KR100714140B1 - Lubricated parts of vehicles and engines, lubricant compositions and methods for lubrication - Google Patents

Abstract

Lubrication methods for lubricated surfaces and moving parts. The lubricated surface contains about 9.5 to about 25 weight percent lubricating viscous base oil and a nitrogen-containing olefin copolymer derived from about 0.15 to about 1.0 carboxyl group grafted olefin copolymer per 1000 number average molecular weight of the copolymer. Thin film coatings of lubricant compositions, comprising% additives. The copolymer has a number average molecular weight in the range of about 10,000 to about 100,000. The amount of additive in the lubricant composition is based on the total weight of the lubricant composition.

Description

Lubrication Parts, Lubricant Compositions and Lubrication Methods for Vehicles and Engines {LUBRICATED PARTS OF VEHICLES AND ENGINES, LUBRICANT COMPOSITIONS AND METHODS FOR LUBRICATION}

The following specification relates to lubricants, lubricant compositions and additives, lubricated parts and engines, and lubrication methods for moving parts to provide improved performance in harsh environments.

Attention to the environment has led to ongoing efforts to reduce CO, hydrocarbon and nitrogen oxide (NO _x ) emissions of engines, especially compression ignition engines such as diesel engines. Several methods are commonly used to reduce this release. One method used to reduce the emissions of diesel engines is known as exhaust gas recirculation or EGR. EGR reduces NO _x emissions by introducing a flame retardant component (exhaust gas) into the engine combustion chamber. The flame retardant component reduces the flame temperature peak and reduces the NO _x formation. An additional reduction in NO _x emissions is obtained by cooling the exhaust gas before it returns to the engine. Cooler combustion mixtures lead to greater power generation and better fuel economy with a fixed NO _x emission value.

While reducing NO _x emissions, the EGR system in the engine increases the levels of NO _x and sulfur oxide (SO _x ) -based and particulate matter in the lubricant circulated between these engines. API CI-4 oil performance specifications were established for use of lubricating oil compositions in cooled EGR equipped diesel engines.

Other methods for reducing emissions include early shutoff of the engine cutout; The use of a pilot fuel injector upstream of the main fuel injector to reduce NO _x generation; Shaping rate of combustion to reduce combustion temperature peaks and reduce NO _x generation; To push excess air into the combustion chamber using a turbocharger to increase power output, and to reduce the levels of soluble organic fractions of unburned hydrocarbons, carbon monoxide, nitrogen oxides and particulate matter in engine exhaust. Control of engine timing to provide for the use of catalyst post-treatment, such as devices containing oxidation catalysts.

However, diesel fuel contains sulfur. When sulfur contained in the fuel is burned in the engine, sulfur is converted into SO _x . Water vapor formed by combustion of the fuel is mixed with NO _x and SO _x to form corrosive acid compounds such as nitric acid and sulfuric acid in the recycled and cooled exhaust gas. These acids attack metals in the engine and cause corrosion of these metals. Improved protection of metal engine components is therefore necessary for these applications.

Other harsh environments for lubricated parts and engines include, for example, marine applications where lubricated parts and engines are constantly exposed to seawater environments. Lubricants with improved corrosion protection properties are needed for this application.

In view of the foregoing, lubricants meet constant demands and always undergo constant improvement to change their needs. However, there is a continuing need for lubricant compositions and additives that can meet the demand for harsh environments as described above.

The present invention therefore relates to lubricants, lubricant compositions and additives, lubricated parts and engines that can meet the demands of harsh environments, and lubrication methods for moving parts to provide improved performance.

Here in one preferred embodiment the lubricated surface is presented. The lubricated surface may comprise an engine drive train, an internal surface or component of an internal combustion engine, and an internal surface or component of a compression ignition engine. The lubricated surface contains about 9.5 to about 25 weight percent lubricating viscous base oil and a nitrogen-containing olefin copolymer derived from about 0.15 to about 1.0 carboxyl group grafted olefin copolymer per 1000 number average molecular weight of the copolymer. Thin film coatings of lubricant compositions, comprising% additives. The copolymer has a number average molecular weight in the range of about 10,000 to about 100,000. The amount of additive in the lubricant composition is based on the total weight of the lubricant composition.

In another embodiment, a vehicle having a moving part and containing a lubricant for moving part lubrication is presented. Lubricants contain about 9.5 to about 25 weight percent of an additive comprising a lubricating viscous oil and a nitrogen containing olefin copolymer derived from an olefin copolymer grafted from about 0.15 to about 1.0 carboxyl groups per 1000 number average molecular weight units of the copolymer. It includes. The copolymer has a number average molecular weight in the range of about 10,000 to about 100,000. The amount of additive in the lubricant composition is based on the total weight of the lubricant composition.

Yet another implementation provides a method for lubricating moving parts. The method includes contacting a moving part with a lubricant composition containing about 9.5 to about 25 weight percent lubricant additive. The lubricant additive contains a nitrogen-containing olefin copolymer derived from an olefin copolymer grafted from about 0.15 to about 1.0 carboxyl groups per 1000 number average molecular weight units of the copolymer. The copolymer has a number average molecular weight in the range of about 10,000 to about 100,000. The amount of additive in the lubricant composition is based on the total weight of the lubricant composition.

 Another embodiment of the present disclosure provides a metal surface that includes a corrosion inhibition amount of a lubricant. The lubricant is sufficiently formulated comprising about 9.5 to about 25% by weight of an additive containing a nitrogen-containing olefin copolymer derived from an olefin copolymer grafted from about 0.15 to about 1.0 carboxyl groups per 1000 number average molecular weight units of the copolymer. Provided by the formulated lubricant composition. The copolymer has a number average molecular weight in the range of about 10,000 to about 100,000, and the amount of additive in the lubricant composition is based on the total weight of the lubricant composition.

Without being bound by theoretical considerations, it is believed that when an additive containing a nitrogen-containing olefin component is present in the lubricant composition in an amount of at least about 9.5% by weight, it forms an effective corrosion barrier film on the metal surface. Corrosion barrier films are effective in reducing or preventing contact between a surface and a caustic such as an acid. The additive may be mixed with oily emulsion and applied to the surface as a protective coating. In other applications, the additive is provided in a fully formulated lubricant composition. Despite the presence of detergents and dispersants in fully formulated lubricant compositions, the nitrogen-containing olefin component remains firmly attached to the metal surface, extending its protective effect on the surface of the metal.

The compositions and methods described herein are particularly suitable for harsh environments such as present in marine applications and large diesel engines equipped with exhaust gas recirculation (EGR). Other features and advantages of the compositions and methods described herein are not limited to the embodiments described herein, and will be apparent by reference in accordance with the following detailed description to illustrate preferred embodiments.

Detailed description of the preferred implementation

As used herein, the term "hydrocarbyl substituent" or "hydrocarbyl group" is used in its general meaning well known to those skilled in the art. In particular, this refers to a group having carbon atoms directly attached to the rest of the molecule and having significant hydrocarbon characteristics. Examples of hydrocarbyl groups include the following:

(1) hydrocarbon substituents, that is, aliphatic (eg, alkyl or alkenyl), alicyclic (eg, cycloalkyl, cycloalkenyl) substituents, and aromatic-, aliphatic-, and cycloaliphatic-substituted aromatic substituents, as well as Cyclic substituents in which the ring is completed through another part of the molecule (eg, two substituents together form an alicyclic radical);

(2) substituted hydrocarbon substituents, ie hydrocarbon substituents (e.g., halo (especially chloro and fluoro), hydroxy, alkoxy, mercapto, alkylmercapto, nitro, nitroso, and sulphate) A substituent including a non-hydrocarbon group that does not significantly alter the foxy);

(3) Hetero-substituents, ie, substituents in the context of the present specification, which include those other than carbon in a ring or chain that does not consist of carbon while having significant hydrocarbon characteristics. Hetero-atoms include sulfur, oxygen, nitrogen and include substituents such as pyridyl, furyl, thienyl and imidazolyl. In general, only two, preferably only one, non-hydrocarbon substituents will be present for each ten carbon atoms in the hydrocarbyl group; Typically, the hydrocarbyl group will be free of non-hydrocarbon substituents.

In all implementations of the present disclosure, certain lubricant components or additives are provided. Additives are generally referred to as multifunctional viscosity index modifiers. However, when used in an amount of at least 9.5% by weight in a fully formulated lubricant composition, the lubricant additive provides an effective corrosion inhibiting film that can coexist with detergents and dispersants in the lubricant composition. In particular, lubricant additives include nitrogen-containing olefin copolymers derived from highly grafted, multifunctional olefin copolymers and polyamine compounds, generally as described in US Pat. No. 6,107,257 (Valcho et al.). The nitrogen-containing olefin copolymer is dissolved in a suitable solvent such as Solvent Neutral 100 to provide the additive component.

One particularly useful nitrogen-containing olefin copolymer is derived from an olefin copolymer derived from an olefin copolymer grafted from about 0.15 to about 1.0 carboxyl groups per 1000 number average molecular weight units of the copolymer. The carboxyl group is subsequently reacted with the amine to give a nitrogen containing olefin copolymer. The olefin copolymer can have a number average molecular weight in the range of 10,000 to about 100,000.

Another nitrogen-containing olefin copolymer for use in the lubricant composition according to the present specification is an olefin copolymer derived from a copolymer grafted with about 0.3 to about 0.75 carboxyl groups per 1000 number average molecular weight units of the copolymer. In this case, the copolymer may have a number average molecular weight ranging from about 30,000 to about 60,000.

Other nitrogen-containing olefin copolymers that may be used in accordance with the present disclosure are described, for example, in US Pat. ). 4,382,007 (Chafetz et al.), 4,144,181 (Elliott et al.), 4,863,623 (Nalesnik), 5,075,383 (Migdal et al.), 5,556,923 (Caines et al.), 5,932,525 (Ney et al.), 5,162,086 (Migdal et al.), 29, and 5,744. Chung et al.). Particularly useful nitrogen containing olefin copolymers are described in US Pat. No. 6,107,257 (Valcho et al.).

The term "polymers and copolymers" is generally used including ethylene copolymers, trimers or interpolymers. Such materials may contain minor amounts of other olefin monomers as long as they do not substantially change the basic properties of the ethylene copolymer.

The polymer or copolymer backbone of the lubricant component is a highly grafted, multifunctional olefin copolymer, which is made from ethylene and propylene or from one or more higher olefins within the range of ethylene and C ₃ to C ₂₃ alpha-olefins. Can be prepared. Most preferred are copolymers of ethylene and propylene. Instead of propylene used to form copolymers or to form trimers together with ethylene and propylene, other suitable alpha-olefins include 1-butene, 1-pentene, 1-hexene, 1-octene and styrene; Α, ω-diolefins such as 1,5-hexadiene, 1,6-heptadiene, 1,7-octadiene; Branched chain alpha-olefins such as 4-methylbutene-1,5-methylpentene-1 and 6-methylheptene-1; And mixtures thereof.

More complex polymer backbones, often referred to as interpolymers, are made using third components. The third component used to make the interpolymer skeleton is generally a polyene monomer selected from non-conjugated dienes and trienes. Non-conjugated diene components have from 5 to 14 carbon atoms in the chain. Preferably, the diene monomer is characterized by the presence of vinyl groups in the structure and may comprise cyclic and bicyclo compounds. Each diene is 1,4-hexadiene, 1,4-cyclohexadiene, dicyclopentadiene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 1,5-heptadiene, and 1,6-octadiene. Mixtures of one or more dienes may be used in the preparation of the interpolymers. Preferred nonconjugated dienes for the preparation of trimer or interpolymer substrates are 1,4-hexadiene.

The triene component will have at least two nonconjugated double bonds and up to about 30 carbon atoms in the chain. Typical trienes useful for preparing interpolymer skeletons include 1-isopropylidene-3α, 4,7,7α-tetrahydroidene, 1-isopropylidenedicyclopentadiene, dihydro-isodicyclopentadiene, and 2- (2-methylene-4-methyl-3-pentyl) [2.2.1] bicyclo-5-heptene.

Ethylene-propylene or higher alpha-olefin copolymers comprise about 15 to 80 mol% ethylene and about 85 to 20 mol% C ₃ to C ₂₃ alpha-olefins about 35 to 75 mol% ethylene and about 65 to 25 mol% C ₃ To a C ₂₃ alpha-olefin, with a preferred molar ratio of 50 to 70 mol% ethylene and 50 to 30 mol% C ₃ to C ₂₃ alpha-olefin, with 55 to 65 mol% ethylene and 45 to It may consist of the most preferable ratio of 35 mol% C ₃ to C ₂₃ alpha-olefin.

Terpolymer modifications of the polymer may include from about 0.1 to 10 mole percent of unconjugated diene or triene.

The polymer backbone, which is an ethylene copolymer or trimer, is an oil-soluble having a number average molecular weight of about 20,000 to 100,000, preferably a number average molecular weight in the range of 30,000 to 60,000, as measured by gel permeation chromatography and global measurement standards. , Linear or branched polymers.

The ethylenically unsaturated carboxylic acid material is grafted to the polymer backbone described above to form acylated ethylene copolymers. These carboxyl reactants suitable for being grafted to the copolymer backbone are converted to said carboxyl groups by the bonding of at least one ethylene and at least one, preferably two, carboxylic acids or their anhydride groups or by oxidation or hydrolysis. It includes a polar group. Preferably, the carboxyl reactant is selected from the group consisting of acrylic reactants, methacryl reactants, cinnamic reactants, male reactants, fumar reactants and itacone reactants. More preferably, the carboxyl reactant is selected from the group consisting of maleic acid, fumaric acid, maleic anhydride, or two or more thereof. Male anhydrides or derivatives thereof are generally most preferred because of their commercial availability and ease of reaction. In the case of unsaturated ethylene copolymers or trimers, itaconic acid or its anhydride is preferred because of its reduced tendency to form crosslinked structures during the free-radical grafting process.

The ethylenically unsaturated carboxylic acid material may typically provide two or one carboxyl groups per mole of reactant to the grafted polymer. That is, methyl methacrylate can provide one carboxyl group per molecule in the grafted polymer and maleic anhydride can provide two carboxyl groups per molecule in the grafted polymer.

The carboxyl reactant is grafted to the polymer backbone described above to provide 0.15 to 1.0 carboxyl groups per 1000 average molecular weights of polymer skeleton units, preferably 0.3 to 0.75 carboxyl groups per 1000 average molecular weights. For example, a copolymer substrate having a number average molecular weight of 20,000 can be grafted with 3 to 20 carboxyl groups per polymer. Copolymers having a number average molecular weight of 10,000 may be grafted with 15 to 100 carboxyl groups per polymer chain.

Polymeric intermediates having carboxylic acid acylation functionality react with the polyamine compound to provide a nitrogen containing olefin copolymer. The polyamine compound may be selected from the group consisting of:

(a) N-arylphenylenediamine represented by the following formula:

Wherein R ¹ is hydrogen, --NH-aryl, --NH-arylalkyl, --NH-alkyl, or alkyl, alkenyl, alkoxy, aralkyl, alkaryl, hydroxyalkyl or aminoalkyl Is a branched or linear chain radical having 4 to 24 carbon atoms which may be R ² is —NH ₂ , CH ₂ — (CH ₂ ) _n —NH ₂ , CH ₂ -aryl-NH ₂ , where n is Has a value from 1 to 10), R ³ is hydrogen, alkyl, alkenyl, alkoxy, aralkyl, alkaryl having 4 to 24 carbon atoms);

(b) aminothiazole from the group consisting of aminothiazole, aminobenzothiazole, aminobenzothiadiazole and aminoalkyl thiazole;

(c) aminocarbazoles represented by the formula:

Wherein R and R ¹ represent hydrogen or an alkyl, alkenyl, or alkoxy radical having 1 to 14 carbon atoms;

(d) aminoindoles represented by the formula:

Wherein R represents hydrogen or an alkyl radical having 1 to 14 carbon atoms;

(e) aminopyrroles represented by the formula:

(Wherein R is a divalent alkylene radical having 2 to 6 carbon atoms and R 1 is hydrogen or an alkyl radical having 1 to 14 carbon atoms);

(f) amino-indazolinones represented by the formula:

Wherein R is hydrogen or an alkyl radical having 1 to 14 carbon atoms;

(g) aminomercaptotriazoles represented by the formula:

Wherein R may be absent or is a C ₁ -C ₁₀ linear or branched hydrocarbon selected from the group consisting of alkyl, alkenyl, arylalkyl, or aryl;

(h) aminoferimidine represented by the formula:

Wherein R represents hydrogen or alkyl or an alkoxy radical having 1 to 14 carbon atoms;

(i) aminoalkyl imidazoles such as 1- (2-aminoethyl) imidazole, 1- (3-aminopropyl) imidazole; And

(j) aminoalkyl morpholines, such as 4- (3-aminopropyl) morpholine.

Particularly preferred polyamines for reacting with olefin copolymers are N-arylphenylenediamines, more particularly N-phenylphenylenediamines, for example N-phenyl-1,4-phenylenediamine, N-phenyl-1,3 -Phenylenediamine, and N-phenyl-1,2-phenylenediamine.

It is preferred that the polyamine contains only one primary amine group to avoid coupling and / or gelling of the olefin copolymer.

Highly grafted, multifunctional olefin copolymers can be post-treated to contain the additional properties essential or desirable for certain lubricant applications. Post-treatment techniques are well known in the art and include boronization, phosphorylation, maleinization, and reaction with anhydrides, ketones, acids or acid anhydrides.

Methods for stabilizing the color of nitrogen-containing olefin copolymers using anhydrides, ketones, acids or acid anhydrides are well known and are described, for example, in US Pat. No. 5,207,938.

The highly grafted, multifunctional olefin copolymer can be incorporated into the base oil in any convenient way. Therefore, highly grafted, multifunctional olefin copolymers can be added directly to the base oil by dispersing or dissolving the same in the lubricating oil at a desired concentration. Such mixing into the base oil can occur at room temperature or at high temperatures. Alternatively, the highly grafted, multifunctional olefin copolymer can be dissolved in a suitable solvent in an amount ranging from 10 to about 20% by weight to form a solution. The solution can be mixed with a suitable oil-soluble solvent / diluent (such as benzene, xylene, toluene, lubricating base oil and petroleum distillate) to form a concentrate, which is then mixed with a lubricant to obtain a final formulation. do. Such additive concentrates are typically from about 5 to about 90 weight percent, preferably from about 40 to (diluents and solutions that exclude the active ingredient (AI) basis, such as the weight of impurities) About 60% by weight, a highly grafted, multifunctional olefin copolymer solution, and typically about 10-90% by weight, preferably about 40-60% by weight, base oil based on concentrated weight.

In the preparation of lubricating oil formulations it is a common practice to incorporate the additives in the form of 5 to 30% by weight active ingredient concentrate in hydrocarbon oils such as mineral lubricants or other suitable solvents. In general, these concentrates may be diluted from 3 to 100, for example 5 to 40, by weight of the lubricant per weight part of the additive package forming the finished lubricant, such as crankcase motor oil. The purpose of concentration is, of course, not only to facilitate the solution or dispersion in the final mixture, but also to make the manipulation of the various materials difficult and unwieldy. Therefore, the highly grafted, multifunctional olefin copolymer solution will typically be used in a concentration form of, for example, 40 to about 60 weight percent in the lubricating oil fraction.

Lubricant compositions prepared with adducts containing the nitrogen-containing olefin copolymers described above are used in a wide range of applications. The lubricant composition may be a low ash, low sulfur lubricant composition suitable for compression ignition engines. For compression ignition engines and spark ignition engines, lubricant compositions that meet or exceed published GF-4 or API-CI-4 standards are preferred. Lubricant compositions according to the GF-4 or API-CI-4 standards include a base oil and an oil additive package to provide a fully formulated lubricant. The base oil for lubricants according to the present specification is a lubricating viscous oil selected from natural lubricants, synthetic lubricants and mixtures thereof. These base oils include those commonly used as crankcase lubricants for spark-ignition and compression-ignition internal combustion engines, such as automotive and truck engines, marine or train diesel engines, and the like.

Natural oils include animal and vegetable oils (eg pizza horse oil, lard oil), liquid petroleum oils and hydrorefined, solvent-treated or acid-treated paraffins, naphthenes and mixed paraffin-naphthenes. Types of mineral lubricants. Lubricated viscous oils derived from coal or shale are also useful base oils. Synthetic lubricating oils used in the present invention are synthetic hydrocarbon oils (poly-alpha-olefins, alkylated) in which the excitonary terminal hydroxy group is conventionally used, modified by esters of dicarboxylic acids and silicon-base oils, such as esterification, etherification, etc. Aromatic, alkylene oxide polymers, interpolymers, copolymers, and derivatives thereof).

Fully formulated lubricants typically include an additive package that will provide the necessary properties in the formulation. Among the types of additives included in the additive package, there are clean / dispersant, friction modifiers, seal inflation agents, abrasion inhibitors, extreme pressure inhibitors, antioxidants, antifoaming agents, lubricants, rust inhibitors, corrosion inhibitors, anti-emulsifiers, viscosity index Enhancers, dyes, and the like. Various of these components are well known to those skilled in the art and are preferably used in the usual amounts of additives and compositions described herein.

For example, suitable cleansing / dispersing agents are selected from the group consisting of, but not limited to, ash-free oil-soluble dispersants having base nitrogen and / or one or more hydroxyl groups in the molecule. Suitable cleaning / dispersing agents include alkenyl succinimides, alkenyl succinic acid esters, alkenyl succinic ester-amides, Mannich bases, hydrocarbyl polyamines, polyamines of polymers, or olefin copolymers.

Alkenyl succinimides in which succinic groups contain hydrocarbyl substituents containing at least 30 carbon atoms are described, for example, in US Pat. 3,202,678; 3,216,936; 3,219,666; 3,254,025; 3,272,746; And 4,234,435.

Alkenyl succinic acid esters and diesters of polyhydric alcohols containing 2-20 carbon atoms and 2-6 hydroxyl groups can be used in the form of ash-free phosphorus-containing dispersants. Each example is described in US Pat. No. 3,331,776; 3,381,022; And 3,522,179.

Suitable alkenyl succinic ester-amides to form ashless phosphorylated dispersants are described, for example, in US Pat. No. 3,184,474; 3,576,743; 3,632,511; 3,804,763; 3,836,471; 3,862,981; 3,936,480; 3,948,800; 3,950,341; 3,957,854; 3,957,855; 3,991,098; 4,071,548; And 4,173,540.

Hydrocarbyl polyamines are described in US Pat. Nos. 3,275,554; 3,394,576; 3,438,757; 3,454,555; 3,565,804; 3,671,511; And 3,821,302.

The Mannich salt dispersant is preferably an alkyl phenol having one or more aliphatic aldehydes (particularly formaldehyde and derivatives thereof) containing 1 to about 7 carbon atoms, typically having a long chain alkyl substituent in the ring, and a polyamine ( In particular polyalkylene polyamines). Examples of Mannich condensation products, and methods for their preparation, are described in US Pat. No. 2,459,112; 2,962,442; 2,984,550; 3,036,003; 3,166,516; 3,236,770; 3,368,972; 3,413,347; 3,442,808; 3,448,047; 3,454,497; 3,459,661; 3,493,520; 3,539,633; 3,558,743; 3,586,629; 3,591,598; 3,600,372; 3,634,515; 3,649,229; 3,697,574; 3,703,536; 3,704,308; 3,725,277; 3,725,480; 3,726,882; 3,736,357; 3,751,365; 3,756,953; 3,793,202; 3,798,165; 3,798,247; 3,803,039; 3,872,019; 3,904,595; 3,957,746; 3,980,569; 3,985,802; 4,006,089; 4,011,380; 4,025,451; 4,058,468; 4,083,699; 4,090,854; 4,354,950; And 4,485,023.

 Polyamine dispersants of polymers suitable as ashless dispersants of the present invention are polymers containing base amine groups and oil soluble groups (eg, pendant alkyl groups having 8 or more carbon atoms). These materials are described by interpolymers formed from aminoalkyl acylates and aminoalkyl acrylamides and various monomers such as decyl methacrylate, vinyl decyl ether or relatively high molecular weight olefins. Examples of polyamine dispersants of polymers are described in U.S. Patents 3,329,658; 3,449,250; 3,493,520; 3,519,565; 3,666,730; 3,687,849; And 3,702,300.

  Olefin copolymer dispersants include US Pat. Nos. 5,075,383 6,117,825; 6,107,258; 5,266,223; 5,350,532; 5,435,926; 4,952,637, 5,356,999, 5,374,364, and 5,424,366.

The various types of ashless dispersants described above are described in US Pat. Nos. 3,184,411; 3,342,735; 3,403,102; 3,502,607; 3,511,780; 3,513,093; 3,513,093; 4,615,826; 4,648,980; Phosphorylated by the procedures described in 4,857,214 and 5,198,133.

Dispersants of the invention may be boronated. Methods for boronating (borating) the various types of ashless dispersants described above are described in US Pat. No. 3,087,936; 3,254,025; 3,281,428; 3,282,955; 2,284,409; 2,284,410; 3,338,832; 3,344,069; 3,533,945; 3,658,836; 3,703,536; 3,718,663; 4,455,243; And 4,652,387.

Preferred procedures for phosphorylating and boronating ashless dispersants such as those mentioned above are described in US Pat. Nos. 4,857,214 and 5,198,133.

Alternatively, the dispersants described above may be used for the glycolation and Mannich base US Pat. No. 4,633,322; And Mannich bases linked as described in US Pat. No. 5,122,161.

The amount of ash-free dispersant relative to the active ingredient is generally within about 0.5 to about 7.5 weight percent, typically within about 0.5 to 5.0 weight percent, preferably within about 0.5 to about 3.0 weight percent, based on the finished oil, most preferred. Preferably within about 2.0 to about 3.0 weight percent.

  Suitable friction modifiers are described in US Pat. No. 5,344,579; 5,372,735; And 5,441,656. Seal inflation agents are described, for example, in US Pat. Nos. 3,794,081 and 4,029,587. Antiwear and / or extreme pressure inhibitors are described in US Pat. No. 4,857,214; 5,242,613; And 6,096,691. Suitable antioxidants are described in US Pat. No. 5,559,265; 6,001,786; 6,096,695; And 6,599,865. Antifoaming agents suitable for the compositions and additives described herein include US Pat. No. 3,235,498; 3,235,499; And 3,235,502. Rust and corrosion inhibitors are described in US Pat. Nos. 2,765,289; 2,749,311; 2,760,933; 2,850,453; 2,910,439; 3,663,561; 3,862,798; And 3,840,549. Viscosity index improvers and methods for their preparation are described, for example, in US Pat. No. 4,732,942; 4,863,623; 5,075,383; 5,112,508; 5,238,588; And 6,107,257. Multifunctional viscosity index enhancers are described in US Pat. No. 4,092,255; 4,170,561; 4,146,489; 4,715,975; 4,769,043; 4,810,754; 5,294,354; 5,523,008; 5,663,126; And 5,814,586; And 6,187,721. Antiemulsifiers are described in US Pat. Nos. 4,444,654 and 4,614,593.

Base oils suitable for use in formulating the compositions, additives and pesticides described herein can be selected from any synthetic or natural oil or mixtures thereof. Synthetic base oils include alkyl esters of dicarboxylic acids, polyglycols and alcohols, poly-alpha-olefins, alkyl benzenes including polybutenes, organic esters of phosphoric acid, and polysilicon oils. Natural base oils include mineral lubricants that may vary depending on whether their crude sources are, for example, paraffins, naphthenes and mixed paraffin-naphthenes. The base oil typically has a viscosity of about 2.5 to about 15 cSt, preferably about 2.5 to about 11 cSt at 100 ° C.

Thus, the base oils that may be used may be selected from any base oil in Group I-V, as specified in the "American Petroleum Institute Base Oil Interchangeability Guidelines". These base oil groups are listed in Table 1:

Base oil group ¹ Sulfur (% by weight) Saturate (wt%) Viscosity index County I > 0.03 And / or <90 80 to 120 Group Ⅱ ≤ 0.03 And ≥ 90 80 to 120 Group Ⅲ ≤ 0.03 And ≥ 90 ≥120 County Ⅳ All Polyalphaolefins (PAO) County Ⅴ Everything else that is not in I-IV

Group ¹ I-III is a mineral oil base stock.

The additives used in the formulation of the compositions described herein can be mixed in the base oil, either individually or at various sub-magnifications. However, it is preferable to combine all components that simultaneously use an additive concentrate (eg, add a diluent such as a hydrocarbon solvent to the additive). The use of additive concentrates has the advantage of intercompatibility provided by the combination of components when the additive concentrate is formed. In addition, the use of concentrates reduces the mixing time and reduces the possibility of mixing errors.

The following examples are provided to illustrate aspects of the implementation and do not limit the implementation in any way.

Example

Large Diesel Lubricant Formulations (SAE 15W-40) are manufactured on CITGO / Yubase base stock and are nitrogen-containing olefins in HiTEC ^® 5777D (solvent neutral 100 diluent) sold by 10% by weight of Ethyl Corporation of Richmond Virginia. Copolymer solution) solution, 0.2 wt% Pour Point Depressant (HiTEC ^® 5789), 14.8 wt% Dispersant Inhibitor Package (HiTEC ^® 1229), and 0.2 wt% amine oxidant (HiTEC ^® 7190). The ASTM D665 carbon steel rust pins are immersed twice in the lubricant formulation described above and in the lubricant formulation lacking the lubricant nitrogen-containing olefin copolymer component. The pins are then placed in 37 wt% hydrochloric acid in a closed glass jar at room temperature. The corrosion potential of the lubricant was evaluated by measuring the amount of gas bubbles generated by the reaction of hydrochloric acid on the metal phase. To compare the results, we used a score system in the 0-10 range with the most bubbles at 10. Lubricant formulations containing nitrogen-containing olefin copolymers received three points, whereas lubricant formulations without nitrogen-containing olefin copolymers received eight points. It was concluded that lubricant formulations containing at least 10 wt.% Nitrogen containing olefin copolymer solutions provided superior corrosion protection in acidic environments.

Throughout this specification, reference is made to a US patent number. All documents mentioned are hereby expressly incorporated in their entirety if they are fully described herein.

The above implementation may be modified to be considered in the practice of this. Therefore, implementations are not intended to be limited to the specific examples mentioned above. Rather, the implementations are within the scope and spirit of the appended claims, including their equivalents as possible as matters of law.

The patent is not intended to provide any disclosed implementation to the public, and any disclosed modifications or variations may not be included literally within the scope of the claims, and they are considered part on equivalent basis.

The lubricant compositions, lubricated surfaces and lubrication methods for moving parts are particularly suitable for use in harsh environments such as large diesel engines that provide improved corrosion protection features and are equipped with marine applications and exhaust gas recirculation (EGR).

Claims (34)

A 9.5 to 25% by weight additive comprising a lubricating viscous base oil and a nitrogen containing olefin copolymer derived from an olefin copolymer grafted from 0.15 to 1.0 carboxyl groups per 1000 number average molecular weight units of the copolymer, wherein The copolymer has a number average molecular weight ranging from 10,000 to 100,000, wherein the amount of additive in the lubricant composition is based on the total weight of the lubricant composition, wherein the lubricated surface comprises a thin film coating of the lubricant composition. The lubricated surface of claim 1, wherein the lubricated surface comprises an engine drive train. The lubricated surface of claim 1, wherein the lubricated surface comprises an internal surface or component of an internal combustion engine. The lubricated surface of claim 1, wherein the lubricated surface comprises an internal surface or component of a compression ignition engine. The lubricated surface of claim 1, wherein the copolymer is grafted with 0.3 to 0.75 carboxyl groups per 1000 number average molecular weight units of the copolymer and has a number average molecular weight in the range of 30,000 to 60,000. An automobile comprising a lubricated surface according to claim 1. A vehicle having a moving part and containing a lubricant for moving part lubrication, wherein the lubricant is a lubricating viscous oil and a nitrogen-containing olefin derived from an olefin copolymer grafted with 0.15 to 1.0 carboxyl groups per 1000 number average molecular weight units of the copolymer. 9.5 to 25% by weight of an additive containing a copolymer, wherein the copolymer has a number average molecular weight in the range of 10,000 to 100,000, wherein the amount of the additive in the lubricant composition is based on the total weight of the lubricant composition. 8. A vehicle according to claim 7, wherein the copolymer is grafted with 0.3 to 0.75 carboxyl groups per 1000 number average molecular weight units of the copolymer and has a number average molecular weight in the range of 30,000 to 60,000. 8. A vehicle according to claim 7, wherein the moving part comprises a large diesel engine comprising exhaust gas recirculation and a lubrication system for the engine. 9.5 to 25% by weight of an additive containing a base oil component of lubricating viscosity and a nitrogen-containing olefin copolymer derived from an olefin copolymer grafted with 0.15 to 1.0 carboxyl groups per 1000 number average molecular weight units of the copolymer, Wherein the copolymer has a number average molecular weight in the range of 10,000 to 100,000, wherein the amount of additive in the lubricant composition is based on the total weight of the lubricant composition. The low ash, low sulfur lubricant composition of claim 10 suitable for compression ignition engines. The lubricant composition of claim 10 wherein the copolymer is grafted with 0.3 to 0.75 carboxyl groups per 1000 number average molecular weight units of the copolymer and has a number average molecular weight in the range of 30,000 to 60,000. 9.5 to 25% by weight of an additive containing a base oil component of lubricating viscosity and a nitrogen-containing olefin copolymer derived from an olefin copolymer grafted with 0.15 to 1.0 carboxyl groups per 1000 number average molecular weight units of the copolymer, Wherein the copolymer has a number average molecular weight in the range of 10,000 to 100,000, wherein the amount of the additive in the lubricant composition is for reducing corrosion of the metal parts in the engine comprising contacting the lubricant composition with the engine part based on the total weight of the lubricant composition. Way. The method of claim 13 wherein the engine comprises a diesel engine providing exhaust gas recirculation. The method of claim 13, wherein the engine comprises an offboard or offboard marine engine. The method of claim 13, wherein the engine comprises exposure to a seawater environment. The method of claim 13, wherein the copolymer is grafted with 0.3 to 0.75 carboxyl groups per 1000 number average molecular weight units of the copolymer and has a number average molecular weight in the range of 30,000 to 60,000. 5 to 5, containing a lubricant additive concentrate containing a diluent or carrier oil and a nitrogen-containing olefin copolymer derived from an olefin copolymer grafted from 0.15 to 1.0 carboxyl groups per 1000 number average molecular weight units of the copolymer dissolved in a suitable solvent. 90% by weight of additive, wherein the copolymer has a number average molecular weight in the range of 10,000 to 100,000, wherein the amount of the additive in the concentrate is based on the total weight of the concentrate, wherein the fully formulated lubricant comprising the concentrate The composition will contain 9.5 to 25% by weight of the additive based on the total weight of the lubricant composition. The additive concentrate of claim 18 wherein the copolymer is grafted with 0.3 to 0.75 carboxyl groups per 1000 number average molecular weight units of the copolymer and has a number average molecular weight ranging from 30,000 to 60,000. A lubricant composition comprising a base oil and an additive concentrate according to claim 18. A method of lubricating moving parts in a vehicle, comprising using a lubricant composition containing a base oil and a lubricating additive as lubricating oil for one or more moving parts of the vehicle, wherein the lubricant additive is dissolved in a diluent or carrier oil, and a suitable solvent. Number-average molecular weight of the copolymer contains nitrogen containing olefin copolymer derived from olefin copolymer grafted 0.15 to 1.0 carboxyl groups per 1000, wherein the copolymer has a number average molecular weight in the range of 10,000 to 100,000, wherein the lubricant composition A method containing from 9.5 to 25% by weight additive based on the total weight of the lubricant composition. 22. The method of claim 21, wherein the vehicle comprises a diesel engine providing exhaust gas recirculation, wherein the moving part comprises a moving part of the engine. The method of claim 21, wherein the vehicle comprises a marine vehicle having an engine, wherein the moving part comprises a moving part of the engine. 22. The method of claim 21 wherein the copolymer is grafted with 0.3 to 0.75 carboxyl groups per 1000 number average molecular weight units of the copolymer and has a number average molecular weight in the range of 30,000 to 60,000. 22. The method of claim 21, wherein the vehicle comprises an internal combustion engine having a crankcase, wherein the lubricant composition comprises crankcase oil present in the crankcase of the vehicle. 22. The method of claim 21, wherein the lubricant composition comprises a power transmission lubricant present in the vehicle power transmission of the vehicle. A lubricating method of a moving part comprising contacting a moving part with a lubricant composition containing a lubricant additive, wherein the lubricant additive is 0.15 per 1000 average molecular weight units of copolymers dissolved in a diluent or carrier oil and a suitable solvent. To 1.0 carboxyl groups containing nitrogen-containing olefin copolymers derived from grafted olefin copolymers, wherein the copolymer has a number average molecular weight ranging from 10,000 to 100,000, wherein the lubricant composition is based on the total weight of the lubricant composition of 9.5 To 25% by weight of additives. 28. The method of claim 27 wherein the moving part comprises a moving part of the vehicle. 29. The method of claim 28, wherein the vehicle comprises a marine vehicle having an engine, wherein the moving part comprises a moving part of the engine. 28. The method of claim 27, wherein the copolymer is grafted with 0.3 to 0.75 carboxyl groups per 1000 number average molecular weight units of the copolymer and has a number average molecular weight in the range of 30,000 to 60,000. 28. The method of claim 27 wherein the moving part comprises an internal combustion engine having a crankcase, wherein the lubricant composition comprises crankcase oil present in the crankcase of the vehicle. 28. The method of claim 27, wherein the lubricant composition comprises a power transmission lubricant present in the vehicle power transmission of the vehicle. 9.5-25 wt% of an additive containing a nitrogen-containing olefin copolymer derived from an olefin copolymer grafted 0.15 to 1.0 carboxyl groups per 1000 number average molecular weight units of the copolymer, wherein the copolymer ranges from 10,000 to 100,000 And a number average molecular weight of wherein the amount of the additives in the composition is based on the total weight of the oily coating composition. 34. The metal surface of claim 33, wherein the copolymer is grafted with 0.3 to 0.75 carboxyl groups per 1000 number average molecular weight units of the copolymer and has a number average molecular weight in the range of 30,000 to 60,000.