JP2016537454A - Lubricating oil composition for protection of silver bearings in medium speed diesel engines - Google Patents

Abstract

Here, a medium speed diesel engine crankcase lubricating oil composition comprising: (a) a major amount of oil of lubricating viscosity; and (b) 0.1 to 5.0 weight percent silver lubricating additive comprising: (Ii) an alkoxylated fatty amine or a salt thereof; (ii) an alkoxylated fatty diamine or a salt thereof; or (iii) a mixture of (i) and (ii) above. Further provided is a method of reducing silver bearing wear and friction in a medium speed diesel engine comprising lubricating a medium speed diesel engine with the lubricating oil composition.

Description

FIELD OF THE INVENTION This invention relates generally to crankcase lubricating oil compositions and methods for protecting silver bearings in medium speed diesel engines.

BACKGROUND OF THE INVENTION High load diesel engines require crankcase lubricants that contain additives that stabilize oxidation and are non-corrosive to bearing materials including silver. Oxidative degradation is undesirable. This is because the engine lubricating oil can be decomposed. This degradation of the lubricating oil has derived problems such as increased viscosity, sludge formation, and increased engine deposits. As the lubricating oil oxidizes, it becomes more acidic and can cause corrosion of engine metal components such as bearing materials. In addition to the use of additives such as sludge to control oxidation, care must be taken to ensure that the additive itself is not corrosive to metal components during engine operation.

  Medium speed diesel engines are special. This is because a significant number of railway diesel engines operating in the United States and other countries contain bearing components with silver or silver surfaces. This is a particular problem. This is because many of the bearing protection additives that are effective in protecting other metal bearing surfaces such as copper lead, bronze, and aluminum are not effective in protecting silver bearing components. In the case of materials such as zinc dithiophosphate, they are very corrosive to silver or silver plated bearings.

  A relatively high degree of alkalinity in the lubricating oil is required to neutralize the acid formed during the combustion process. However, some additives that contribute to high alkalinity, such as overbased phenates or sulfonates, are aggressive to silver. This aggressive nature can result in excessive corrosion or wear of the silver-containing components of the engine. Therefore, a unique silver lubricant for medium speed diesel engines is required as part of the complex balance of additives to protect against the undesirable effects of lubricants on silver bearings.

  A number of patents have disclosed lubricating oil compositions for silver protection, but nothing has provided the improved protection observed with the lubricating oil compositions of the present invention.

  US Pat. No. 8,084,404 discloses a silver-protecting lubricating oil composition for a locomotive diesel engine containing a mixture of a hydrocarbylamine salt of an alkyl acid phosphate and a hydrocarbylamine salt of a dialkyldithiophosphoric acid. The hydrocarbyl on the hydrocarbylamine salt of the alkyl acid phosphate may be aliphatic, alicyclic, aromatic or mixtures thereof. However, there is no teaching as to whether the amine contains a hydroxyalkyl group.

  US Patent No. 5,902,776 discloses a lubricating oil or functional fluid composition comprising a thiocarbamate compound and a phosphate compound of a specific structure. The phosphate compound includes an ammonium salt of phosphate. The compositions are useful in providing lubricating oil compositions and functional fluids, particularly engine lubricating oils, with improved anti-wear properties, which in one form are improved antioxidant properties.

  US Patent Application No. 20080125336 discloses a lubricating composition for improving the phosphorus retention of spent oil and a method for reducing catalyst deactivation in an exhaust gas catalyst system. The lubricating oil composition is provided by an additive composition containing a phosphorus-containing additive mixture and a base oil. The phosphorus-containing additive mixture includes an ash-containing phosphorus compound and an ashless phosphorus compound. Ashless phosphorus compounds include amine salts of phosphates. The lubricating oil composition is useful for engine oil lubricating oil such as railway diesel engines.

  German Patent No. DE 2,357,199 discloses a lubricating oil composition consisting of phosphorothionic acid triesters and phosphate esters. The phosphate ester can be obtained by neutralizing a diester of phosphoric acid with a monovalent N-containing base of the formula. The lubricating oil additive has anti-wear properties and does not corrode silver or its alloys.

  European Patent No. 1,299,509 describes lubricating oils and functional fluids, in particular power transmission fluids such as gear oils, continuously variable transmission fluids, and in particular automatic transmission oils for electronic transmissions with electronically controlled converters, Disclosed is a combination of friction modifier additives comprising an oil soluble fatty amine and an oil soluble fatty amide used as ingredients.

  US Patent No. 5,286,394 discloses a crankcase lubricating oil composition containing Cu carboxylate and Na sulfonate and a friction modifier. The friction modifier is selected from glycerol monooleate, pentaerythritol monooleate, oleamide, bis (2-hydroxyethyl) -oleylamine and cocodiethanolamide.

  US Patent Application No. 20060030498 is a lubricant additive used in the formulation of a lubricating oil composition for crankcase engine oils comprising a surfactant containing a hydroxyl or amino group, a polyalkenyl acylating agent, and a base metal complex. A concentrate is disclosed. Surfactants include ethoxylated tallow amine which is Ethomeen O / 12.

  US Pat. No. 5,906,969 discloses a lubricating oil composition for an internal combustion engine comprising a molybdenum dithiocarbamate of a specific formula, a mixture of salicylates, one or more sulfonates and an alkylated (alkoxy) amine. The alkoxyamine can be an Ethomeen O / 12 or Ethodomeen T / 13 compound.

  European Patent No. 0,638,117 discloses a lubricating oil composition comprising a phenolic compound and an alkoxylated amine of a specific formula for improving the friction properties of the lubricating composition. The amine can be Ethomeen O / 12 or Ethodomeen T / 13.

  European Patent No. 0,649,458 discloses a lubricating oil composition for automobile engines and transmissions containing an oil of lubricating viscosity with a mixed friction modifier. The mixed friction modifier comprises a mixture of a polyol partial ester of a fatty acid and an alkoxylated hydrocarbylamine, which may be Ethomeen O / 12 or Ethodomeen T / 13.

  Japanese Patent No. 2005146010 discloses a lubricating oil composition containing a particular type of ashless antioxidant and / or an amine compound. The amine compound can be Ethomeen O / 12 or Ethodomeen T / 13 compound. The composition can be useful for diesel engines.

  Therefore, a crankcase lubricating oil composition that protects silver bearings in medium speed diesel engines is desired. A method of lubricating a medium speed diesel engine with a crankcase lubricating oil composition that protects a silver bearing is also desired.

SUMMARY OF THE INVENTION According to one aspect of the present invention, a lubricating oil composition is provided that reduces friction in a medium speed diesel engine to protect a silver bearing. In addition, a method of reducing silver bearing wear and friction in a medium speed diesel engine is also provided.

  Among other factors, the present invention is based on the surprising discovery of lubricating oil compositions that reduce silver bearing wear and friction in medium speed diesel engines.

Definition:
The following terms are used in the specification and have the following meanings unless otherwise indicated.

  As used herein, the term “medium speed diesel engine crankcase lubricant composition” refers to engine oil lubrication used in medium speed diesel engines as commonly found in railway locomotives, marine tugboats, and stationary power applications. Refers to an oil additive composition.

As used herein, the term “silver protection” refers to the ability of the medium speed crankcase lubricating oil composition of the present invention to protect silver and silver plated bearings against wear in a medium speed diesel engine crankcase.

  The term “major amount” of base oil refers to the case where the amount of base oil is at least 40 wt% of the lubricating oil composition. In some forms, a “major amount” of base oil refers to an amount of base oil greater than 50 wt%, greater than 60 wt%, greater than 70 wt%, greater than 80 wt%, or 90 wt% of the lubricating oil composition. To say more than.

  In the following description, all numbers disclosed herein are approximate values, regardless of whether the word "about" or "approximately" is used in connection therewith. They may vary 1%, 2%, 5%, or sometimes 10-20%.

DETAILED DESCRIPTION OF THE INVENTION Generally speaking, what is provided here is:
A medium speed diesel engine crankcase lubricating oil composition comprising:
(A) a major amount of oil of lubricating viscosity; and (b) 0.1 to 5.0% by weight of a silver lubricating additive comprising:
(I) alkoxylated fatty amines or salts thereof;
(Ii) an alkoxylated fatty diamine or a salt thereof; or (iii) a mixture of (i) and (ii) above.
What further provides:
(A) a major amount of oil of lubricating viscosity; and (b) 0.1 to 5.0% by weight of a silver lubricating additive comprising:
(I) alkoxylated fatty amines or salts thereof;
(Ii) an alkoxylated fatty diamine or a salt thereof; or (iii) a mixture of (i) and (ii) above;
Is a method of reducing silver bearing wear and friction in a medium speed diesel engine by lubricating the medium speed diesel engine with a lubricating oil composition comprising

  In one form, the medium speed diesel engine is selected from the group comprising railroad locomotives, marine tugboats and stationary power engines. In another form, the medium speed diesel engine is a railway locomotive engine. In another form, the medium speed diesel engine is a marine tugboat engine. In another form, the medium speed diesel engine is a stationary power engine.

In one form, the medium speed diesel engine operates at 250 rpm to 1000 rpm.
In one form, the medium speed diesel engine crankcase lubricant composition reduces silver bearing wear and friction in medium speed diesel engines.

In one form, the alkoxylated fatty amine is Formula 1;

Wherein R ₁ is an aliphatic fatty acid chain in the range of C8-C24; R ₂ is independently hydrogen or a C1-C8 alkyl chain; and wherein x and y are each independently at least 1 and x + y ≦ 50.
In one form, x and y are independently at least 1 and x + y ≦ 40, respectively. In other forms, x + y is ≦ 30, ≦ 20, ≦ 10, and ≦ 5.

In another form, the alkoxylated fatty diamine is of formula 2:

Where R ₃ is an aliphatic fatty acid chain in the range of C8-C24; each R ₄ is independently hydrogen or C1-C8 alkyl; and R ₅ is C1-C8 divalent alkylene; Wherein a + b + c are each independently at least 1 and a + b + c ≦ 50.
In one form, a and b are independently at least 1 and a + b + c ≦ 40, respectively. In other forms, a + b + c is ≦ 30, ≦ 20, ≦ 10, and ≦ 5.

In another form, the alkoxylated fatty amine salt is Formula 3;

Wherein R ₁ is an aliphatic fatty acid chain in the range of C8-C24; R ₂ is independently hydrogen or C1-C8 alkyl; where x and y are each independently at least 1 and x + y ≦ 50; and where Z is an anion of an organic or inorganic acid.
In one form, x and y are independently at least 1 and x + y ≦ 40, respectively. In other forms, x + y is ≦ 30, ≦ 20, ≦ 10, and ≦ 5.
In one form, Z is selected from the group comprising phosphates, phosphites, dithiophosphates, sulfates, sulfonates, carbonates, and anions from carboxylic acids and fatty acids.

In another form, the alkoxylated fatty diamine salt is Formula 4:

Where R ₃ is an aliphatic fatty acid chain in the range of C8-C24; each R ₄ is independently hydrogen or C1-C8 alkyl; and R ₅ is C1-C8 divalent alkylene; Wherein a + b + c is independently at least 1 and a + b + c ≦ 50; and where Z is an anion of an organic or inorganic acid.
In one form, a and b are independently at least 1 and a + b + c ≦ 40, respectively. In other forms, a + b + c is ≦ 30, ≦ 20, ≦ 10, and ≦ 5.
In one form, Z is selected from the group comprising phosphates, phosphites, dithiophosphates, sulfates, sulfonates, carbonates, and anions from carboxylic acids and fatty acids.

In one form, suitable alkoxylated fatty amines are propoxylated monoamines, butoxylated monoamines, alkoxylated alkyldiisopropanolamines, ethoxylated monoamines such as ethoxylated octadecylamine, ethoxylated cocoalkylamines, ethoxylated oleylamines, diethoxylated Includes oleylamine, ethoxylated soya alkylamine, and ethoxylated tallow alkylamine.
In one form, suitable alkoxylated fatty diamines are commonly known as Ethodomeen T / 13, Ethodomeen T / 20, and Ethodomeen T / 25 (also known as ethoxylated N-tallow-1,3-diaminopropane). Ethoxylated diamines such as tris (2-hydroxyethyl) -N-tallow alkyl-1,3-diaminepropane.
In one form, the silver lubricating additive is an organic or inorganic alkoxylated fatty amine or diamine selected from the group comprising phosphates, phosphites, dithiophosphates, sulfates, sulfonates, carbonates, and anions from carboxylic acids and fatty acids. Salt.

In one form, the alkoxylated fatty amine or diamine salt group is an alkyl acidic phosphate group. In another form, the alkyl acidic phosphate group is a dialkyl monohydrogen phosphate or monoalkyl dihydrogen phosphate according to the following formulas 5 and 6:

Here, R ₆ , R ₇ and R ₈ are independently linear, branched alkyl or alkylated aromatic groups having from about 3 to about 40 carbon atoms.

In another form, the alkyl acidic phosphate group is selected from the group comprising:
Di-2-ethylhexyl hydrogen phosphate, dihexyl hydrogen phosphate, propyl dihydrogen phosphate, dipropyl hydrogen phosphate, butyl dihydrogen phosphate, butyl dihydrogen phosphate, dipentyl hydrogen phosphate, hexyl dihydrogen phosphate, dihexyl hydrogen phosphate, heptyl dihydrogen phosphate, diheptyl Hydrogen phosphate, octyl dihydrogen phosphate, dioctyl hydrogen phosphate, decyl dihydrogen phosphate, didecyl hydrogen phosphate, decyl dihydrogen phosphate, didecyl hydrogen phosphate and the like.

In one form, the alkoxylated fatty salt is diethoxylated oleyl ammonium bis (2-ethylhexyl) phosphate.
In one form, the alkoxylated fatty amine or alkoxylated fatty diamine contains a saturated or unsaturated C ₁₂ -C ₂₄ alkyl radical that is branched or linear. In one form, the saturated or unsaturated alkyl radical contains 14 to 20 carbon atoms. In one form, the saturated or unsaturated alkyl radical contains 16 to 18 carbon atoms.
In one form, the silver lubricity additive is present at 0.20-4% by weight. In one form, the silver lubricity additive is present at 0.20 to 3 weight percent. In one form, the silver lubricity additive is present at 0.20-2% by weight. In one form, the silver lubricity additive is present at 0.20 to 1 wt%.

In one form, the alkoxylated fatty amine, alkoxylated fatty diamine, or salt thereof is an N-hydroxyalkyl substituted hydrocarbylamine compound. In another form, the N-hydroxyalkyl substituted hydrocarbylamine compound is an N-hydroxyalkyl substituted hydrocarbyl monoamine or diamine or a salt thereof. Such N-hydroxyalkyl-substituted hydrocarbyl monoamines or diamines or salts thereof are derived from coconut oil, beef tallow, soybean oil and palm nut oil, laurin, caprin, capryl, capryl / caprin, decanoic, myristin, palmitic, stearin, Derived from isostearin, olein, linole, octidedecanoic, 2-heptylundecanoic, and N-hydroxyalkyl substituted fatty monoamines or diamines or salts thereof. Among them, those from oleyl and beef tallow are preferred.
Typically, N-hydroxyalkyl substituted hydrocarbyl monoamines or diamines are commercially available from Akzo Nobel.
In one form, the N-hydroxyalkyl substituted hydrocarbyl monoamine or diamine or salt thereof is a diethoxylated or polyoxyethylene monoamine or diamine or salt thereof. Specific samples of suitable amine compounds are diethoxylated cocoamine, diethoxylated tallow amine, diethoxylated soyamine, diethoxylated oleylamine, polyoxyethylene cocoamine, polyoxyethylene tallow amine, polyoxyethylene soyamine, polyoxyethylene oleylamine, etc. including.
N-hydroxyalkyl substituted hydrocarbylamine compounds may be prepared by methods well known in the art. Alkyl alkanolamines are described in US Pat. No. 4,085,126; 7,479,473 and other methods well known in the art; or they may be purchased from Akzo Nobel.

In one form, the silver lubricity additive is an N-hydroxyalkyl-substituted hydrocarbylamine or a hydrocarbylamine salt of a diamine compound, where the salt group is an alkyl acidic phosphate group. Alkyl acidic phosphates can include dialkyl monohydrogen phosphates and monoalkyl dihydrogen phosphates having the formula:

Here, R ₆ , R ₇ and R ₈ are independently linear, branched alkyl or alkylated aromatic having from about 3 to about 40 carbon atoms.

  Examples of alkyl acidic phosphates that may be used to produce the hydrocarbyl amines of the present invention include propyl dihydrogen phosphate, dipropyl hydrogen phosphate, butyl dihydrogen phosphate, butyl dihydrogen phosphate, dipentyl hydrogen phosphate, hexyl dihydrogen phosphate, Dihexyl hydrogen phosphate, heptyl dihydrogen phosphate, diheptyl hydrogen phosphate, octyl dihydrogen phosphate, dioctyl hydrogen phosphate, decyl dihydrogen phosphate, didecyl hydrogen phosphate, decyl dihydrogen phosphate, didecyl hydrogen phosphate and the like. Preferably, the hydrocarbyl amine salt is dihexyl hydrogen phosphate.

  In many cases it may be advantageous to form a concentrate of the lubricating oil-soluble additive composition of the present invention in a carrier liquid. These additive concentrates provide a convenient way to handle, transport, and ultimately blend into a lubricant base oil to provide a finished lubricant. In general, the lubricant-soluble additive concentrates of the present invention by themselves cannot be used and are not suitable as finished lubricants. Rather, the lubricant-soluble additive concentrate is blended with a lubricant base stock to provide a finished lubricant. It is desirable for the carrier liquid to readily increase the solubility of the lubricating oil soluble additives of the present invention to provide a readily soluble oil additive concentrate in the lubricating base oil stock. Furthermore, the carrier liquid should not introduce any undesirable features including impurities such as, for example, high volatility, high viscosity, and heteroatoms into the lubricant base stock and thus ultimately into the finished lubricant. Is desirable. Accordingly, the present invention further provides an oil soluble additive concentrate composition comprising 2.0-90% by weight of the oil soluble additive composition of the present invention and an inert carrier fluid, based on the total concentrate. The inert carrier fluid may be a lubricating oil.

  These concentrates usually contain about 2.0% to about 90% by weight, preferably 10% to 50% by weight, of the oil-soluble additive composition of the present invention and are known in the art and below It may further contain one or more other additives described in 1. The remainder of the concentrate is a substantially inert carrier liquid.

Oils of lubricating viscosity The lubricating oil compositions disclosed herein generally comprise at least one oil of lubricating viscosity. Any base oil known to those skilled in the art can be used as the oil of lubricating viscosity disclosed herein. Some suitable base oils for preparing such lubricating oil compositions are Mortier et al., “Chemistry and Technology of Lubricants,” 2nd Edition, London, Springer, Chapters 1 and 2 (1996); and A. Sequeria, Jr., “Lubricant Base Oil and Wax Processing,” New York, Marcel Decker, Chapter 6, (1994); and DV Brock, Lubrication Engineering, Vol. 43, pages 184-5, (1987). All of which are incorporated herein by reference. In general, the amount of base oil in the lubricating oil composition may be from about 70 to about 99.5 wt%, based on the total weight of the lubricating oil composition. In some forms, the amount of base oil in the lubricating oil composition is from about 75 to about 99 wt%, from about 80 to about 98.5 wt%, or from about 80 to about based on the total weight of the lubricating oil composition. 98 wt%.

  In some forms, the base oil is or includes any natural or synthetic lubricating base oil fraction. Some non-limiting examples of synthetic oils are prepared from the polymerization of at least one alpha olefin, such as ethylene, or from a hydrocarbon synthesis procedure using carbon monoxide and hydrogen gas, such as the Fischer-Tropsch process. Contains prepared oils such as polyalphaolefins or PAO. In some forms, the base oil comprises less than about 10 wt% of one or more heavy fractions based on the total weight of the base oil. The heavy fraction refers to a lubricating oil fraction having a viscosity of at least about 20 cSt at 100 ° C. In some forms, the heavy fraction has a viscosity of at least about 25 cSt or at least about 30 cSt at 100 ° C. In further embodiments, the amount of one or more heavy fractions in the base oil is less than about 10 wt%, less than about 5 wt%, less than about 2.5 wt%, less than about 1 wt%, based on the total weight of the base oil. Or less than about 0.1 wt%. In the next further form, the base oil does not contain any heavy fraction.

  In one form, the lubricating oil composition comprises a major amount of a base oil of lubricating viscosity. In some forms, the base oil is about 2.5 centistokes (cSt) to about 20 cSt, about 5 centistokes (cSt) to about 20 cSt, about 7 cSt to about 16 cSt, or about 9 cSt to about 15 cSt at 100 ° C. Has kinematic viscosity. The kinematic viscosity of the lubricating oil composition or base oil (base oil) disclosed herein can be measured by ASTM D445, incorporated herein by reference.

  In other forms, the base oil is or includes a base stock or a blend of base stocks. In a further form, the base stock is manufactured using a variety of different processes including, but not limited to, distillation, solvent purification, hydrogen processing, oligomerization, esterification, and repurification. In some forms, the base stock includes a repurified stock. In a further form, the repurified stock should be substantially free of material introduced through manufacturing, contamination, or previous use.

  In some forms, base oils are incorporated herein by reference, the American Petroleum Institute (API) Publication 1509, Fourteen Edition, December 1996 (ie, API Base Oil Interchangeability Guidelines for Passenger Car Motor Oils and Diesel Engine Oils) One or more bases of one or more Groups IV identified in 1. The API guidelines define base stock as a lubricant component that may be manufactured using a variety of different processes. Groups I, II and III basestocks are mineral oils with a specific range of saturation, sulfur content and viscosity index, respectively. Group IV base stock is polyalphaolefin (PAO). Group V base stock includes all other base stocks not included in Group I, II, III, or IV.

  The saturation level, sulfur level and viscosity index of Group I, II and III basestocks are listed in Table 1 below.

  In some forms, the base oil comprises one or more base stocks of Group I, II, III, IV, V, or combinations thereof. In other forms, the base oil comprises one or more base stocks of Group II, III, IV, or combinations thereof. In a further form, the base oil comprises one or more base stocks of Group II, III, IV, or combinations thereof, wherein the base oil is about 5 centistokes (cSt) to about 20 cSt at 100 ° C. It has a kinematic viscosity of about 7 cSt to about 16 cSt, or about 9 cSt to about 15 cSt.

  The base oil may be selected from the group consisting of natural oils of lubricating viscosity, synthetic oils of lubricating viscosity, and mixtures thereof. In some forms, the base oil is an isomeric of synthetic waxes and slack waxes, as well as hydrocracking basestocks made by hydrocracking the crude aromatic and polar components (rather than solvent extraction). Including base stock obtained by conversion. In other forms, base oils of lubricating viscosity include natural oils such as animal oils, vegetable oils, mineral oils, oils derived from coal or shale, and combinations thereof. Some non-limiting examples of animal oils include bone oil, lanolin, fish oil, lard oil, dolphin oil, seal oil, shark liver oil, tallow oil, and whale oil. Some non-limiting examples of vegetable oils are castor oil, olive oil, peanut oil, rapeseed oil, corn oil, sesame oil, cottonseed oil, soybean oil, sunflower oil, safflower oil, cannabis oil, flaxseed oil, gill oil, sea lion Includes oil, jojoba oil, and grassland foam oil. Such oils may be partially or fully hydrogenated. Some non-limiting examples of mineral oils include Group I, II, and III basestocks, liquefied petroleum and paraffinic, naphthenic or mixed paraffinic-naphthenic type solvent or acid treated mineral oils. In some forms, the mineral oil is a neat or low viscosity mineral oil.

In some forms, synthetic oils of lubricating viscosity are carbonized such as polymerized and copolymerized olefins, alkylbenzenes, polyphenyls, alkylated diphenyl ethers, alkylated diphenyl sulfides, as well as their derivatives, analogs and homologs thereof. Includes hydrogen oil and halo-substituted hydrocarbon oil. In other forms, synthetic oils include alkylene oxide polymers, interpolymers, copolymers, and derivatives thereof, where the terminal hydroxyl groups can be modified by esterification, etherification, and the like. In a further form, the synthetic oil comprises esters of dicarboxylic acids with various alcohols. In one form, the synthetic oils include esters made from C ₅ -C ₁₂ monocarboxylic acids and polyols and polyol ethers. In a further form, the synthetic oil comprises trialkyl phosphate ester oils such as tri-n-butyl phosphate and triisobutyl phosphate.

  In some forms, synthetic oils of lubricating viscosity include silicone-based oils (such as polyalkyl-, polyaryl-, polyalkoxy-, polyaryloxy-siloxane oils and silicate oils). In other forms, synthetic oils include liquid esters of phosphorus-containing acids, polymeric tetrahydrofurans, polyalphaolefins, and the like.

  Base oils derived from the hydroisomerization of waxes may also be used either alone or in combination with the natural and / or synthetic base oils described above. Such wax isomerate oils are produced by hydroisomerization of natural or synthetic waxes or mixtures thereof over a hydroisomerization catalyst.

  In a further form, the base oil comprises polyalphaolefin (PAO). Generally speaking, the polyalphaolefin may be derived from an alpha olefin having from about 2 to about 30, from about 4 to about 20, or from about 6 to about 16 carbon atoms. Non-limiting examples of suitable polyalphaolefins include those derived from octene, decene, mixtures thereof and the like. These polyalphaolefins may have a viscosity of about 2 to about 15, about 3 to about 12, or about 4 to about 8 centistokes at 100 ° C. In some cases, polyalphaolefins may be used with other base oils such as mineral oil.

  In a further form, the base oil comprises a polyalkylene glycol or a polyalkylene glycol derivative, wherein the terminal hydroxyl group of the polyalkylene glycol may be modified by esterification, etherification, acetylation, and the like. Non-limiting examples of suitable polyalkylene glycols include polyethylene glycol, polypropylene glycol, polyisopropylene glycol, and combinations thereof. Non-limiting examples of suitable polyalkylene glycol derivatives include polyalkylene glycol ethers (eg, polyisopropylene glycol methyl ether, polyethylene glycol diphenyl ether, polypropylene glycol diethyl ether, etc.), polyalkylene glycol mono and poly Including carboxylic acid esters, and combinations thereof. In some cases, polyalkylene glycols or polyalkylene glycol derivatives may be used with other base oils such as polyalphaolefins and mineral oils.

  In a further form, the base oil is a dicarboxylic acid (eg, phthalic acid, succinic acid, alkyl succinic acid, alkenyl succinic acid, maleic acid, azelaic acid, suberic acid, sebacic acid, fumaric acid, adipic acid, linoleic acid dimer. Body, malonic acid, alkylmalonic acid, alkenylmalonic acid, etc.) with any alcohol (eg butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, ethylene glycol, diethylene glycol monoether, propylene glycol, etc.) Contains esters. Non-limiting examples of these esters include dibutyl adivic acid, di (2-ethylhexyl) sebacic acid, di-n-hexyl fumaric acid, dioctyl sebacic acid, diisooctyl azelaic acid, diisodecyl azelaic acid, dioctyl phthalic acid , Didecyl phthalic acid, dieicosyl sebacic acid, 2-ethylhexyl diester of linoleic acid dimer, and the like.

  In a further form, the base oil comprises hydrocarbons prepared by a Fischer-Tropsch process. The Fischer-Tropsch process uses a Fischer-Tropsch catalyst to prepare hydrocarbons from a gas containing hydrogen and carbon monoxide. These hydrocarbons may require further processing to be useful as base oils. For example, the hydrocarbon may be dewaxed, hydroisomerized, and / or hydrocracked using processes known to those skilled in the art.

  In a further form, the base oil comprises unrefined oil, refined oil, rerefined oil, or mixtures thereof. Unrefined oils are those obtained directly from natural or synthetic sources without further purification. Non-limiting examples of unrefined oils include shale oil obtained directly from dry distillation operations, petroleum oil obtained directly from primary distillation, and ester oil obtained directly from the esterification process and used without further treatment . Refined oils are similar to unrefined oils except that they have been further processed by one or more refining processes to improve one or more properties. Many such purification processes are known to those skilled in the art, such as solvent extraction, secondary distillation, acid or base extraction, filtration, percolation and the like. The rerefined oil is obtained by applying to a refined oil process similar to that used to obtain the refined oil. Such rerefined oils are also known as reclaimed or reprocessed oils and are often further processed by processes directed to removal of spent additives and oil breakdown products.

Additional Lubricant Additives Optionally, the lubricating oil composition of the present invention further comprises at least an additive or modifier (hereinafter referred to as “additive”) that can improve or provide any desired property of the lubricating oil composition. May be included. Any additive known to those skilled in the art may be used in the lubricating oil compositions disclosed herein. Some suitable additives are incorporated herein by reference, Mortier et al., “Chemistry and Technology of Lubricants,” 2nd Edition, London, Springer, (1996); and Leslie R. Rudnick, “Lubricant Additives: Chemistry and Applications, ”New York, Marcel Dekker (2003).

  In some forms, the additive is an antioxidant, antiwear agent, cleaning agent, rust inhibitor, demulsifier, friction modifier, multifunctional additive, viscosity index improver, pour point depressant, foam inhibitor, Consists of metal deactivators, dispersants, corrosion inhibitors, lubricity improvers, thermal stability improvers, anti-haze additives, anti-icing agents, dyes, markers, static dissipation agents, biocides and combinations thereof You can choose from a group. Various additives are known and commercially available. These additives or similar compounds may be used for the preparation of the lubricating oil composition of the present invention by conventional blending procedures.

  Examples of antioxidants are amine-based, such as diphenylamine, phenyl-alpha-naphthyl-amine, N, N-di (alkylphenyl) amine; and alkylated phenylene-diamines; phenolic, such as BHT, sterically hindered alkylphenols. For example, 2,6-di-tert-butylphenol, 2,6-di-tert-butyl-p-cresol and 2,6-di-tert-butyl-4- (2-octyl-3-propanoic) phenol And mixtures thereof; but are not limited thereto.

  Examples of antiwear agents include, but are not limited to: zinc dialkyl dithiophosphates and zinc diaryl dithiophosphates, such as Born et al. Entitled “Relationship between Chemical Structure and, found in Lubrication Science 4-2 January 1992. Effectiveness of some Metallic Dialkyl- and Diaryl-dithiophosphates in Different Lubricated Mechanisms (see eg pages 97-100); aryl phosphates and phosphites, sulfur-containing esters, phosphosulfur compounds, metals or ashless dithio Carbamates, xanthates, alkyl sulfides and the like and mixtures thereof.

  Representative examples of ashless dispersants include, but are not limited to, ester polar sites attached to the polymer backbone through amines, alcohols, amides, or cross-linking groups. The ashless dispersant of the present invention may be selected, for example, from: oil-soluble salts, esters, aminoesters, amides, imides, and long-chain hydrocarbon-substituted mono- and dicarboxylic oxazolines or their anhydrides; A long chain aliphatic hydrocarbon having an attached polyamine, a thiocarboxylate derivative of the long chain hydrocarbon; and a Mannich reaction product formed by condensing a long chain substituted phenol with a polyalkylene polyamine and formaldehyde.

  Carboxylic acid dispersants include nitrogen-containing compounds (such as amines), organic hydroxy compounds (such as aliphatic compounds including mono- and polyhydric alcohols, or aromatic compounds including phenol and naphthol), and / or basic inorganic materials, Reaction products of carboxylic acylating agents (acids, anhydrides, esters, etc.) containing at least about 34 and preferably at least about 54 carbon atoms. These reaction products include imides, amides, esters, and salts.

  Succinimide dispersants are a type of carboxylic acid dispersant. They are prepared by reaction of an organic hydroxy compound or an amine containing at least one hydrogen atom attached to a nitrogen atom, or a mixture of the hydroxy compound and an amine, with a hydrocarbyl-substituted succinic agent. The term “succinic acylating agent” (succinic acylating agent) refers to a hydrocarbon-substituted succinic acid or a compound that produces succinic acid, the latter including the acid itself. Such materials typically include hydrocarbyl-substituted succinic acids, anhydrides, esters (including half esters) and halides.

Succinic base dispersants (succinic acid dispersants) have various chemical structures. One class of succinic base dispersants may be represented by Equation 7:

Here, each R ₉ is independently a hydrocarbyl group such as a polyolefin-derived group. Typically, the hydrocarbyl group is an alkenyl group such as a polyisobutenyl group. Expressed another way, the R ₉ group can contain from about 40 to about 500 carbon atoms, and these atoms may be present in an aliphatic form. R ₁₀ is an alkylene group, generally an ethylene (C ₂ H ₄ ) group; and p is 1-11. Examples of succinimide dispersants include, for example, U.S. Pat. S. Patent Nos. 3,172,892, 4,234,435 and 6,165,235.

  The polyalkenes from which the substituents are derived are typically homopolymers and interpolymers of polymerizable olefin monomers of usually 2 to 6 carbon atoms but 2 to about 16 carbon atoms. is there. The amine that reacts with the succinic acylating agent to form the carboxylic acid dispersant composition can be a monoamine or a polyamine.

  Succinimide dispersants refer to themselves as nitrogen functionality is usually in the form of imide functionality, although nitrogen functionality may be in the form of amines, amine salts, amides, imidazolines as well as mixtures thereof. . To prepare the succinimide dispersant, one or more succinic acid-producing compounds and one or more amines are heated and optionally in the presence of a substantially inert organic liquid solvent / diluent, typically Water is removed. The reaction temperature can range from about 80 ° C. to the decomposition temperature of the product or mixture, typically between about 100 ° C. and about 300 ° C. Additional details and examples of procedures for preparing succinimide dispersants of the present invention are described in, for example, US Pat. S. Patent Nos. 3,172,892, 3,219,666, 3,272,746, 4,234,435, 6,165,235 and 6,440,905.

  Suitable ashless dispersants may also include amine dispersants, which are reaction products of relatively high molecular weight aliphatic halides and amines, preferably polyalkylene polyamines. Examples of such amine dispersants are described, for example, in U.S. Pat. S. Patent Nos. 3,275,554, 3,438,757, 3,454,555 and 3,565,804.

  Suitable ashless dispersants further include “Mannic dispersants” which are the reaction products of aldehydes (particularly formaldehyde) and amines (particularly polyalkylene polyamines) with alkylphenols in which the alkyl group contains at least about 30 carbon atoms. But you can. Examples of such dispersants are described, for example, in US Pat. S. Patent Nos. 3,036,003, 3,586,629, 3,591,598 and 3,980,569.

  Suitable ashless dispersants are described, for example, in US Pat. S. Patent Nos. Post-treatment ashless dispersants such as post-treatment succinimides, such as post-treatment processes including borate or ethylene carbonate disclosed in US Pat. Nos. 4,612,132 and 4,746,446, as well as other post-treatment processes may be used. The carbonated alkenyl succinimides have a molecular weight of about 450 to about 3000, preferably about 900 to about 2500, more preferably about 1300 to about 2400, and most preferably about 2000 to about 2400, as well as mixtures of these molecular weights. It is polybutene succinimide derived from polybutene.

  Ashless dispersants are described in U.S. Pat. S. Patent No. Polyamines and mixtures of unsaturated acidic reagent copolymers of olefins and unsaturated acidic reagents, such as those disclosed in US Pat. No. 5,716,912, polybutene succinic acid derivatives can be prepared by reacting under reaction conditions.

  Suitable ashless dispersants may be polymers, which are interpolymers of monomers containing polar substitution and oil-solubilized monomers such as decyl methacrylate, vinyl decyl ether and high molecular weight olefins. Examples of polymer dispersants are described in U.S. Pat. S. Patent Nos. 3,329,658; 3,449,250 and 3,666,730.

  Generally, the one or more ashless dispersants are present in the lubricating oil composition in an amount ranging from about 0.01 wt% to about 10 wt%, based on the total weight of the lubricating oil composition.

Representative examples of metal detergents include sulfonates, alkyl phenates, sulfurized alkyl phenates, carboxylates, salicylates, phosphonates, and phosphinates. Commercial products are commonly referred to as neutral or overbased. Overbased metal detergents include hydrocarbons, detergent acids such as: sulfonic acids, alkylphenols, carboxylates, metal oxides or hydroxides (eg calcium oxide or calcium hydroxide) and promoters such as xylene, methanol and water Is generally produced by carbonating a mixture of For example, to prepare an overbased calcium sulfonate, in carbonation, calcium oxide or hydroxide reacts with gaseous carbon dioxide to form calcium carbonate. The sulfonic acid is neutralized with excess CaO or Ca (OH) ₂ to form a sulfonate.

  Other examples of suitable cleaning agents include boronated sulfonates. Generally speaking, the boronated sulfonate used herein can be any boronated sulfonate known in the art. The boronated sulfonate used herein can have a total base number (total alkali number) (TBN) of about 10 to about 500. In one form, the boronated sulfonate has a TBN of about 10 to about 100. In one form, the boronated sulfonate has a TBN of about 100 to about 250. In one form, the boronated sulfonate has a TBN of about 250 to about 500.

  Boron alkaline earth metal sulfonates are described, for example, in U.S. Pat. S. Patent Application Publication No. It can be prepared by methods known in the art as disclosed in 20070123437, the contents of which are incorporated herein by reference. For example, the boronated alkaline earth metal sulfonate is prepared in the following manner: (a) (i) at least one oil-soluble sulfonic acid or alkaline earth metal sulfonate salt or mixture thereof; (ii) at least one An alkaline earth metal source; and (iii) at least one boron source; (iv) in the presence of at least one hydrocarbon solvent; and (v) less than 0-10 mol% of the boron source, other than the boron source. (B) heating the reaction product of (a) to a temperature higher than the distillation temperature of (iv) to distill the water of the reaction and (iv).

  Metal-containing or ash-forming cleaning agents function both as cleaning agents that reduce or eliminate deposits and as acid neutralizers or rust inhibitors, thereby reducing wear and corrosion and extending engine life. Cleaning agents generally include a polar head with a long hydrophobic tail. The polar head includes a metal salt of an acidic organic compound. The salt may contain a substantial stoichiometric amount of metal when normally described as a normal or neutral salt and has a total alkali number of 0 to about 80 or TBN (ASTM Typically measured by D2896). Large amounts of metal bases may be incorporated by reacting excess metal compounds (eg, oxides or hydroxides) with acid gases (eg, carbon dioxide). The resulting overbased detergent comprises a neutralized detergent as the outer layer of a metal base (eg, carbonate) micelle. Such overbased detergents may have a TBN of about 150 or greater and typically will have a TBN of about 250 to about 450 or greater.

  Detergents that can be used are oil-soluble neutral and overbased sulfonates, phenates, sulfurized phenates, thiophosphonates of metals, especially alkali or alkaline earth metals such as barium, sodium, potassium, lithium, calcium and magnesium. , Salicylates, and naphthenates and other oil-soluble carboxylates. The most commonly used metals are calcium and magnesium that may be present in the detergent used in the lubricating oil, and calcium and / or a mixture of magnesium and sodium. Particularly convenient metal detergents are neutral and overbased calcium sulfonates having a TBN of about 20 to about 450, neutral and overbased calcium phenates and sulfurized phenates having a TBN of about 50 to about 450, and about Neutral and overbased magnesium or calcium salicylates having a TBN of 20 to about 450. A combination of detergents may be used, whether overbased or neutral or both.

  In one form, the detergent may be one or more alkali or alkaline earth metal salts of alkyl-substituted hydroxyaromatic carboxylic acids. Suitable hydroxyaromatic compounds include mononuclear monohydroxy and polyhydroxy aromatic hydrocarbons having 1 to 4, and preferably 1 to 3 hydroxyl groups. Suitable hydroxyaromatic compounds include phenol, catechol, resorcinol, hydroquinone, pyrogallol, cresol and the like. A preferred hydroxyaromatic compound is phenol.

  The alkyl substitution site of the alkali or alkaline earth metal salt of the alkyl-substituted hydroxyaromatic carboxylic acid is derived from an alpha olefin having from about 10 to about 80 carbon atoms. The olefin used may be linear or branched. The olefin may be a mixture of linear olefins, a mixture of isomerized linear olefins, a mixture of branched olefins, a partially branched linear mixture, or a mixture of any of the foregoing.

  In one form, the mixture of linear olefins that can be used is a mixture of normal alpha olefins selected from olefins having from about 12 to about 30 carbon atoms per molecule. In one form, the normal alpha olefin is isomerized using at least one solid or liquid catalyst.

  In another form, the olefin is a branched olefinic propylene oligomer having from about 20 to about 80 carbon atoms, or a mixture thereof, that is, a branched olefin derived from the polymerization of propylene. The olefin may be substituted with other functional groups such as a hydroxy group, a carboxylic acid group, and a hetero atom. In one form, the branched olefinic propylene oligomer or mixture thereof has from about 20 to about 60 carbon atoms. In one form, the branched olefinic propylene oligomer or mixture thereof has from about 20 to about 40 carbon atoms.

In one form, at least about 75 mole percent of the alkyl groups contained in the alkali or alkaline earth metal salt of an alkyl-substituted hydroxyaromatic carboxylic acid, such as the alkyl group of an alkaline earth metal salt of an alkyl-substituted hydroxybenzoic acid detergent. (e.g., at least about 80 mole%, at least about 85 mole%, at least about 90 mole%, at least about 95 mole%, or at least about 99 mole%) _{is C 20} or greater. In another form, the alkyl alkali or alkaline earth metal salt of substituted hydroxyaromatic carboxylic acids, alkyl-substituted alkyl group is the residue of normal alpha olefins containing C ₂₀ or more normal alpha-olefins of at least 75 mol% Alkali or alkaline earth metal salts of alkyl-substituted hydroxybenzoic acids derived from hydroxybenzoic acid.

In another form, at least about 50 moles of the alkyl group contained in the alkali or alkaline earth metal salt of the alkyl-substituted hydroxyaromatic carboxylic acid, such as the alkyl group of an alkali- or alkaline earth metal salt of the alkyl-substituted hydroxybenzoic acid. % (E.g., at least about 60 mol%, at least about 70 mol%, at least about 80 mol%, at least about 85 mol%, at least about 90 mol%, at least about 95 mol%, or at least about 99 mol%) is about it is a C ₁₄ ~ about _{C 18.}

  The resulting alkali or alkaline earth metal salt of the alkyl-substituted hydroxyaromatic carboxylic acid will be a mixture of ortho and para isomers. In one form, the product will contain about 1-99% ortho isomer and 99-1% para isomer. In another form, the product will contain about 5-70% ortho and 95-30% para isomer.

  Alkali or alkaline earth metal salts of alkyl-substituted hydroxyaromatic carboxylic acids can be neutral or overbased. Generally, an overbased alkali or alkaline earth metal salt of an alkyl-substituted hydroxyaromatic carboxylic acid is alkyl-substituted by a process such as the addition of a base source (eg, lime) and an acidic overbasing compound (eg, carbon dioxide). This is an increase in TBN of an alkali or alkaline earth metal salt of a hydroxy aromatic carboxylic acid.

  The overbased salt may be low overbased, eg, an overbased salt having a TBN of less than about 100. In one form, the TBN of the low overbased salt may be from about 5 to about 50. In another form, the TBN of the low overbased salt may be from about 10 to about 30. In yet another form, the TBN of the low overbased salt may be from about 15 to about 20.

The overbased detergent may be medium overbased, for example, an overbased salt having a TBN of about 100 to about 250. In one form, the TBN of the medium overbased salt may be about 100 to about 200. In another form, the TBN of the medium overbased salt may be from about 125 to about 175.
Overbased detergents may be overbased, for example, overbased salts having a TBN greater than about 250. In one form, the TBN of the highly overbased salt may be about 250 to about 450.

  Sulfonates may be prepared from sulfonic acids typically obtained by alkylation of aromatic hydrocarbons or by sulfonation of alkyl-substituted aromatic hydrocarbons such as those obtained from petroleum fractionation. Examples include those obtained by alkylating benzene, toluene, xylene, naphthalene, diphenyl or their halogen derivatives. Alkylation may be carried out in the presence of a catalyst with an alkylating agent having more than about 3 to 70 carbon atoms. The alkaryl sulfonate usually contains from about 9 to about 80 or more carbon atoms, preferably from about 16 to about 60 carbon atoms, per alkyl-substituted aromatic moiety.

  Oil soluble sulfonates or alkaryl sulfonic acids may be neutralized with oxides, hydroxides, alkoxides, carbonates, carboxylates, sulfides, hydrosulfides, nitrates and borates. The amount of metal compound is selected in view of the desired TBN of the final product, but typically ranges from about 100 to about 220 wt% of that required stoichiometrically (preferably at least about about 125 wt%).

  Sulfurized phenols and metal salts of phenols are prepared by reaction with suitable metal compounds such as oxides or hydroxides and neutral or overbased products that may be obtained by methods well known in the art. . Reacting sulfur-containing compounds such as hydrogen sulfide, sulfur monohalides or sulfur dihalides or reacting sulfur with phenol to form a product that is generally a mixture of compounds in which two or more phenols are crosslinked by sulfur-containing crosslinking. By doing so, a sulfurized phenol may be prepared.

  Generally, the one or more detergents are present in the lubricating oil composition in an amount ranging from about 0.01 wt% to about 10 wt%, based on the total weight of the lubricating oil composition.

  Examples of rust inhibitors include, but are not limited to: nonionic polyoxyalkylene materials such as polyoxyethylene lauryl ether, polyoxyethylene higher alcohol ether, polyoxyethylene nonyl phenyl ether, polyoxyethylene octyl phenyl Ether, polyoxyethylene octyl stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene sorbitol monostearate, polyoxyethylene sorbitol monooleate, and polyethylene glycol monooleate; stearic acid and other fatty acids; dicarboxylic acid; metal soap Fatty acid amine salt; metal salt of heavy sulfonic acid; partial carboxylic acid ester of polyhydric alcohol; phosphorus ester; (short chain) alkenyl succinic acid; Ester and nitrogen-containing derivatives thereof; synthetic alkaryl sulphonate, for example, metal dinonylnaphthalene sulfonates; and the like and mixtures thereof.

Examples of friction modifiers include, but are not limited to: alkoxylated fatty amines; boronated fatty epoxides; fatty phosphites, fatty epoxides, fatty amines, boronated alkoxylated fatty amines, fatty acid metal salts, fatty acid amides Glycerol esters, boronated glycerol esters; and fatty imidazolines (as disclosed in US Pat. No. 6,372,696, the contents of which are incorporated herein by reference); ammonia and alkanolamines, etc. and nitrogen-containing compounds and _C 4 _{-C 75} is selected from the group consisting of a mixture thereof, preferably _C 6 _{-C 24,} and most preferably _C 6 _{-C 20} fatty acid friction modifier derived from the reaction product of the ester .

  Examples of antifoaming agents include, but are not limited to: polymers of alkyl methacrylates; polymers of dimethyl silicone and the like and mixtures thereof.

  Examples of pour point depressants include, but are not limited to: polymethacrylate, alkyl acrylate polymer, alkyl methacrylate polymer, di (tetra-paraffin phenol) phthalate, condensate of tetra-paraffin phenol, naphthalene and chlorinated paraffin Condensates and combinations thereof. In one form, the pour point depressant comprises ethylene-vinyl acetate copolymer, condensate of chlorinated paraffin and phenol, polyalkylstyrene, and the like and combinations thereof. The amount of pour point depressant can vary from about 0.01 wt% to about 10 wt%.

  Examples of demulsifiers include but are not limited to: anionic surfactants (eg, alkyl-naphthalene sulfonates, alkyl benzene sulfonates, etc.), nonionic alkoxylated alkylphenol resins, polymers of alkylene oxides (eg, polyethylene oxide) Block copolymers such as polypropylene oxide, ethylene oxide, and propylene oxide), esters of oil-soluble acids, polyoxyethylene sorbitan esters, and the like, and combinations thereof. The amount of demulsifier can vary from about 0.01 wt% to about 10 wt%.

  Examples of corrosion inhibitors include, but are not limited to: dodecyl succinic acid half-esters or amides, phosphate esters, thiophosphates, alkyl imidazolines, sarcosine, and combinations thereof. The amount of corrosion inhibitor can vary from about 0.01 wt% to about 5 wt%.

  Examples of extreme pressure additives include, but are not limited to: sulfurized animal or vegetable oils, sulfurized animal or vegetable fatty acid esters, fully or partially esterified of trivalent or pentavalent acids of phosphorus Esters, sulfurized olefins, dihydrocarbyl polysulfides, sulfurized Diels-Alder adducts, sulfurized dicyclopentadiene, sulfurized or cosulfided mixtures of monounsaturated olefins and fatty acid esters, cosulfurized blends of fatty acids, fatty acid esters and alpha olefins, functionally Substituted dihydrocarbyl polysulfides, thia-aldehydes, thia-ketones, epithio compounds, sulfur-containing acetal derivatives, cosulfurized blends of terpenes and acyclic olefins, and polysulfide olefin products, amine salts of phosphate esters or thiophosphate esters Etc. and These combinations. The amount of extreme pressure additive can vary from about 0.01 wt% to about 5 wt%.

  Each of the additives, when used, is used in a functionally effective amount to impart the desired properties to the lubricating oil. Thus, for example, if the additive is a friction modifier, a functionally effective amount of this friction modifier will be sufficient to provide the desired friction modifying (adjusting) properties to the lubricating oil. In general, when used, the concentration of each of these additives is about 0.001 wt% to about 10 wt%, in one form about 0.005 wt, unless otherwise specified, based on the total weight of the lubricating oil composition. % To about 5 wt%, or in one form about 0.1 wt% to about 2.5 wt%. Further, the total amount of additives in the lubricating oil composition may be 0.001 wt% to about 20 wt%, about 0.01 wt% to about 10 wt%, or about 0.1 wt%, based on the total weight of the lubricating oil composition. It may be in the range of ~ 5 wt%.

  The end use of the lubricating oil composition of the present invention is, for example, a marine cylinder lubricating oil in a crosshead diesel engine, a crankcase lubricating oil, an automobile, a heavy oil lubricating oil in a steel mill, etc. It may be used as grease. Whether the lubricating oil composition is fluid or solid will usually depend on whether a thickener is present. Typical thickeners include polyurea acetate, lithium stearate and the like.

  In another form of the invention, the lubricating oil composition of the invention may be provided as an additive package or concentrate, wherein the additive is, for example, mineral oil, naphtha, benzene, toluene or xylene, etc. Incorporated in a substantially inert, usually liquid organic diluent, forms an additive concentrate. These concentrates usually contain about 20% to about 80% by weight of such diluent. Typically, neutral oils having a viscosity of from about 4 to about 8.5 cSt at 100 ° C., preferably from about 4 to about 6 cSt at 100 ° C. are used as diluents, but are compatible with additives and finished lubricants. Synthetic oils can be used as well as other soluble organic liquids. The additive package will typically also contain one or more of a variety of other additives as described above, in desired amounts and ratios that facilitate direct combination with the required amount of base oil. .

  The following examples are presented to illustrate embodiments of the invention, but are not intended to limit the invention to the particular forms described. Unless stated to the contrary, all parts and percentages are by weight. All numbers are approximate. When a numerical range is indicated, it should be understood that forms outside the range are still within the scope of the invention. Specific details described in each example should not be construed as necessary features of the invention.

Examples The following examples are intended for illustrative purposes only, and in no way limit the scope of the invention.

  In order to evaluate the silver lubricity additive composition of the present invention using silver wear and friction tests, a lubricating oil composition formulation was prepared as described in Table 2 below.

Silver wear assessment using silver disc wear and friction test (Amoco modified silver disc wear and friction test)
The lubricant additives of Examples 1-3 and Comparative Example A were evaluated using an Amoco modified silver disk wear and friction test. Four formulations were tested with the Amoco modified silver disc wear and friction test known to those skilled in the art. This wear test procedure is a laboratory test to determine the wear resistance characteristics of a lubricating oil. The tester is a silver pin insert bearing manufactured by the Electromotive Division (EMD) of General Motors, Inc. or a 1/4 inch silver disc 3 of the same quality and size used in the plating of railway diesel engines. Includes a system in which one half inch diameter 52100 steel balls assembled together are placed. These discs are in a fixed triangular position in the reservoir containing the oil sample to be tested for silver wear resistance properties. The steel ball is located above and is in contact with the three silver disks. In carrying out these tests, the sphere rotates with the appropriate weight on the lever arm and against the three discs with a certain pressure. The test result is determined by using a low power microscope to examine and measure the scar on the disk. A wear scar diameter of 2.2 mm or less is considered to indicate sufficient silver wear protection. The rotation of the steel ball on the silver disc continues for 30 minutes at 600 revolutions per minute under a 23 kilogram static load. Each oil was tested at 500F. The coefficient of friction is measured for each formulation.

  Silver disk wear and friction test data are summarized in Table 2 below. The data obtained with formulation A was used as a baseline.

  The results illustrated in Table 3 show that the lubricating oil compositions of the present invention (Examples 1-3) have very good wear resistance and very good anti-friction properties (anti-resisting) compared to the baseline formulation (Comparative Example A). (Friction) properties are illustrated.

  It will be understood that various modifications may be made to the form disclosed herein. Therefore, the above description should not be construed as limiting, but merely as exemplifications of preferred forms. For example, the functions implemented as the best mode for practicing the present invention and described above are for illustrative purposes only. Other arrangements and methods may be practiced by those skilled in the art without departing from the scope and spirit of the invention. Moreover, those skilled in the art will envision other modifications within the scope and spirit of the claims appended hereto.

Claims (15)

Medium speed diesel engine crankcase lubricant composition including:
(A) a major amount of oil of lubricating viscosity; and (b) 0.1 to 5.0% by weight of a silver lubricating additive comprising:
(I) alkoxylated fatty amines or salts thereof;
(Ii) an alkoxylated fatty diamine or a salt thereof; or (iii) a mixture of (i) and (ii) above. The lubricating oil composition of claim 1, wherein the alkoxylated fatty amine is Formula 1:

Wherein, _{R 1} is an aliphatic fatty acid chain ranging from C8 to C24; _{R 2} is independently hydrogen or C1~C8 alkyl; and wherein x and y are each independently at least 1 and x + y ≦ 50; and where the alkoxylated fatty diamine is of formula 2:

Here, R3 is an aliphatic fatty acid chain ranging from C8 to C24; each R4 is independently hydrogen or C1~C8 alkyl; and _{R 5} is C1~C8 divalent alkylene; wherein a + b + c Each independently is at least 1 and a + b + c ≦ 50. The lubricating oil composition of claim 1, wherein the alkoxylated fatty amine salt is Formula 3.

Wherein R ₁ is an aliphatic fatty acid chain in the range of C8-C24; R ₂ is independently hydrogen or C1-C8 alkyl; where x and y are each independently at least 1 and x + y ≦ And wherein Z is an anion of an organic or inorganic acid; and wherein the alkoxylated fatty diamine salt is of formula 4:

Where R ₃ is an aliphatic fatty acid chain in the range of C8-C24; each R ₄ is independently hydrogen or C1-C8 alkyl; and R ₅ is C1-C8 divalent alkylene; Wherein a + b + c is independently at least 1 and a + b + c ≦ 50; and where Z is an anion of an organic or inorganic acid.   The lubricating oil composition of claim 3, wherein Z is selected from the group comprising phosphates, phosphites, dithiophosphates, sulfates, sulfonates, carbonates, and anions from carboxylic acids and fatty acids.   Alkoxylated fatty amines are propoxylated monoamines, butoxylated monoamines, alkoxylated alkyldiisopropanolamines, ethoxylated monoamines such as ethoxylated octadecylamine, ethoxylated cocoalkylamines, ethoxylated oleylamines, diethoxylated oleylamines, ethoxylated soyaalkyls The lubricating oil composition of claim 1, selected from the group comprising an amine and an ethoxylated tallow alkyl amine.   Alkoxylated fatty diamines include ethoxylated diamines such as tris (2-hydroxyethyl) -N-tallow alkyl-1,3-diamine propane, commonly known as Ethodomeen T / 13, Ethodomeen T / 20, and Ethodomeen T / 25 The lubricating oil composition of claim 1, selected from the group.   The lubricating oil composition of claim 1, wherein the alkoxylated fatty salt is diethoxylated oleyl ammonium bis (2-ethylhexyl) phosphate.   The silver lubricity additive is an organic or inorganic alkoxylated fatty amine or diamine salt selected from the group comprising phosphates, phosphites, dithiophosphates, sulfates, sulfonates, carbonates, and anions from carboxylic acids and fatty acids, The lubricating oil composition of claim 1.   9. The lubricating oil composition of claim 8, wherein the alkoxylated fatty amine salt group is an alkyl acidic phosphate group. The lubricating oil composition of claim 9, wherein the alkyl acidic phosphate group is a dialkyl monohydrogen phosphate or monoalkyl dihydrogen phosphate according to Formulas 5 and 6 below:

Here, R ₆ , R ₇ and R ₈ are independently linear, branched alkyl or alkylated aromatic having from about 3 to about 40 carbon atoms. The lubricating oil composition of claim 10, wherein the alkyl acidic phosphate group is selected from the group comprising:
Di-2-ethylhexyl hydrogen phosphate, dihexyl hydrogen phosphate, propyl dihydrogen phosphate, dipropyl hydrogen phosphate, butyl dihydrogen phosphate, butyl dihydrogen phosphate, dipentyl hydrogen phosphate, hexyl dihydrogen phosphate, dihexyl hydrogen phosphate, heptyl dihydrogen phosphate, diheptyl Hydrogen phosphate, octyl dihydrogen phosphate, dioctyl hydrogen phosphate, decyl dihydrogen phosphate, didecyl hydrogen phosphate, decyl dihydrogen phosphate, didecyl hydrogen phosphate and the like. The lubricating oil composition of claim 1, wherein the alkoxylated fatty amine or alkoxylated fatty diamine contains a saturated or unsaturated C ₁₂ -C ₂₄ alkyl radical that is branched or linear.   The lubricating oil composition of claim 1, wherein the silver lubricity additive is present at 0.20 to 4 wt%.   The lubricating oil composition of claim 1, wherein the medium speed diesel engine is selected from the group comprising railroad locomotives, marine tugboats and stationary power engines. (A) a major amount of oil of lubricating viscosity; and (b) 0.1 to 5.0% by weight of a silver lubricating additive comprising:
(I) alkoxylated fatty amines or salts thereof;
(Ii) an alkoxylated fatty diamine or a salt thereof; or (iii) a mixture of (i) and (ii) above;
A method of reducing silver bearing wear and friction in a medium speed diesel engine comprising lubricating the medium speed diesel engine with a lubricating oil composition comprising: