylene oxide (PO), ethylene oxide (EO), butylene oxide (BO), and mixtures thereof. In mixed structures, the ratio can be any desired ratio and can be arranged in a block form (e.g., repeating or alternating) or randomly distributed. In a non-limiting example, in a mixed EO / PO structure, the EO:PO ratio can range from about 1:1 to about 1:50, and vice versa. Thus, alkoxylated monoamines can be substantially defined as mono- or poly(ethylene oxide), mono- or poly(propylene oxide), and / or mono- or poly(butylene oxide). The molecular weight of the alkylalkoxylated monoamine can vary and can range up to about 6000.

[0040] In one particular embodiment, the alkylalkoxylated monoamine is a compound having the following general formula:

[0041]

[0042] Where Z is alkyl, alicyclic, or aryl, each Z' is independently hydrogen, methyl, or ethyl, and e is an integer from about 1 to about 100. In some embodiments, Z is C1-C 40 Alkyl or C1-C 20 Group. In yet another embodiment, Z is optionally separated by C1-C. 40 Alkyl or C1-C 20 Alkyl-substituted aryl groups. In other embodiments, e is an integer from about 1 to about 50, from about 1 to about 20, or from about 1 to about 15. Specific examples include, but are not limited to, compounds having the following formula:

[0043]

[0044] Where Me is methyl, Et is ethyl; f is an integer from about 13 to about 14; and e is an integer from about 2 to about 3. Such polyoxyalkylene monoamines included in the above formulas include... M-600 amine, having formula (1), wherein the PO / EO molar ratio is 9 / 1 and the molecular weight is about 600; M-1000 amine, having formula (1), wherein the PO / EO molar ratio is 3 / 19 and the molecular weight is about 1000; M-2005, having formula (1), wherein the PO / EO molar ratio is 29 / 6 and the molecular weight is about 2000; M-2070 amine, having formula (1), wherein the PO / EO molar ratio is 10 / 31 and the molecular weight is about 2000; FL-1000 amine, having formula (3), wherein f is 14 and Me or Et is methyl; C-300 amine, having formula (4), wherein e is about 2.5; XTJ-435 amine, having formula (2); and XTJ-436 amine, having formula (3), wherein Me or Et is methyl and f is about 13.5.

[0045] Depending on the starting materials, the reaction between the organic amine and glycidyl ether can be carried out at a temperature of about 25°C to about 300°C and a pressure of about 1 psi to about 2000 psi for a period of about 0.5 hours to 24 hours. In one embodiment, the temperature is maintained in the range of about 125°C to about 175°C. The reaction can be carried out at a molar ratio of organic amine to glycidyl ether of about 0.1 to about 2. In another embodiment, the amounts of organic amine and glycidyl ether are selected to produce at least one reaction product (or compound) having the following formula:

[0046] Amine monoglycidyl reaction product

[0047]

[0048]

[0049] Z, Z', and e are defined as above. In one implementation, R is C1-C 50 Alkyl or C1-C 25 Alkyl. In another embodiment, R is cyclopentyl or cyclohexyl. In yet another embodiment, R is phenyl or C1-C6. 20 Alkyl-substituted phenyl. In yet another embodiment, R is an alkylalkoxy group, wherein Z is C1-C. 20Alkyl group, each Z' being independently hydrogen or methyl, and e being an integer from about 1 to about 50 or from about 1 to about 25. Therefore, in one embodiment, the friction modifier is selected from compounds having formula (5), compounds having formula (6), compounds having formula (7), compounds having formula (8), compounds having formula (9), and mixtures thereof. In a preferred embodiment, the friction modifier comprises one of the following substances: 2,3-dihydroxypropylamine, 1,3-dihydroxypropylamine, bis(2,3-dihydroxypropyl)amine, bis(1,3-dihydroxypropyl)amine, and (2,3-dihydroxypropyl)(1,3-dihydroxypropyl)amine.

[0050] The reaction products of this disclosure have been found to be surprisingly effective as friction modifiers in non-aqueous lubricant compositions. Therefore, this disclosure also provides non-aqueous lubricant compositions comprising a base oil and a friction modifier comprising the reaction products according to this disclosure.

[0051] According to one embodiment, the total amount of base oil incorporated into the non-aqueous lubricant composition may be at least about 50% by weight, or at least 60% by weight, or at least 70% by weight, or at least 80% by weight, or at least 90% by weight, or at least about 95% by weight, based on the total weight of the non-aqueous lubricant composition.

[0052] In another embodiment, the amount of base oil incorporated into the non-aqueous lubricant composition may be in the range of about 50% to about 99% by weight, and in other embodiments about 60% to about 92% by weight, in still other embodiments about 70% to about 90% by weight, and in yet another embodiment about 75% to about 88% by weight, relative to the total weight of the non-aqueous lubricant composition.

[0053] In another embodiment, the total amount of the friction modifier comprising the reaction product of the present disclosure incorporated into the non-aqueous lubricant composition is in the range of about 0.0001% by weight to about 20% by weight, and in other embodiments from about 0.001% by weight to 10% by weight, in still other embodiments from about 0.01% by weight to about 5% by weight, and in other embodiments from about 0.1% by weight to about 1.5% by weight, relative to the total weight of the non-aqueous lubricant composition.

[0054] In some embodiments, the base oils that can be used in this disclosure include known synthetic oils and mineral oils and mixtures thereof.

[0055] Examples of synthetic oils include alkyl esters of dicarboxylic acids, polyglycols and alcohols, polyalphaolefins including polybutene, alkylbenzenes, organic esters of phosphoric acid, and polysilicone oils. Synthetic oils include hydrocarbon oils, such as polymerized and copolymerized olefins (e.g., polybutene, polypropylene, propylene-isobutylene copolymers, etc.); poly(1-hexene), poly(1-octene), poly(1-decene), etc., and mixtures thereof; alkylbenzenes (e.g., dodecylbenzene, tetradecylbenzene, dinonylbenzene, di-(2-ethylhexyl)benzene, etc.); polyphenylene (e.g., biphenyl, terphenyl, alkylated polyphenylene, etc.); alkylated diphenyl ethers and alkylated diphenyl sulfides and their derivatives, analogues, and homologues, etc.

[0056] Another class of known synthetic oils that can be used consists of epoxide polymers and interpolymers and their derivatives whose terminal hydroxyl groups have been modified through esterification, etherification, etc. Examples of such oils are those prepared by polymerization of ethylene oxide or propylene oxide, using alkyl and aryl ethers of these polyoxyethylene polymers (e.g., methyl-polyisopropylene glycol ethers with an average molecular weight of about 1000, diphenyl ethers of polyethylene glycol with a molecular weight of about 500-1000, diethyl ethers of polypropylene glycol with a molecular weight of about 1000-1500, etc.) or their monocarboxylic acid esters and polycarboxylic acid esters, such as acetate esters, mixed C3-C8 fatty acid esters, or oxyacid diesters of tetraethylene glycol.

[0057] Another class of synthetic oils that can be used includes esters of dicarboxylic acids (such as phthalic acid, succinic acid, alkyl succinic acid, alkenyl succinic acid, maleic acid, azelaic acid, octanoic acid, sebacic acid, fumaric acid, adipic acid, linoleic acid dimer, malonic acid, alkyl malonic acid, alkenyl malonic acid, etc.) and various alcohols (such as butanol, hexanol, dodecyl alcohol, 2-ethylhexanol, ethylene glycol, diethylene glycol monoether, propylene glycol, etc.). Specific examples of these esters include dibutyl adipate, di(2-ethylhexyl) sebacate, di-n-hexyl fumarate, dioctyl sebacate, diisooctyl azelate, diisodecyl azelate, dioctyl phthalate, didecyl phthalate, di(eicosyl) sebacate, 2-ethylhexyl diester of linoleic acid dimer, and complex esters formed by reacting one mole of sebacate with two moles of tetraethylene glycol and two moles of 2-ethylhexanoic acid, etc.

[0058] Esters that can be used as synthetic oils also include those prepared from the following substances: C5-C 12 Monocarboxylic acids and polyols, as well as polyol ethers, such as neopentyl glycol, trimethylolpropane, pentaerythritol, dipentaerythritol, tripentaerythritol, etc.

[0059] The base oil may contain a minor or major amount of polyalphaolefin (PAO). Typically, this PAO is derived from a monomer having about 4 to about 30, about 4 to about 20, or about 6 to about 16 carbon atoms. Useful examples of PAO include those derived from octene, decene, mixtures thereof, etc. PAO may have a viscosity of about 2 to about 15 centistokes (cSt) at 100°C, or about 3 to about 12 cSt, or about 4 to about 8 cSt. Examples of PAO include polyalphaolefins with a viscosity of 4 cSt at 100°C, polyalphaolefins with a viscosity of 6 cSt at 100°C, and mixtures thereof. Mixtures of mineral oil with the above-mentioned PAO can be used.

[0060] The base oil can be derived from Fischer-Tropsch hydrocarbons. Fischer-Tropsch hydrocarbons are produced using a Fischer-Tropsch catalyst from a synthesis gas containing H2 and CO. These hydrocarbons typically require further processing before they can be used as base oils. For example, the hydrocarbons can be hydroisomerized using the methods disclosed in U.S. Patent Nos. 6,103,099 or 6,180,575; hydrocracking and hydroisomerized using the methods disclosed in U.S. Patent Nos. 4,943,672 or 6,096,940; dewaxed using the methods disclosed in U.S. Patent No. 5,882,505; or hydroisomerized and dewaxed using the methods disclosed in U.S. Patent Nos. 6,013,171, 6,080,301, or 6,165,949.

[0061] Unrefined, refined, and re-refined oils of the types disclosed herein, whether mineral or synthetic (and mixtures of two or more of these substances), can be used in base oils. Unrefined oils are those obtained directly from natural or synthetic sources without further purification. Examples include shale oil obtained directly from a dry distillation operation, petroleum obtained directly from primary distillation, or esterified oil obtained directly from an esterification process and used without further treatment. Refined oils are similar to unrefined oils, except that they undergo further processing in one or more purification steps to improve one or more properties. Many such purification techniques are known to those skilled in the art, such as solvent extraction, double distillation, acid or alkali extraction, filtration, percolation, etc. Re-refined oils are obtained by applying methods similar to those used to obtain refined oils that are already in operation. Such re-refined oils are also called regenerated oils or reprocessed oils and are typically subjected to additional treatment using techniques designed to remove waste additives, contaminants, and oil decomposition products.

[0062] Mineral oils include liquid petroleum and solvent- or acid-treated mineral lubricating oils of the alkanes, cycloalkanes, or mixed alkanes / cycloalkanes types, which may be further refined by hydrorefining processes and / or dewaxing.

[0063] Naphthenic base oils have low viscosity index (VI) (typically 40-80) and low pour point. These base oils are produced from feedstocks rich in naphthenes and low in wax content, and are primarily used in lubricants where color and color stability are important, while VI and oxidation stability are of secondary importance.

[0064] Alkane base oils have high VI (typically >95) and high pour points. These base oils are produced from alkane-rich feedstocks and are used in lubricants where VI and oxidation stability are important.

[0065] In some embodiments, the base oil comprises mineral oil and / or synthetic oil containing more than 80% by weight of saturates, and in other embodiments contains more than 90% by weight of saturates, as measured according to ASTM D2007. In other embodiments, the base oil contains less than 1.0% by weight of sulfur, and in other embodiments contains less than 0.1% by weight of sulfur, calculated as elemental sulfur and measured according to ASTM D2622, ASTM D4294, ASTM D4927, or ASTM D3120.

[0066] As will be readily understood by those skilled in the art, the viscosity of base oils depends on the application. Therefore, the viscosity of base oils used herein is typically in the range of about 2 cSt to about 2000 cSt at 100°C. Typically, base oils used alone as engine oils will have a kinematic viscosity range of about 2 cSt to about 30 cSt at 100°C, about 3 cSt to about 16 cSt in some embodiments, and about 4 cSt to about 12 cSt in other embodiments. They will be selected or blended according to the desired end use and additives in the finished oil to obtain the desired grade of engine oil, such as lubricant compositions having SAE viscosity grades of 0W, 0W-20, 0W-30, 0W-40, 0W-50, 0W-60, 5W, 5W-20, 5W-30, 5W-40, 5W-50, 5W-60, 10W, 10W-20, 10W-30, 10W-40, 10W-50, 15W, 15W-20, 15W-30, or 15W-40. Base oils used as gear oils may have a viscosity range of about 2 cSt to about 2000 cSt at 100°C.

[0067] This non-aqueous lubricant composition can be used to lubricate virtually any spark-ignition or compression-ignition internal combustion engine, including automobile and truck engines, two-stroke engines, diesel engines, aircraft piston engines, marine and railway engines, etc. Non-aqueous lubricant compositions for gas engines, alcohol (e.g., methanol) powered engines, stationary engines, turbines, etc., are also envisioned. This non-aqueous lubricant composition can also be used as an automatic transmission fluid, gear lubricant, compressor lubricant, metalworking lubricant, or hydraulic fluid.

[0068] The non-aqueous lubricant composition may further comprise additional additives such as antioxidants, anti-wear additives, detergents, dispersants, secondary friction modifiers (which may include one or more other friction modifiers), viscosity index improvers, pour point depressants, corrosion inhibitors, defoamers, and seal fixes or seal compatibility agents, mixtures thereof. Examples of such additives can be found, for example, in U.S. Patent Nos. 5,498,809 and 7,696,136, the relevant contents of each of which are incorporated herein by reference; however, those skilled in the art will clearly understand that this constitutes only a partial list of available lubricant additives. It is also well known that an additive can provide or improve more than one property; for example, an anti-wear agent may also act as an anti-fatigue and / or extreme pressure additive.

[0069] The readily available antioxidants include those selected from amine antioxidants and / or phenolic antioxidants. In one embodiment, the antioxidant is present in an amount of 0.1% by weight to about 5.0% by weight, while in other embodiments the amount is 0.3% by weight to about 3.0% by weight, based on the total weight of the non-aqueous lubricant composition.

[0070] Examples of readily available amine antioxidants include alkylated diphenylamine, phenyl-α-naphthylamine, phenyl-p-naphthylamine, and alkylated α-naphthylamine.

[0071] In one embodiment, the amine antioxidant includes dialkyl diphenylamines, such as p,p'-dioctyl-diphenylamine, p,p'-di-a-methylbenzyl-diphenylamine, and Np-butylphenyl-N-p'-octylaniline; monoalkyl diphenylamines, such as monotert-butyldiphenylamine and monooctyldiphenylamine; bis(dialkylphenyl)amines, such as di-(2,4-diethylphenyl)amine and di-(2-ethyl-4-nonylphenyl)amine; and alkylphenyl... -1-naphthylamines, such as octylphenyl-1-naphthylamine and n-tert-dodecylphenyl-1-naphthylamine, 1-naphthylamine, arylnaphthylamines, such as phenyl-1-naphthylamine, phenyl-2-naphthylamine, N-hexylphenyl-2-naphthylamine and N-octylphenyl-2-naphthylamine, phenylenediamines, such as N,N'-diisopropyl-p-phenylenediamine and N,N'-diphenyl-p-phenylenediamine, and phenothiazines, such as phenothiazines and 3,7-dioctylphenothiazines.

[0072] Examples of readily available phenolic antioxidants include C7-C9 branched alkyl esters of 3,5-bis(1,1-dimethyl-ethyl)-4-hydroxyphenylpropionic acid, 2-tert-butylphenol, 2-tert-butyl-4-methylphenol, 2-tert-butyl-5-methylphenol, 2,4-di-tert-butylphenol, 2,4-dimethyl-6-tert-butylphenol, 2-tert-butyl-4-methoxyphenol, 3-tert-butyl-4-methoxyphenol, 2,5-di-tert-butylhydroquinone, 2,6-di-tert-butyl-4-alkylphenol, such as 2,6-di-tert-butylphenol, 2,6-di-tert-butyl-4-methylphenol and 2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-alkoxyphenol, such as 2,6-di-tert-butyl- 4-Methoxyphenol and 2,6-di-tert-butyl-4-ethoxyphenol, 3,5-di-tert-butyl-4-hydroxybenzyl mercaptooctyl acetate, alkyl-3-(3,5-di-tert-butyl-A-hydroxyphenyl)propionate, such as n-octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, n-butyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate and 2'-ethylhexyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 2,6-di-tert-butyl-A-dimethylamino-p-cresol, 2,2'-methylenebis(4-alkyl-6-tert-butylphenol), such as 2,2'-methylenebis(4-methyl-6-tert-butylphenol and 2,2-methylenebis(4-ethyl-6-tert-butylphenol) -tert-butylphenol), bisphenols, such as 4,4'-butylidene bis(3-methyl-6-tert-butylphenol, 4,4'-methylene bis(2,6-tert-butylphenol), 4,4'-bis(2,6-di-tert-butylphenol), 2,2-(di-p-hydroxyphenyl)propane, 2,2-bis(3,5-di-tert-butyl-4-hydroxyphenyl)propane, 4,4'-cyclohexylene bis(2,6-tert-butylphenol), hexamethylene glycol-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], triethylene glycol bis[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate], 2,2'-thio-[diethyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 3,9-bis[1 1-Dimethyl-2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]ethyl]2,4,8,10-tetraoxaspiro[5,5]undecane, 4,4'-thiobis(3-methyl-6-tert-butylphenol) and 2,21-thiobis(4,6-di-tert-butylresorcinol), polyphenols, such as tetra[methylene-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]methane, 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, bis-[3,3'-bis(4'-hydroxy-3'-tert-butylphenyl)butyrate]diol ester, 2-(3',5'-Di-tert-butyl-4-hydroxyphenyl)methyl-4-(2',4'-di-tert-butyl-3'-hydroxyphenyl)methyl-6-tert-butylphenol and 2,6-bis(2'-hydroxy-3'-tert-butyl-5'-methylbenzyl)-4-methylphenol, as well as p-tert-butylphenol-formaldehyde condensate and p-tert-butylphenol-acetaldehyde condensate.

[0073] In another embodiment, the non-aqueous lubricant composition may comprise a single zinc dithiophosphate or a combination of two or more zinc dithiophosphates as an anti-wear additive, each zinc dithiophosphate being selected from dialkyl-, diaryl-, or alkylaryl-zinc dithiophosphate. The non-aqueous lubricant composition may typically contain about 0.4% by weight to about 1.0% by weight of zinc dithiophosphate, based on the total weight of the non-aqueous lubricant composition. Additional or alternative known anti-wear additives may also be conveniently used in the non-aqueous lubricant composition.

[0074] Detergents that can be used in this non-aqueous lubricant composition include one or more salicylates and / or phenolates and / or sulfonates. However, since the organic and inorganic alkali salts used as detergents can contribute to the sulfuric acid ash content of the non-aqueous lubricant composition, in one embodiment, the amount of such additives is minimized. Furthermore, salicylates are preferred to maintain a low sulfur level. Therefore, in one embodiment, the non-aqueous lubricant composition may contain one or more salicylates. The amount of the detergent may be from about 0.05% by weight to about 12.5% ​​by weight, in some embodiments from about 1.0% by weight to about 9.0% by weight, and in other embodiments from about 2.0% by weight to about 5.0% by weight, based on the total weight of the non-aqueous lubricant composition.

[0075] Second friction modifiers, which may contain one or more additional friction modifiers, may be used, including metal-based friction modifiers comprising one or more organomolybdenum compounds, such as molybdenum dialkyldithiocarbamate, molybdenum dialkyldithiophosphate, molybdenum disulfide, trimolybdenum dialkyldithiocarbamate clusters, non-sulfur molybdenum compounds, etc.; for example, molybdenum dialkyldithiocarbamate friction modifiers may be present. Many of these molybdenum compounds are well known and many are commercially available. Second friction modifiers that may also be present include organic fatty acids and derivatives of organic fatty acids, amides, imides, and other organometallic substances, such as zinc and boron compounds, etc. The amount of these second friction modifiers that may be added to the non-aqueous lubricant composition ranges from about 0.001% by weight to about 5% by weight, based on the total weight of the non-aqueous lubricant composition.

[0076] The non-aqueous lubricant compositions disclosed herein may additionally include an ashless dispersant, which may be blended in an amount of about 5% to about 15% by weight based on the total weight of the non-aqueous lubricant composition.

[0077] Examples of ashless dispersants that can be used include polyolefin succinimide and polyolefin succinate. In one embodiment, the ashless dispersant comprises borate succinimide.

[0078] Examples of viscosity index improvers that can be readily used in the non-aqueous lubricant compositions of this disclosure include styrene-butadiene copolymers, styrene-isoprene star copolymers, and polymethyl methacrylate copolymers and ethylene-propylene copolymers. Based on the total weight of the non-aqueous lubricant composition, such viscosity index improvers can be readily used in amounts from about 1% to about 20% by weight.

[0079] Polymethacrylates can be conveniently used in the non-aqueous lubricant compositions of the present invention as an effective pour point depressant.

[0080] In addition, compounds such as alkenyl succinic acid or its ester moiety, benzotriazole compounds and thiadiazole compounds can be conveniently used as corrosion inhibitors in the non-aqueous lubricant compositions disclosed herein.

[0081] Compounds such as polysiloxane, dimethyl polycyclohexane, and polyacrylate can be conveniently used as defoamers in the non-aqueous lubricant compositions disclosed herein.

[0082] Compounds that can be readily used in the non-aqueous lubricant compositions disclosed herein as sealing fixatives or sealing compatibility agents include, for example, commercially available aromatic esters.

[0083] As described above, the non-aqueous lubricant composition may contain any number of these additives. Therefore, in some embodiments, the final non-aqueous lubricant composition of this disclosure typically comprises a combination of additives, including the reaction product according to this disclosure and other common additives, at a concentration of about 0.1% by weight to about 30% by weight, for example, about 0.5% by weight to about 10% by weight, based on the total weight of the non-aqueous lubricant composition. In other embodiments, the combined reaction product and additives are present in an amount of about 1% by weight to about 5% by weight, based on the total weight of the non-aqueous lubricant composition. The oil concentrate of the reaction product and additives may contain about 30% by weight to about 75% by weight of the additives, based on the total weight of the non-aqueous lubricant composition.

[0084] According to another embodiment, a non-aqueous lubricant composition is provided, comprising: A) a base oil comprising about 70% to about 99.9% by weight based on the total weight of the non-aqueous lubricant composition; B) a friction modifier as disclosed herein; and C) one or more additional additives, wherein the combined amount of B) and C) present in the composition comprises about 0.1% to about 30% by weight based on the total weight of the non-aqueous lubricant composition.

[0085] In another embodiment, the base oil may be present in an amount of about 90% by weight to about 99.5% by weight, and the combined amount of B) and C) is about 0.5% by weight to about 10% by weight; and in another embodiment, the base oil is present in an amount of about 95% by weight to about 99% by weight, and the combined amount of B) and C) is about 1% by weight to about 5% by weight, based on the total weight of the non-aqueous lubricant composition.

[0086] Friction modifiers containing the reaction products of this disclosure can be added directly to base oils or in combination with one or more additives. Therefore, in one embodiment, a friction-reducing additive package is provided, comprising a friction modifier containing the reaction products of this disclosure and one or more additives. Friction modifiers containing the reaction products of this disclosure can also be added to pre-formulated non-aqueous lubricant compositions that already contain all or most of the other formulation components and additives.

[0087] Because friction modifiers containing the reaction products of this disclosure exhibit surprisingly improved anti-friction properties, the non-aqueous lubricant compositions of this disclosure can be used to improve the fuel economy of gas engines and diesel engines. Therefore, a method is also provided to improve the anti-friction properties of a non-aqueous lubricant composition by adding a friction modifier containing the reaction products of this disclosure to a non-aqueous lubricant, and thus a method is provided to reduce friction between sliding parts of an engine by bringing the engine into contact with the non-aqueous lubricant composition of this disclosure. In some embodiments, the sliding parts may be piston rings / cylinder liners, crankshaft and connecting rod bearings, and valve mechanisms, including cams and valve tappets.

[0088] In yet another embodiment, a friction modifier (and optionally one or more of the above-mentioned additives) may be added to a petroleum distillate fuel (e.g., but not limited to gasoline, diesel, etc.) to form a lubricating composition for lubricating sliding parts that the non-aqueous lubricant composition cannot reach. In such an embodiment, the petroleum distillate fuel, such as gasoline fuel, may also contain an antiknock agent such as methylcyclopentadienylmanganese tricarbonyl, tetramethyl, or tetraethyl lead, or other dispersants or detergents such as various substituted succinimides, amines, etc. The lubricant composition can be readily prepared, for example, by dispersing a friction modifier containing the reaction product of this disclosure in a selected petroleum distillate fuel, such as by adding the friction modifier to the petroleum distillate and stirring or agitating the resulting solution to uniformly disperse the reaction product in the composition. In this regard, any conventional fuel blending method can be used. The amount of friction modifier containing the reaction product of this disclosure dispersed in the fuel can be from about 0.1% by weight to about 30% by weight, for example, greater than about 0.5% by weight to about 10% by weight, based on the total weight of the lubricant composition. In other embodiments, the amount of friction modifier combined is about 1% to about 5% by weight based on the total weight of the lubricant composition.

[0089] This disclosure will now be further described with reference to the following non-limiting embodiments. Example

[0090] Example 1

[0091] Tallow fatty amines were reacted with glycidyl ether to prepare two reaction products (FM-A and FM-B). The reaction was carried out by adding glycidyl ether to the tallow fatty amine at 150°C, followed by a digestion time of 4 hours. The two reaction products prepared from the ring-opening reaction of tallow fatty amine with glycidyl ether are listed in the table below:

[0092] Residual tallow fatty amines 41.1% by weight 0 Amine monoglycidyl accumulation 30.8% by weight 62.2% by weight diglycidol accumulation 28.2% by weight 37.8% by weight

[0093] The alkylalkoxylated monoamine is then reacted with glycidyl to prepare two additional reaction products (FM-C and FM-D). The structure of the alkylalkoxylated monoamine is as follows:

[0094]

[0095] Where Z is C 12 -C 14 Alkyl, Z' is methyl, and e is an integer averaging from about 2 to about 5. The reaction is carried out by adding glycidyl to an alkylalkoxylated monoamine at 150 °C, followed by a digestion time of 4 hours. The two reaction products prepared from the glycidyl ring-opening reaction of the alkylalkoxylated monoamine are listed in the table below:

[0096] Residual alkylalkoxylated monoamines 2.3% by weight 0.1% by weight Amine monoglycidyl accumulation 75.2% by weight 15.3% by weight diglycidol accumulation 22.5% by weight 84.6% by weight

[0097] The coefficients of friction of commercially available oils and those further containing 0.5% of the aforementioned reaction products were then determined at 100°C and 130°C using a Mini Traction Machine with a 3 / 4-inch ball on a smooth disk. The applied load was 36 N (1 GPa contact pressure), and the rotational speed ranged from 0.01 m / s to 2 m / s. The results at 130°C are shown in Tables 1 and 2 below:

[0098] Table 1: Results in Mobil 1 5W-30 oil at 130°C

[0099]

[0100]

[0101] Table 2: Results in Pennzoil 0W-20 oil at 130°C

[0102]

[0103] The results in Tables 1 and 2 show that the friction modifiers of this invention, containing the reaction products (FM-A, B, C, and D), significantly reduce the coefficient of friction for Mobil 1 5W-30 and Pennzoil 0W-20 oils. For better presentation of the results, the coefficients of friction for FM-A and B are shown in the table below. Figure 1 and 2 As shown in the image.

[0104] Because the reaction products of this invention contain multiple OH groups in their polar heads, they can be strongly adsorbed onto surfaces. The linear structure of the hydrophobic tails in FM-A, B, C, and D allows the reaction products to align well on surfaces despite strong van der Waals forces between their tails. These unique molecular structures make these reaction products excellent friction modifiers in oils.

Claims

1. A non-aqueous lubricant composition comprising a base oil and a friction modifier, wherein the friction modifier comprises a reaction product of: (i) an alkylalkoxylated amine having the following formula Where Z is C 12 -C 14 Alkyl, each Z' being independently methyl, and e being an integer of average value from 2 to 5; (ii) glycidyl; and optionally, (iii) an amine selected from alkylamines, alicyclic amines, arylamines, and alkylalkoxylated monoamines.

2. The non-aqueous lubricant composition of claim 1, wherein the (iii) amine is an alkylamine having the formula N(R1)3, wherein each R1 is hydrogen or C1-C2. 50 Alkyl group, provided that at least one R1 is hydrogen.

3. The non-aqueous lubricant composition of claim 2, wherein the (iii) amine is an alicyclic amine selected from cyclopentylamine, cyclohexylamine, cycloheptylamine, cyclododecylamine, 4-methylcyclohexylamine, N,N-dimethylcyclohexylamine, hexamethyleneimine, piperidine, and isophorone diamine.

4. The non-aqueous lubricant composition of claim 1, wherein the (iii) amine is formed by C1-C2. 20 Alkyl-substituted arylamines.

5. The non-aqueous lubricant composition of claim 1, wherein the friction modifier is present in an amount of 0.1% to 1.5% by weight, based on the total weight of the non-aqueous lubricant composition.

6. The non-aqueous lubricant composition of claim 1, wherein the base oil is a synthetic oil.

7. The non-aqueous lubricant composition of claim 1, wherein the base oil is a mineral oil.

8. A method for reducing friction between sliding parts of an engine, which is carried out by contacting the engine with the non-aqueous lubricant composition of claim 1.

9. A friction-reducing additive package comprising the friction modifier of claim 1 and one or more additives, the additives being selected from antioxidants, anti-wear additives, detergents, dispersants, second friction modifiers, viscosity index improvers, pour point depressants, corrosion inhibitors, defoamers, sealing and fixing agents, sealing compatibility agents, and mixtures thereof.

10. A non-aqueous lubricant composition comprising a base oil and a friction modifier, wherein the friction modifier comprises a compound having the following formula: Where R is an alkylalkoxy group having the following formula. Where Z is C 12 -C 14 Alkyl, each Z' is independently methyl, and e is an integer from 2 to 5 on average.

11. The non-aqueous lubricant composition of claim 10, further comprising a second friction modifier compound, wherein R is C1-C2. 25 alkyl.

12. The non-aqueous lubricant composition of claim 10, further comprising a second friction modifier compound, wherein R is a phenyl group or a C1-C2 bonded compound. 20 Alkyl-substituted phenyl groups.

13. The non-aqueous lubricant composition of claim 10, wherein the friction modifier comprises at least one of the following substances: 2,3-dihydroxypropylamine, 1,3-dihydroxypropylamine, bis(2,3-dihydroxypropyl)amine, bis(1,3-dihydroxypropyl)amine or (2,3-dihydroxypropyl)(1,3-dihydroxypropyl)amine.

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