JP2008144142A - Additive and lubricant composition to improve wear resistance - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for reducing wear between a lubricating surface and a moving part, and to provide a lubricant concentrate containing a lubricant and a wear-reducing agent. <P>SOLUTION: The lubricating surface comprises a base oil having lubricating viscosity, with an amount of at least one hydrocarbon soluble magnesium compound effectively providing greater surface ware reduction than that obtained from a lubricant composition free of the magnesium compound. The lubricant composition contains ≤0.05 wt.% phosphorus and is free of a calcium detergent. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The examples described herein relate to specific oil-soluble magnesium additives and the usage of the magnesium additives in lubricating oil compositions to improve the wear resistance of the composition.

  In the field of next-generation passenger car motor oils and heavy duty diesel engine oils, equivalent wear resistance at lower phosphorus and sulfur levels in the composition is required to reduce the pollution of more severe pollution control devices. Yes. It is well known that additives containing sulfur and phosphorus provide abrasion resistance to the finished oil, and further harm or otherwise reduce the effectiveness of pollution control devices.

  For many years, zinc dialkyldithiophosphate ("Zn DDP") has been used in lubricating oils. Zn DDP also has excellent wear resistance and has been used to pass cam wear tests such as Seq IVA and TU3 wear tests. A number of patents, including U.S. Patent Nos. 5,099,086, 5, and 6,397, all of which are incorporated herein by reference in their entirety, deal with the manufacture and use of Zn DDP.

  Sulfur-containing antiwear agents are well known and include dihydrocarbyl polysulfides; sulfurized olefins; sulfurized fatty acid esters of both natural and synthetic origins; trithiones; sulfurized thienyl derivatives; sulfided terpenes; sulfided polyynes; Addenda, etc. are included. Specific examples include sulfurized isobutylene, sulfurized diisobutylene, sulfurized triisobutylene, dicyclohexyl polysulfide, diphenyl polysulfide, dibenzyl polysulfide, dinonyl polysulfide, and among others di-t-butyl trisulfide, di-t-butyl tetrasulfide tetrasulfide, And mixtures of di-t-butyl polysulfides, such as mixtures of di-t-butyl pentasulfides. Of the above, sulfurized olefins are used in many applications. Methods for producing sulfurized olefins are described in Patent Literature 4, Patent Literature 5, Patent Literature 6, Patent Literature 7, Patent Literature 8, and Patent Literature 9. The sulfurized olefin derivative described in Patent Document 10 is also useful. Other sulfur-containing antiwear agents are described in Patent Document 11, Patent Document 12, and Patent Document 13.

  There is a need for lubricants that provide excellent wear resistance and are compatible with pollution control devices used for automobiles and diesel engines.

US Pat. No. 4,904,401 U.S. Pat. No. 4,957,649 US Pat. No. 6,114,288 US Pat. No. 2,995,569 US Pat. No. 3,673,090 US Pat. No. 3,703,504 US Pat. No. 3,703,505 U.S. Pat. No. 3,796,661 U.S. Pat. No. 3,873,454 US Pat. No. 4,654,156 U.S. Pat. No. 4,857,214 US Pat. No. 5,242,613 US Pat. No. 6,096,691

  In view of the foregoing, the exemplary embodiments disclosed herein provide a lubricant concentrate that includes a lubricating surface, a method for reducing wear between moving parts, a lubricant, and a wear reducing agent. is doing. The lubricated surface comprises a base oil of lubricating viscosity and at least one hydrocarbon in an amount effective to further reduce surface wear than reduced surface wear by a lubricant composition lacking a magnesium compound. Contains soluble magnesium compound doors. The lubricant composition contains no more than about 0.05% by weight phosphorus and is substantially devoid of calcium detergent.

  In one exemplary embodiment, a vehicle having moving parts is provided, the car including a lubricant that lubricates the moving parts. The lubricant may be present in an amount of at least one hydrocarbon that is effective to further reduce wear on the surface of the moving part rather than reducing wear on the surface of the moving part with a lubricant composition lacking a magnesium compound. An oil of lubricating viscosity containing an amount of an anti-wear agent that provides a soluble magnesium compound. The lubricant composition contains no more than about 0.05% by weight phosphorus and is substantially devoid of calcium detergent.

  In another embodiment, the base oil component of lubricating viscosity and an amount of at least one hydrocarbon that is effective to further reduce wear is less than that caused by a lubricant composition lacking a magnesium compound. A fully formulated lubricant composition is provided that includes an amount of an anti-wear agent that provides a soluble magnesium compound. The lubricant composition contains no more than about 500 ppm phosphorus and is substantially devoid of calcium detergent.

  A further embodiment of the present disclosure provides a lubricant concentrate for providing improved abrasion resistance to a lubricant composition. The concentrate is substantially devoid of calcium compounds and at least one hydrocarbon in an amount sufficient to provide about 120 ppm to about 2000 ppm magnesium in a hydrocarbyl carrier fluid and a lubricant composition comprising the concentrate. Contains a magnesium compound that is soluble in water.

  As briefly described above, the examples of the present disclosure significantly improve the wear resistance of the lubricant composition, thereby providing the same in the antiwear agent required to obtain equivalent wear resistance. An antiwear agent comprising a magnesium compound soluble in hydrocarbons capable of reducing the amount of phosphorus and sulfur is provided. This additive may be mixed with an oily fluid applied to the surface to reduce surface wear. In another application, the additive is provided in a fully formulated lubricant composition. The additive is specifically intended to meet the currently proposed GF-4 standard for passenger car motor oils and the PC-10 standard for heavy duty diesel engine oils.

  The compositions and methods described herein are particularly suitable for reducing the pollution of automotive pollution control devices, while the compositions reduce the performance of antiwear agents in lubricant compositions. Suitable for improvement. Other features and advantages of the compositions and methods described herein are set forth in the following detailed description, which is intended to exemplify aspects of the examples without limiting the examples described herein. It becomes clear by reference.

  It is understood that both the foregoing summary and the following detailed description are for purposes of illustration and description only and are intended to provide further explanation of the disclosed and claimed embodiments.

Detailed Description of Examples

  In one example, a magnesium compound useful as a component in a lubricating oil composition is introduced. The magnesium compound comprises a hydrocarbon soluble magnesium compound selected from the group consisting of magnesium sulfonate, magnesium phenate, magnesium salicylate, and mixtures thereof.

  The term “hydrocarbon soluble” means that the compound is substantially suspended or dissolved in the hydrocarbon material by reaction or complexation of the magnesium compound with the hydrocarbon material. As used herein, the term “hydrocarbon” refers to any of a number of compounds containing various combinations of carbon, hydrogen, and / or oxygen.

The term “hydrocarbyl” refers to a group in which a carbon atom is attached to the rest of the molecule and has predominantly hydrocarbon character. Examples of hydrocarbyl groups include the following:
(1) substituted by hydrocarbon substituents, ie, aliphatic (eg, alkyl or alkenyl) substituents, alicyclic (eg, cycloalkyl, cycloalkenyl) substituents, and aromatic, aliphatic, and alicyclic groups An aromatic substituent, or a cyclic substituent such that the ring is completed by another part of the molecule (eg, the two substituents together form an alicyclic radical);
(2) Substituted hydrocarbon substituents, ie, substituents that are primarily hydrocarbons in the context of the present invention (eg halo (especially chloro and fluoro), hydroxy, alkoxy, mercapto, alkyl mercapto, nitro, nitroso , And sulfoxy), etc., and substituents containing non-hydrocarbon groups;
(3) Hetero substituents, i.e., mainly in the context of the present invention, having predominantly hydrocarbon properties, but otherwise containing non-carbon atoms in rings or chains consisting of carbon atoms. Such substituents. Heteroatoms include sulfur, oxygen, and nitrogen, and include substituents such as pyridyl, furyl, thienyl, and imidazolyl. Usually, there will be no more than two, generally no more than one, non-hydrocarbon substituent per 10 carbon atoms in the hydrocarbyl group. Generally, there are no non-hydrocarbon substituents in the hydrocarbyl group.

  The magnesium compound is desirably a basic or overbased magnesium salt containing an excess amount of magnesium cation. Usually, the metal ratio of the basic or overbased salt is about 40 or less, more specifically about 2 to about 30 or 40.

  Commonly used methods for producing basic (or overbased) magnesium salts include mineral oil solutions of salts containing a stoichiometric excess of metal neutralizer, such as metal oxides, hydroxides, carbonates, heavy metals. It consists of heating carbonates, sulfides, etc. above about 50 ° C. In addition, various promoters are used during the overbasing process to facilitate the uptake of excess metal. These promoters include phenolic materials such as phenol, naphthol, alkylphenols, thiophenols, sulfurized alkylphenols, and various condensation products of formaldehyde with phenolic materials; methanol, 2-propanol, octyl alcohol, cellosolve carbitol And alcohols such as ethylene, glycol, stearyl alcohol, and cyclohexyl alcohol; and compounds such as amines such as aniline, phenylenediamine, phenothiazine, phenyl beta naphthylamine, and dodecylamine.

  The organic acidic compound from which the magnesium salt is derived is at least one sulfur acid, carboxylic acid, phosphoric acid, phenol, or a mixture thereof. Sulfuric acids include sulfonic acid, thiosulfonic acid, sulfinic acid, sulfenic acid, partially esterified sulfuric acid, sulfurous acid, and thiosulfuric acid. Sulfonic acids are particularly suitable for use in the production of magnesium compounds that are soluble in hydrocarbons.

Among the sulfonic acids useful for the preparation of component (B) are those represented by the following formula:
R _x T (SO ₃ H) _y (I)
and
R ¹ (SO ₃ H) _y (II)

In these formulas, R ¹ is an aliphatic compound or an aliphatic-substituted alicyclic hydrocarbon, or a hydrocarbon group having essentially no acetylenic unsaturation and having about 60 or less carbon atoms. When R ¹ is an aliphatic compound, its carbon number is usually at least about 15, and when it is an aliphatic-substituted alicyclic group, the total number of carbon atoms of this aliphatic substituent is at least about 12. . Examples of R ¹ include alkyl, alkenyl, and alkoxyalkyl radicals, and aliphatic substituted alicyclic groups, where the aliphatic substituent is alkyl, alkenyl, alkoxy, alkoxyalkyl, carboxyalkyl, and the like. Usually the alicyclic nuclei are obtained from cycloalkanes or cycloalkenes such as cyclopentane, cyclohexane, cyclohexene or cyclopentene. Specific examples of R ¹ include cetylcyclohexyl, laurylcyclohexyl, cetyloxyethyl, octadecenyl, and petroleum, saturated and unsaturated paraffin waxes, and polymerized monoolefins containing 2 to 8 carbons per olefin monomer unit and Examples thereof include groups obtained from olefin polymers containing diolefins. R ¹ also has a loss of phenyl, cycloalkyl, hydroxy, mercapto, halo, nitro, amino, nitroso, low alkoxy, low alkyl mercapto, carboxy, carbalkoxy, oxo, thio, or essentially hydrocarbon properties. If not, other substituents such as blocking groups such as --NH--, --O-- or --S-- are also included.

R in formula I is usually a hydrocarbon or an aliphatic hydrocarbon group such as alkyl or alkenyl, which is essentially free of acetylenic unsaturation and contains from about 4 to about 60 aliphatic carbon atoms. . However, this compound contains the blocking groups listed above, provided that the substituents and hydrocarbon properties are not inherently impaired. Usually, any atom other than carbon present in R ¹ or R does not occupy 10% or more of the total weight.

  In the above formula, T is a cyclic nucleus obtained from an aromatic hydrocarbon such as benzene, naphthalene, anthracene, or biphenyl, or a heterocyclic compound such as pyridine, indole, or isoindole. Usually, T is an aromatic hydrocarbon nucleus, especially a benzene or naphthalene nucleus.

  The subscript “x” in the above formula is at least 1, usually 1 to 3. The subscripts “r” and “y” average about 1 to 2, usually 1 for each molecule.

The sulfonic acid is usually petroleum sulfonic acid or synthetically produced alkaryl sulfonic acid. The most useful of the petroleum sulfonic acids are those produced by sulfonating a portion of the appropriate petroleum, followed by removal and production of acidic sludge. Synthetic alkaryl sulfonic acids are usually made from alkylated benzenes such as the product of a Friedel-Crafts reaction of benzene with a polymer such as tetrapropylene. Listed below are specific examples of sulfonic acids that are useful in preparing the hydrogen soluble magnesium compounds described herein. Such sulfonic acids include mahogany sulfonic acid, bright stock sulfonic acid, petrolatum sulfonic acid, mono and poly wax substituted naphthalene sulfonic acid, cetyl chlorobenzene sulfonic acid, cetyl phenol sulfonic acid, cetyl phenol disulfide sulfonic acid, cetoxycapryl benzene Sulfonic acid, dicetyl thianthrene sulfonic acid, dilauryl beta naphthol sulfonic acid, dicapryl nitronaphthalene sulfonic acid, saturated paraffin wax sulfonic acid, unsaturated paraffin wax sulfonic acid, hydroxy substituted paraffin wax sulfonic acid, tetra-isobutylene sulfonic acid, tetra Amylene sulfonic acid, chloro-substituted paraffin wax sulfonic acid, nitroso-substituted paraffin wax sulfonic acid, petroleum naphthene sulfone Acid, cetyl cyclopentyl sulfonic acids, lauryl cyclohexyl sulfonic acids, mono- and poly-wax-substituted cyclohexyl sulfonic acids, dodecylbenzene sulfonic acids, including but "dimeric alkylated" sulfonic acids such as, but not limited to.

Particularly useful are alkyl-substituted benzene sulfonic acids, including dodecyl benzene “bottom” sulfonic acids, wherein the alkyl group has at least 8 carbon atoms. Dodecylbenzene “bottom” sulfonic acids are alkylated with propylene tetramer or isobutene trimer to incorporate one, two, three or more branched C ₁₂ substituents in the benzene ring. It is an acid obtained from benzene. Dodecylbenzene bottom, which is primarily a mixture of mono and didodecylbenzene, is available as a by-product in the manufacture of household detergents. Similar products obtained from alkylated bottoms formed during the production of linear alkyl sulfonates (LAS) are also useful for the production of sulfonates described herein.

  Suitable carboxylic acids for the production of hydrocarbon soluble magnesium compounds are aliphatic, cycloaliphatic and aromatic mono- and polybasic carboxylic acids free of acetylenic unsaturation; alkyl-substituted or alkenyl-substituted cyclohexanes. Mention may be made of pentanoic acid, alkyl-substituted or alkenyl-substituted cyclohexane acids and alkyl-substituted or alkenyl-substituted aromatic carboxylic acids. The fatty acids typically contain from about 8 to about 50, desirably from about 12 to about 25 carbon atoms. Alicyclic and aliphatic carboxylic acids are particularly preferred and may be saturated or unsaturated. Specific examples include 2-ethylhexanoic acid, linolenic acid, propylene tetramer substituted maleic acid, behenic acid, isostearic acid, pelargonic acid, capric acid, palmitoleic acid, linoleic acid, lauric acid, oleic acid, ricinoleic acid, By oxidation of undecanic acid, dioctylcyclopentanecarboxylic acid, myristic acid, dilauryldecahydronaphthalene-carboxylic acid, stearyl-octahydroindenecarboxylic acid, palmitic acid, alkyl and alkenyl succinic acids, petrolatum or hydrocarbon waxes Included are the formed acids and commercial mixtures of two or more carboxylic acids such as tall oil acid, resin acid, and the like.

  Further, magnesium compounds soluble in hydrocarbons are also produced from phenol, that is, a compound containing a hydroxyl group directly bonded to an aromatic ring. The term “phenol” as used herein includes compounds having one or more hydroxy groups attached to the aromatic ring, such as catechol, resorcinol, and hydroquinone. Also included are alkylphenols such as cresol and ethylphenol, and alkenylphenols. Phenols containing alkyl substituents having about 3 to 100 carbon atoms, especially about 6 to 50 carbon atoms, such as heptylphenol, octylphenol, dodecylphenol, tetrapropene-alkylated phenol, octadecylphenol, and polybutenylphenol Is particularly preferred. Although phenols containing one or more alkyl substituents may be used, monoalkylphenols are more preferred because they are more readily available and easier to produce.

  Also useful are condensation products of the above-described phenols with at least one lower aldehyde or ketone. Here, the term “lower” means that the aldehyde or ketone contains 7 or less carbon atoms. Suitable aldehydes include formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, valeraldehyde, and benzaldehyde. Also suitable are reagents that produce aldehydes, such as paraformaldehyde, trioxane, methylol, methyl formcel, and paraaldehyde.

  The amount of hydrocarbon soluble magnesium compound contained in the lubricants of the exemplary embodiments also varies, and useful amounts in a particular lubricating oil composition can be easily determined by those skilled in the art. It is determined. The amount of magnesium compound contained in the lubricant described herein is from about 0.15% to about 2.0% by weight. The amount of magnesium compound contained in the oil composition is sufficient to provide the desired antiwear properties.

  In the manufacture of lubricating oil compositions, additives in the form of active ingredients in the form of 1% to 99% by weight concentrate, for example in hydrocarbons such as mineral lubricating oils and other suitable solvents, are a common practice. Added. Usually these concentrates are added together with 0.05 to 10 parts by weight of lubricant as part of the additive package when forming a finished lubricant, eg crankcase motor oil. The purpose of the concentrate is, of course, to make it easier and easier to handle than the handling of various substances, but also to facilitate the dissolution or dispersion of the various substances in the final mixture. .

  Lubricant compositions made of the above-described hydrocarbon soluble magnesium compounds are used in a wide range of applications. For compression ignition engines and spark added engines, it is desirable that the lubricant composition meet or exceed the published GF-4 or API-CI-4 standards. Lubricant compositions in accordance with the GF-4 or API-CI-4 standards described above include base oils and oil additive packages to provide a fully formulated lubricant. The lubricant base oil in accordance with the present disclosure is an oil of lubricating viscosity selected from natural lubricating oils, synthetic lubricating oils, and mixtures thereof. Such base oils include those conventionally used as crankcase lubricating oils for spark addition and compression ignition internal combustion engines, such as automobile and truck engines, ship and railway diesel engines, and the like.

  Natural oils include animal and vegetable oils (for example, castor oil and lard oil), liquid petroleum, hydrorefined, solvent-treated or acid-treated, paraffinic, naphthenic, and paraffin / naphthenic mixed lubricating oils, etc. There is. Oils of lubricating viscosity obtained from coal or shale are also useful base oils. Synthetic lubricating oils used in exemplary embodiments of the present disclosure included, but are not limited to, polyalphaolefins, alkylated aromatics, alkylene oxide polymers, interpolymers, copolymers, and derivatives thereof. , Including any of the many commonly used synthetic hydrocarbon oils, where the terminal hydroxyl groups are modified by esterification, etherification, etc., and esters of dicarboxylic acids with silicon-based oils.

  Fully formulated lubricants conventionally include additive packages, referred to herein as dispersant / inhibitor packages or DI packages, which provide the necessary properties for the composition. Suitable DI packages are described, for example, in US Pat. Nos. 5,204,012 and 6,034,040. The types of additives contained in the additive package include dispersants, friction reducers, seal expansion agents, antioxidants, antifoaming agents, lubricants, rust inhibitors, corrosion inhibitors, demulsifiers, viscosity There are index improvers. Some of these compounds are well known to those skilled in the art and are usually used in conventional amounts with additives and compositions described herein.

Another component of the dispersant lubricant composition is at least one dispersant obtained from a polyalkylene compound. The number average molecular weight of the polyalkylene compound is from about 400 to about 5000 or more. Dispersants used include, but are not limited to, amines, alcohols, amides, or polar moieties of esters often attached to the polymer backbone through cross-linking groups. Examples of the dispersant include Mannich dispersants described in U.S. Pat. Nos. 3,697,574 and 3,736,357; U.S. Pat. Nos. 4,234,435 and 4,6.
Ashless succinimide dispersant described in US Pat. No. 36,322; amine dispersant described in US Pat. Nos. 3,219,666, 3,565,804, and 5,633,326; US Pat. , 936,041, 5,643,859, and 5,627,259, as well as US Pat. Nos. 5,851,965, 5,853,434, and 5,792, Selected from the polyalkylene succinimide dispersants described in No. 729, and the like.

  A suitable dispersing agent is a polyalkylene succinimide dispersant obtained from a polyisobutene (PIB) compound. The dispersant may be a mixture of dispersants having a number average molecular weight of about 800 to about 3000 and a reactive PIB content of about 50% to about 60%. The total amount of dispersant in the lubricant composition is from about 1 weight percent to about 10 weight percent of the total weight of the lubricant composition.

Friction reducing agents Oil-soluble friction reducing agents may be incorporated into the lubricating oil compositions described herein. The friction reducer is selected from among nitrogen containing or nitrogen containing and / or amine free friction reducing agents. Generally, the friction reducing agent is used in an amount of 0.02% to 2.0% by weight of the lubricating oil composition. Preferably 0.05% to 1.0% by weight, more preferably 0.1% to 0.5% by weight of a friction reducing agent is used.

  Examples of such nitrogen-containing friction reducers used include imidazoline, amide, amine, succinimide, alkoxylated amine, alkoxylated ether amine, amine oxide, amidoamine, nitrile, betaine, quaternary amine, imine , Amine salts, aminoguanazine, alkanolamide, and the like, but are not limited thereto.

  Such friction reducing agents include hydrocarbyl groups selected from linear, branched, or aromatic hydrocarbyl groups and mixtures thereof, and saturated or unsaturated hydrocarbyl groups. Hydrocarbyl groups are primarily composed of carbon and hydrogen, but may contain one or more heteroatoms such as sulfur and oxygen. Suitable hydrocarbyl groups have 12 to 25 carbon atoms and can be saturated or unsaturated. More desirably, these are linear hydrocarbyl groups.

  Exemplary friction reducing agents include polyamine amides. Such compounds have a linear, saturated or unsaturated or mixed hydrocarbyl group and have from about 12 to about 25 carbon atoms.

  Other exemplary friction reducers include alkoxylated amines and alkoxylated ether amines, most preferably the alkoxylated amine contains about 2 moles of alkylene oxide per mole of nitrogen. Such compounds can have linear, saturated or unsaturated or mixed hydrocarbyl groups. These carbon atoms are about 12 to about 25 or less, and one or more heteroatoms may be contained in the hydrocarbyl chain. Ethoxylated amines and ethoxylated ether amines are particularly suitable nitrogen-containing friction reducers. Amines and amides can be reacted as is or with addition compounds or boron compounds such as boron oxide, boron halide, metaborate, boric acid, or monoalkyl borate, dialkyl borate, or trialkyl borate. Used in the form of things.

As an ashless organic polysulfide compound used as a friction reducing agent, an oil sulfide or fat represented by the following formula, in which a sulfur atom group having two or more adjacent sulfur atoms is present in the molecular structure: Alternatively, there are organic compounds such as polyolefins.

In the above formula, each of R ² and R ³ is a straight chain, branched chain, alicyclic group, which optionally contains a straight chain, branched chain, alicyclic unit, or aromatic unit in any combination, Or it represents an aromatic hydrocarbon group. An unsaturated bond may be contained, but a saturated hydrocarbon group is preferable. Of these, alkyl groups, allyl groups, alkylallyl groups, benzyl groups, and alkylbenzyl groups are particularly preferred.

Each of R ³ and R ⁴ has two binding sites, and includes a straight chain, a branched chain, and an alicyclic ring selectively containing a straight chain, a branched chain, an alicyclic unit, or an aromatic unit in any combination. It represents a formula or an aromatic hydrocarbon group. An unsaturated bond may be contained, but a saturated hydrocarbon group is preferable. Among these, an alkylene group is particularly preferable.

R ⁶ and R ⁷ each represent a linear or branched hydrocarbon group. The subscripts “x” and “y” each represent an integer of 2 or more.

For example, thiadiazoles such as sulfurized sperm whale oil, sulfurized pinene oil, sulfurized soybean oil, sulfurized polyolefin, dialkyl disulfide, dialkyl polysulfide, dibenzyl disulfide, di-t-butyl disulfide, polyolefin polysulfide, and bis-alkyl polysulfanyl thiadiazole. References may be made to system compounds, sulfurized phenols and the like. Among these compounds, dialkyl polysulfide, dibenzyl disulfide, and thiadiazole-based compounds are preferable. Particularly preferred is bis-alkyl polysulfanyl thiadiazole.

  As the lubricant, a metal-containing compound such as Ca phenate having a polysulfide bond may be used. However, since this compound has a high coefficient of friction, the use of such a compound is not always appropriate. On the contrary, the organic polysulfide compound described above is an ashless compound that does not contain any metal, but exhibits excellent performance of maintaining a low coefficient of friction for a long time when used in combination with other friction reducing agents.

  The above ashless organic polysulfide compound (hereinafter simply referred to as “polysulfide compound”), when calculated as sulfur (S), is 0.01 wt% to 0.4 wt% based on the total amount of the lubricant composition. In general, it is added in an amount of 0.1% to 0.3% by weight, and preferably 0.2% to 0.3% by weight. If the addition amount is 0.01% by weight or less, it is difficult to obtain the intended effect, and if it is 0.4% by weight or more, there is a risk that corrosion wear increases.

  The nitrogen-free, organic, ashless (metal-free) friction reducers used in the lubricating oil compositions disclosed herein are generally known and include carboxylic acids and anhydrous Esters formed by reacting products with alkanols or glycols are included, with carboxylic acids being particularly preferred at this time. Other useful friction reducing agents typically include terminally polar groups (eg, carboxyl groups or hydroxyl groups) covalently bonded to the lipophilic hydrocarbon chain. Esters of carboxylic acids and anhydrides with alkanols are described in US Pat. No. 4,702,850. Particularly suitable friction reducing agents for use in combination with a magnesium compound are esters such as glycerol monooleate (GMO).

  The friction reducer described above, in combination with a magnesium compound, is included in the lubricating oil composition disclosed herein in an amount effective to ensure that the composition passes the high frequency reciprocating rig test (HFRR). It is. For example, the friction reducer is added to a lubricating oil composition containing magnesium in an amount sufficient to bring the average HFRR wear scar to about 100 square microns or less. Generally, the friction reducer is added in an amount of about 0.25 wt% to about 2.0 wt% (AI), based on the total weight of the lubricating oil composition, to achieve the desired effect.

The antiwear metal dihydrocarbyl dithiophosphate antiwear agent may be added to the lubricating oil composition according to the illustrative examples in combination with a magnesium compound. Such antiwear agents comprise dihydrocarbyl dithiophosphate metal salts, where the metal is an alkali metal or alkaline earth metal, or aluminum, lead, tin, molybdenum, manganese, nickel, copper, titanium, or zinc. is there. The most commonly used lubricants are zinc salts.

Dihydrocarbyl dithiophosphate metal salts were formed according to well-known techniques, first forming dihydrocarbyl dithiophosphate (DDPA), usually by reacting P ₂ S ₅ with one or more alcohols or phenols. It is produced by neutralizing DDPA with a metal compound. For example, dithiophosphoric acid is made by reacting a mixture of primary and secondary alcohols. On the other hand, a plurality of dithiophosphoric acids may be produced, and the characteristics of one hydrocarbyl group may be completely secondary and the characteristics of the other hydrocarbyl group may be completely primary. Any basic or neutral metal compound may be used to make the metal salt, but oxides, hydroxides, and carbonates are most commonly used. Commercial additives often contain excessive amounts of metal because excessive amounts of basic metal compounds are used in the neutralization reaction.

式中Ｒ^８およびＲ^９は、炭素数が１から１８、一般的には２から１２であり、アルキルラジカル、アルケニルラジカル、アリルラジカル、アリルアルキルラジカル、アルカリルラジカル、および脂環式ラジカルなどのラジカルを含んだ、同一のあるいは別々のヒドロカルビルラジカルである。従ってこのラジカルは、例えばエチル、ｎ−プロピル、ｉ−プロピル、ｎ−ブチル、ｉ−ブチル、ｓｅｃ−ブチル、アミル、ｎ−ヘキシル、ｉ−ヘキシル、ｎ−オクチル、デシル、ドデシル、オクタデシル、２−エチルヘキシル、フェニル、ブチルフェニル、シクロヘキシル、メチルシクロペンチル、プロペニル、ブテニルなどである。油溶性を得るためのジチオリン酸中の炭素原子の総数（すなわちＲ^８およびＲ^９）は、通常５以上である。従ってジンクジヒドロカルビルジチオホスフェートは、ジンクジアルキルジチオホスフェートを含むことができる。 Commonly used zinc dihydrocarbyl dithiophosphate (ZDDP) is an oil-soluble salt of dihydrocarbyl dithiophosphate and is represented by the following formula.

Wherein R ⁸ and R ⁹ have 1 to 18 carbon atoms, generally 2 to 12 carbon atoms, such as alkyl radicals, alkenyl radicals, allyl radicals, allylalkyl radicals, alkaryl radicals, and alicyclic radicals. The same or separate hydrocarbyl radicals containing radicals. Thus, for example, this radical is ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, amyl, n-hexyl, i-hexyl, n-octyl, decyl, dodecyl, octadecyl, 2- And ethylhexyl, phenyl, butylphenyl, cyclohexyl, methylcyclopentyl, propenyl, butenyl and the like. The total number of carbon atoms (ie R ⁸ and R ⁹ ) in dithiophosphoric acid to obtain oil solubility is usually 5 or more. Thus, zinc dihydrocarbyl dithiophosphate can include zinc dialkyldithiophosphate.

  In order to limit the amount of phosphorus introduced into the lubricating oil composition by ZDDP to 0.1 wt% (1000 ppm), ZDDP is desirably in an amount of about 1.0 wt% or less based on the total weight of the lubricating oil composition. It should be added to the lubricating oil composition. In combination with a magnesium-containing cleaning agent, the amount of phosphorus in the lubricating oil obtained from ZDDP is desirably about 500 ppm or less, more desirably from about 250 ppm to about 500 ppm for best wear scar results.

  Other additives listed below may also be present in the lubricating oil compositions disclosed herein.

Viscosity modifiers Viscosity modifiers (VMs) function to give the lubricating oil operability at high and low temperatures. The VM used may be monofunctional or multifunctional.

  Multifunctional viscosity modifiers that also function as dispersants are also known. Suitable viscosity modifiers include polyisobutylene, ethylene and propylene copolymers, higher alpha olefins, polymethacrylates, polyalkylmethacrylates, methacrylate copolymers, copolymers of unsaturated dicarboxylic acids and vinyl compounds, styrene and acrylic ester interpolymers, And partially hydrogenated styrene / isoprene copolymers, styrene / butadiene, and isoprene / butadiene, and partially hydrogenated butadiene / isoprene / isoprene / divinylbenzene homopolymers.

Antioxidants Antioxidants or antioxidants reduce the tendency of the base stock to deteriorate during use, but this degradation is due to oxidation products such as sludge and varnish deposits on the metal surface, and viscosity You can prove by increasing. Such oxidation inhibitors include hindered phenols, alkaline earth metal salts of alkylphenolthioesters C ₅ having an alkyl side chain of C _12, calcium nonylphenol sulfide, ashless oil soluble phenates and sulfurized phenates, phosphosulfurized or sulfurized Examples include hydrocarbons, phosphate esters, metal thiocarbamates, and oil-soluble copper compounds described in US Pat. No. 4,867,890.

Rust inhibitor A rust inhibitor selected from the group consisting of non-sulfuric polyoxyalkylene polyols and esters thereof, polyoxyalkylene phenols, and negative sulfur alkyl sulfonic acids may be used.

Corrosion Inhibitors Corrosion inhibitors containing copper and lead may be used, but are generally not required in the disclosed example compositions. In general, such compounds include thiadiazole polysulfides having 5 to 50 carbon atoms, derivatives thereof, and polymers thereof. Derivatives of 1,3,4 thiadiazole are common, as described in US Pat. Nos. 2,719,125, 2,719,126, and 3,087,932. For other similar materials, U.S. Pat. Nos. 3,821,236, 3,904,537, 4,097,387, 4,107,059, 4,136,043, 4,188,299. And 4,193,882. Other additives include thio and polythiosulfenamides of thiadiazole, as described in GB-A-1,560,830. Benzotriazole derivatives are also included in this type of additive. When these compounds are included in the lubricating composition, they are usually present in an amount not exceeding 0.2% by weight of the active ingredient.

A small amount of a demulsifying component may be used. Suitable demulsifying components are described in EP 330,522. The demulsifying component is made by reacting an alkylene oxide, an addition compound obtained by reacting a bis-epoxide and a polyhydroxyl alcohol. The demulsifying component is used at a level where the active ingredient does not exceed 0.1 mass%. A treat rate of 0.001% to 0.05% by weight of active ingredient is convenient.

Pour point depressants , also known as lube oil flow improvers, lower the minimum temperature at which the fluid can flow or be poured. Such additives are well known. Typical examples of these additives that improve the low temperature fluidity of the fluid include C ₈ to C ₁₈ dialkyl fumarate / vinyl acetate copolymers, polyalkyl methacrylates, and the like.

Antifoam foam control is accomplished by a number of compounds including polysiloxane antifoams such as polydimethylsiloxane silicone oil.

  Some of the above-mentioned additives provide multiple effects, so for example a single additive acts as a dispersant / antioxidant. Since this approach is well known, no further explanation is required.

  Individual additives are incorporated into the base stock in any convenient manner. Thus, each component can be added directly to the base stock or base oil blend by dispersing or dissolving it in the base stock or base oil blend at the desired concentration level. Such mixing occurs at room temperature or at an elevated temperature.

The magnesium compound additive is added directly to the lubricating oil composition. However, in one embodiment, these form substantially an additive concentrate, such as mineral oil, synthetic oil, naphtha, alkylated (eg, C ₁₀ to C ₁₃ alkyl) benzene, toluene or xylene. Inert and generally diluted with liquid organic diluent. These concentrates usually contain about 1% to about 100% by weight, and in one embodiment about 10% to about 90% magnesium compound.

  Base oils suitable for use in formulating the compositions, additives, and concentrates described herein may be selected from either synthetic or natural oils, or mixtures thereof. Synthetic base oils include dicarboxylic acid alkyl esters, polyglycols and alcohols, as well as polybutenes, alkylbenzenes, phosphoric acid organic esters, and polyalphaolefins including polysilicon oil. Natural base oils include a wide variety of mineral lubricants under crude oil, for example as to whether they are paraffinic, naphthenic, or mixtures thereof. The viscosity of the base oil is generally from about 2.5 cSt to about 15 cSt at 100 ° C., desirably from about 2.5 cSt to about 11 cSt.

Accordingly, the base oil used is selected from any of the Group I to Group V base oils specified in the American Petroleum Institute (API) Baseline Compatibility Guidelines. A group of such base oils is shown below.

  The additives used in formulating the compositions described herein are incorporated into the base oil individually or in various combinations. However, it is desirable to use an additive concentrate (ie, an additive and a diluent such as a hydrocarbon solvent) to mix all ingredients simultaneously. The use of additive concentrates takes advantage of the interchangeability obtained by the combination of ingredients when in the form of additive concentrates. Also, the use of the concentrate reduces the mixing time and reduces the possibility of mixing errors.

This embodiment provides a lubricating oil for an internal combustion engine that has a relatively low concentration of added hydrocarbon-soluble magnesium compound and provides about 120 ppm to about 2000 ppm of magnesium as an element in the oil. To do. In one embodiment, the magnesium compound is present in the lubricating oil composition in an amount sufficient to provide from about 250 ppm to about 1500 ppm magnesium, and in further embodiments from about 450 ppm to about 1000 ppm.
Present in the lubricating oil composition in an amount sufficient to provide a sufficient amount of magnesium metal.

  The following examples are intended to illustrate embodiments of the examples and are not intended to limit the examples in any way.

EXAMPLE Twelve fully formulated lubricant compositions were made and the wear properties of those compositions were compared using a high frequency reciprocating test device (HFRR). In the HFRR test, a steel disk dipped in oil was vibrated to hit a 1 mm path at a rate of 20 Hz. The test was conducted at 120 ° C. for 1 hour with the addition of 7 Newton (˜1.0 GPa) between the ball and the disk. After testing, the wear scar surface and lace on the HFRR disc were obtained from Precision Devices, Inc., Middleton, Wisconsin. Measurements were made using a Microanalyzer 2000 (MICRO ANALYZER 2000), commercially available from (Precision Devices, Inc., Middleton, Wisconsin). The wear scar cross-sectional area was reported by the analyzer at an additional 700 grams at 120 ° C. The standard deviation of the wear scar measurements is also listed in the table. Each lubricant composition included a conventional DI package that provided about 9 weight percent of the lubricant composition. The DI package contained conventional amounts of detergents, dispersants, antiwear agents, friction reducers, antifoam agents, and antioxidants. Compositions may also contain a small amount of ZDDP or no ZDDP, and may or may not contain 0.35 of glycerol monooleate friction reducer. It was. Samples 1 to 4 did not contain ZDDP and contained either calcium or magnesium detergent. Samples 5 through 8 contained 0.05 weight percent ZDDP and either a calcium or magnesium detergent. Samples 9 through 12 contained 0.025 weight percent ZDDP and either a calcium or magnesium detergent. The composition and test results are shown in the table below.

  As shown in the foregoing results, samples 6, 8, 10, and 12 formulated with magnesium-containing detergent and ZDDP are samples 5.7, 9, and 11 formulated with calcium-containing detergent and ZDDP. In comparison, there were few wear scars. Compared to the lubricant containing 0.05% by weight of ZDDP (samples 5 to 8), the wear scars were the least with the lubricant containing 0.025% by weight of ZDDP (samples 9 to 12). there were.

  More specifically, Sample 1 and Sample 3 have less wear scars than Sample 2 and Sample 4, which is more abraded than calcium-containing detergents without calcium containing ZDDP. It means that well is prevented. Comparison of sample 3 and sample 4 wear results with sample 1 and sample 2 results shows that the addition of surface active friction reducers interferes with the wear resistance of both calcium and magnesium detergents became. However, friction reducers are necessary to improve the fuel efficiency characteristics of oils and are generally included in fully formulated oils.

  Surprisingly, despite the presence of the magnesium-containing detergent in Sample 6 and Sample 8, Sample 6 and Sample 8 had less wear scars than Sample 5 and Sample 7, respectively. Compared to Sample 5 and Sample 8, Sample 9 and Sample 12 with less ZDDP content had even fewer wear scars. Furthermore, the presence of the glycerol monooleate friction reducer in sample 12 along with the magnesium-containing cleaner prevented wear better than sample 11 formulated with calcium cleaner.

  Compositions containing from about 120 ppm to about 2000 ppm magnesium compound in the form of a hydrocarbon soluble magnesium compound make it possible to reduce conventional phosphorus and sulfur antiwear agents, thereby improving the same It is expected to be able to improve the performance of vehicle pollution control equipment while realizing the improved wear resistance and benefits.

  At numerous places throughout this specification, reference has been made to a number of US patents. All such references are expressly incorporated into the present disclosure as fully explained.

  The foregoing embodiment has considerable room for change in its implementation. Accordingly, the examples are not intended to be limited to the specific illustrations described above. Rather, the foregoing embodiments are within the spirit and scope of the appended claims, including their legally usable counterparts.

  This patentee does not intend to provide any disclosed embodiments in general, and that any disclosed modifications or changes are not fully within the scope of the claims. Until now, it is considered to be part of this example by the doctrine of equivalents.

  The main features and aspects of the present invention are as follows.

1. A base oil of lubricating viscosity and an amount of at least one hydrocarbon-soluble magnesium compound effective to further reduce surface wear than reduction of surface wear by a lubricant composition lacking magnesium compound; A lubricating surface comprising a lubricant composition comprising a lubricant composition, wherein the lubricant composition contains about 0.05 wt% or less of phosphorus.

2. The lubricating surface of claim 1 wherein the lubricating surface comprises an engine drive train.

3. The lubricating surface of claim 1 wherein the lubricating surface comprises an internal surface or component of an internal combustion engine.

4). The lubricating surface of claim 1 wherein the lubricating surface comprises an inner surface or component of a compression ignition engine.

5. The lubricating surface of claim 1, wherein the magnesium compound comprises magnesium sulfonate.

6). The lubricating surface of claim 2, wherein the magnesium sulfonate comprises an overbased sulfonate having a total base number (TBN) of between about 300 and about 500.

7. The lubricating surface of claim 1, wherein the phosphorus content in the lubricant composition is from about 250 ppm to about 500 ppm.

8). The lubricating surface of claim 1, wherein the lubricant composition further comprises a metal-free friction reducing agent selected from glycerol esters and amine compounds.

9. 2. An automobile comprising the lubricating surface according to 1 above.

10. The lubricating surface of claim 1, wherein the amount of hydrocarbon soluble magnesium compound in the lubricant composition is from about 0.15 weight percent to about 2.0 weight percent.

11. Lubricant composition having a movable part and containing a lubricant for lubricating the movable part, the lubricant comprising an oil of lubricating viscosity, and a certain amount of antiwear agent lacking a magnesium compound Providing at least one hydrocarbon soluble magnesium compound in an amount effective to further reduce wear of the surface of the moving part than reduction of wear of the surface of the moving part by the object, and said lubricant composition A car that contains about 500 ppm or less of phosphorus.

12 The vehicle of claim 11, wherein the magnesium compound comprises magnesium sulfonate.

13. The vehicle of claim 12, wherein the magnesium sulfonate comprises an overbased sulfonate having a total base number (TBN) of between about 300 and about 500.

14 The vehicle of claim 11, wherein the content of phosphorus in the lubricant composition is from about 250 ppm to about 500 ppm.

15. The vehicle of claim 11, wherein the lubricant composition further comprises a metal-free friction reducing agent selected from glycerol esters and amine compounds.

16. The vehicle of claim 11, wherein the amount of magnesium compound in the lubricant composition is from about 0.15 weight percent to about 2.0 weight percent.

17. 12. The vehicle according to 11 above, wherein the movable part is a heavy duty diesel engine.

18. A base oil component of lubricating viscosity and magnesium soluble in at least one hydrocarbon in an amount effective to reduce surface wear more than reduced surface wear by a lubricant composition lacking a magnesium compound. A fully composed lubricant composition comprising an amount of anti-wear agent to provide a compound, wherein the lubricant composition contains no more than about 500 ppm phosphorus and lacks a calcium detergent and an organomolybdenum compound. A fully formulated lubricant composition.

19. 19. The lubricant composition of claim 18, wherein the lubricant composition comprises a low ash, low sulfur, and low phosphorus lubricant composition suitable for a compression ignition engine.

20. 19. The lubricant composition of claim 18, wherein the magnesium compound comprises an overbased magnesium sulfonate having a total base number (TBN) of between about 300 and about 500.

21. 19. The lubricant composition of claim 18, wherein the phosphorus content in the lubricant composition is from about 250 ppm to about 500 ppm.

22. 19. The lubricant composition of claim 18, further comprising a metal-free friction reducing agent selected from glycerol esters and amine compounds.

23. The lubricant composition of claim 18, wherein the amount of magnesium compound in the lubricant composition is from about 0.15 weight percent to about 2.0 weight percent.

24. A lubricant concentrate that provides improved abrasion resistance to the lubricant composition, wherein the concentrate is substantially devoid of calcium, and the hydrocarbyl carrier fluid, and the lubricant composition comprising the concentrate, from about 120 ppm to about A lubricant concentrate such as consisting of a magnesium compound soluble in at least one hydrocarbon sufficient to provide 2000 ppm magnesium.

25. 25. The additive concentrate of claim 24, wherein the magnesium compound comprises overbased magnesium sulfonate having a total base number (TBN) of between about 300 and about 500.

26. A lubricant composition comprising a base oil and the additive concentrate as described in 24 above.

27. A method of lubricating moving parts with lubricating oil, which shows increased wear resistance, and as a lubricating oil for one or more moving parts, wear resistance that is substantially devoid of base oil and calcium. An antiwear agent is soluble in a hydrocarbyl carrier fluid and a sufficient amount of hydrocarbons to provide from about 120 ppm to about 2000 ppm magnesium in the lubricating oil. A method comprising a magnesium compound.

28. 28. The method of claim 27, wherein the moving part comprises an engine moving part.

29. 29. The method of claim 28, wherein the engine is selected from the group consisting of a compression ignition engine and a spark addition engine.

30. 29. The method of claim 28, wherein the engine comprises an internal combustion engine having a crankcase, and wherein the lubricating oil comprises crankcase oil present in the engine crankcase.

31. 28. The method of claim 27, wherein the lubricant comprises a drive train lubricant present in a vehicle drive train including the engine.

32. 28. The method of claim 27, wherein the lubricating oil further comprises a metal-free friction reducer selected from glycerol esters and amine compounds.

Claims (10)

  A base oil of lubricating viscosity and an amount of at least one hydrocarbon-soluble magnesium compound effective to further reduce surface wear than reduction of surface wear by a lubricant composition lacking magnesium compound; A lubricating surface comprising a lubricant composition comprising a lubricant composition, wherein the lubricant composition contains about 0.05 wt% or less of phosphorus.   The lubricating surface of claim 1, wherein the magnesium compound comprises magnesium sulfonate.   The lubricating surface of claim 1, wherein the magnesium sulfonate comprises an overbased sulfonate having a total base number (TBN) of between about 300 and about 500.   The lubricating surface of claim 1, wherein the phosphorus content in the lubricant composition is from about 250 ppm to about 500 ppm.   Lubricant composition having a movable part and containing a lubricant for lubricating the movable part, the lubricant comprising an oil of lubricating viscosity, and a certain amount of antiwear agent lacking a magnesium compound Providing at least one hydrocarbon soluble magnesium compound in an amount effective to further reduce wear of the surface of the moving part than reduction of wear of the surface of the moving part by the object, and said lubricant composition A car that contains about 500 ppm or less of phosphorus.   The vehicle of claim 5, wherein the lubricant composition further comprises a metal-free friction reducer selected from glycerol esters and amine compounds.   The vehicle of claim 5, wherein the amount of magnesium compound in the lubricant composition is from about 0.15 weight percent to about 2.0 weight percent.   A base oil component of lubricating viscosity and magnesium soluble in at least one hydrocarbon in an amount effective to reduce surface wear more than reduced surface wear by a lubricant composition lacking a magnesium compound. A fully composed lubricant composition comprising an amount of anti-wear agent to provide a compound, wherein the lubricant composition contains no more than about 500 ppm phosphorus and lacks a calcium detergent and an organomolybdenum compound. A fully formulated lubricant composition.   A lubricant concentrate that provides improved abrasion resistance to the lubricant composition, wherein the concentrate is substantially devoid of calcium, and the hydrocarbyl carrier fluid, and the lubricant composition comprising the concentrate, from about 120 ppm to about A lubricant concentrate such as consisting of a magnesium compound soluble in at least one hydrocarbon sufficient to provide 2000 ppm magnesium.   A method of lubricating moving parts with lubricating oil, which shows increased wear resistance, and as a lubricating oil for one or more moving parts, wear resistance that is substantially devoid of base oil and calcium. An antiwear agent is soluble in a hydrocarbyl carrier fluid and a sufficient amount of hydrocarbons to provide from about 120 ppm to about 2000 ppm magnesium in the lubricating oil. A method comprising a magnesium compound.