KR20090086612A - Tartaric acid derivatives as fuel economy improvers and antiwear agents in crankcase oils and preparation thereof - Google Patents

Abstract

Formulations using tartaric compounds of the present invention in a low sulfur, low ash and low phosphorous lubricant lower wear, and friction and improves fuel economy. ® KIPO & WIPO 2009

Description

Tartaric acid derivative as a fuel economy improver and abrasion resistant agent in crankcase oil, and a method for preparing the same {TARTARIC ACID DERIVATIVES AS FUEL ECONOMY IMPROVERS AND ANTIWEAR AGENTS IN CRANKCASE OILS AND PREPARATION THEREOF}

The present invention relates to a lubricant composition with a low sulfur, ash and phosphorus content and a method for lubricating an internal combustion engine for providing fuel economy improvement, fuel economy maintenance and wear and friction reduction.

Fuel economy is very important, and lubricants that can improve fuel economy by reducing friction in the engine are of significant value. The present invention provides a low sulfur, low ash, low phosphorus lubricant composition comprising an additive package that leads to improved fuel economy of an internal combustion engine. This improvement is made possible by the provision of an additive package in which the friction modifier component is predominantly or exclusively tartrate.

US Pat. No. 4,237,022 to Barrer, Dec. 2, 1980 discloses tartrimide useful as an additive in fuels and lubricants for improved fuel economy as well as effective reduction of squeaks and friction.

U.S. Patent 4,952,328 (Davis et al., Aug. 28, 1990) is a lubricating oil composition for an internal combustion engine, comprising: (A) an oil of lubricity viscosity, (B) a carboxyl derivative produced by reacting a specific amine with a succinic acylating agent, and (C) Disclosed is a composition comprising a basic alkali metal salt of sulfonic acid or carboxylic acid. Exemplary lubricant compositions (lubricants III) include base oils comprising viscosity index modifiers; Basic magnesium alkylated benzene sulfonates; Overbased sodium alkylbenzene sulfonate; Basic calcium alkylated benzene sulfonates; Succinimide dispersants; And zinc salts of phosphorodithioic acid.

US Patent 4,326,972 (Chamberlin, April 27, 1982) discloses a lubricant composition for improving fuel economy of an internal combustion engine. This composition comprises a specific sulfurized composition (based primarily on esters of carboxylic acids) and basic alkali metal sulfonates. The additional component may include at least one oil dispersible detergent or dispersant, a viscosity modifier, and certain salts of phosphoric acid.

Summary of the Invention

The present invention

(a) oils of lubricity viscosity, and

(b) a low sulfur, low phosphorus, low ash lubricant composition suitable for lubrication of an internal combustion engine comprising a condensation product of a substance represented by formula (I) with an alcohol of 6 to 12 carbon atoms, wherein the ash value of sulfuric acid is about 1.0 or less; A lubricant composition having a phosphorus content of about 0.08% by weight or less and a sulfur content of about 0.4% by weight or less is provided:

Formula I

In this formula, each R is independently H or a hydrocarbyl group, or R groups together form a ring, and if R is H, the condensation product is optionally further functionalized by reaction with an acylated or boron compound. .

The present invention also provides a method for lubricating an internal combustion engine, comprising supplying a lubricant composition to an engine.

Various preferred features and embodiments will be illustrated by the following non-limiting examples.

The present invention provides a composition as described above. Often, the composition has less than 0.4% by weight of total sulfur in one aspect, less than 0.3% by weight in another aspect, 0.2% by weight or less in another aspect, and 0.1% by weight or less in another aspect. Often the main source of sulfur present in the compositions of the present invention is from conventional diluent oils. The total content of sulfur is in the typical range of 0.1 to 0.01% by weight.

Often, the composition has a total content of phosphorus of 800 ppm or less of the composition, 500 ppm or less in another aspect, 300 ppm or less in another aspect, 200 ppm or less in another aspect, and 100 ppm or less in another aspect. The total content of phosphorus is typically in the range 500 to 100 ppm.

Often, the composition has a total content of ash content of 1.0% by weight or less of the composition as determined by ASTM D-874, 0.7% by weight or less in one aspect, 0.4% by weight or less in another aspect, 0.3% by weight or less in another aspect, It is 0.05 weight% or less from another viewpoint. The total content of sulfuric acid ash is in the typical range of 0.7 to 0.05% by weight.

Oil of lubricity viscosity

Low sulfur, low phosphorus, low ash lubricating oil compositions generally comprise one or more base oils present in major amounts (ie, greater than about 50% by weight). Generally, the base oil is present in an amount greater than about 60%, or greater than about 70%, or greater than about 80% by weight of the lubricating oil composition. The sulfur content of base oils is usually less than 0.2% by weight.

Low sulfur, low phosphorus, low ash lubricating oil compositions have a viscosity of about 16.3 mm 2 / s or less at 100 ° C., in one embodiment 5 to 16.3 mm 2 / s (cSt) at 100 ° C., and in one embodiment 6 to 13 mm 2 at 100 ° C. / s (cSt) may be. According to one aspect, the lubricating oil composition has a SAE viscosity grade of 0W, 0W-20, 0W-30, 0W-40, 0W-50, 0W-60, 5W, 5W-20, 5W-30, 5W-40, 5W- 50, 5W-60, 10W, 10W-20, 10W-30, 10W-40 or 10W-50.

The low sulfur, low phosphorus, low ash lubricating oil composition has a high temperature / high shear viscosity at 150 ° C., measured according to the procedure of ASTM D4683, 4 mm 2 / s (cSt) or less, in one embodiment 3.7 mm 2 / s (cSt), According to one aspect, it may be 2 to 4 mm 2 / s (cSt), in one aspect to 2.2 to 3.7 mm 2 / s (cSt), and in one aspect to 2.7 to 3.5 mm 2 / s (cSt).

The base oil used in the low sulfur, low phosphorus, low ash lubricant composition may be natural oil, synthetic oil or mixtures thereof, provided that the sulfur content of the oil does not exceed the aforementioned sulfur concentration ranges required for the low sulfur, low phosphorus, low ash lubricant composition of the present invention. have. Useful natural oils include animal and vegetable oils (eg castor oil, lard oil) as well as inorganic lubricating oils such as liquid petroleum oils and solvent treated or acid treated inorganic lubricating oils of paraffinic, naphthenic or mixed paraffinic-naphthenic type. . Oils derived from coal or shale are also useful. Synthetic lubricants include hydrocarbon oils such as polymerized and interpolymerized olefins (eg, polybutylene, polypropylene, propylene isobutylene copolymers, etc.); Poly (1-hexene), poly- (1-octene), poly (1-decene) and the like and mixtures thereof; Alkylbenzenes (eg, dodecylbenzene, tetradecylbenzene, dinonylbenzene, di- (2-ethylhexyl) benzene, etc.); Polyphenyls (eg, biphenyls, terphenyls, alkylated polyphenyls, etc.); Alkylated diphenyl ethers and derivatives, analogs and homologs thereof, and the like.

Alkylene oxide polymers and derivatives in which interpolymers and terminal hydroxy groups have been modified by esterification, etherification, etc. are another class of known synthetic lubricants that can be used. Examples include oils prepared through the polymerization of ethylene oxide or propylene oxide, alkyl and aryl ethers of such polyoxyalkylene polymers (eg, methyl-polyisopropylene glycol ethers having an average molecular weight of about 1000, molecular weights of about 500 to 1000 Diphenyl ethers of phosphorus polyethylene glycols, diethyl ethers of polypropylene glycols having a molecular weight of about 1000 to 1500), or mono- and polycarboxy clock esters thereof, such as carboxylic acid diesters, acetic acid esters or mixed C3-8 of tetraethylene glycol Fatty acid esters.

Other suitable classes of synthetic lubricants that may be used are dicarboxylic acids (e.g., phthalic acid, succinic acid, alkylsuccinic acid, alkenylsuccinic acid, maleic acid, azelaic acid, suberic acid, sebacic acid, fumaric acid, adipic acid, linoleic acid dimers). , Malonic acid, alkyl malonic acid, alkenyl malonic acid, etc.) and various alcohols (e.g. butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, ethylene glycol, diethylene glycol monoether, propylene glycol, etc.) Esters. Specific examples of such esters include dibutyl adipate, di (2-ethylhexyl) sebacate, di-n-hexyl fumarate, dioctyl sebacate, diisooctyl azelate, diisodecyl azelate, dioctyl phthalate , Didecyl phthalate, diecosyl sebacate, 2-ethylhexyl diester of linoleic acid dimer, 1 mol of sebacic acid and 2 mol of tetraethylene glycol and 2 mol of 2-ethylhexanoic acid.

In addition, esters useful as synthetic oils include those prepared from C5 to C12 monocarboxylic acids and polyols and polyol ethers such as neopentyl glycol, trimethylol propane, pentaerythritol, dipentaerythritol, tripentaerythritol, and the like.

The oil may be poly-alpha-olefin (PAO). Typically, PAOs are derived from monomers having 4 to 30, or 4 to 20, or 6 to 16 carbon atoms. Examples of useful PAOs include those derived from octenes, decenes, mixtures thereof and the like. Such PAOs may have a viscosity of 2 to 15 mm 2 / s, or 3 to 12 mm 2 / s, or 4 to 8 mm 2 / s (cSt) at 100 ° C. Examples of useful PAOs include poly-alpha-olefins having a 100 ° C. viscosity of 4 mm 2 / s (cSt), poly-alpha-olefins having a 100 ° C. viscosity of 6 mm 2 / s (cSt) and mixtures thereof. Mixtures of one or more of the above PAOs and mineral oils may be used.

Natural or synthetic crude, refined and refined oils (as well as mixtures of any two or more thereof) of the types disclosed above may be used in the lubricants of the present invention. Crude oils are oils obtained directly from natural or synthetic sources without further purification. For example, shale oil obtained directly in the retort treatment operation, petroleum oil obtained directly in the first distillation or ester oil obtained directly from the esterification process and used without further treatment may be crude oil. Refined oils are similar to crude oils except that they are further processed to improve one or more properties through one or more purification steps. Many such purification techniques are known to those skilled in the art and include solvent extraction, secondary distillation, acid or base extraction, filtration, osmosis and the like. The refined oil is obtained by a process similar to that used for obtaining the refined oil, which is applied to the refined oil already in use. Such refined oils are also known as regenerated or reprocessed oils and are often further treated with techniques for the removal of spent additives and oil degradation products.

In addition, oils produced by Fischer-Tropsch gas to liquid synthesis procedures are also known and can be used.

Friction modifier

The tartrate of the present invention may be prepared by the reaction of tartaric acid with one or more alcohols.

Alcohols useful for the preparation of tartrate may contain 6 to 12, or 6 to 10, or 8 to 10 carbon atoms. The alcohol used may be linear or branched, and if branched, branching may occur at any point in the chain and may be branched to any length. In one embodiment, the alcohol is a linear alcohol having 8 to 10 carbon atoms.

The use of alcohols having six or more carbon atoms is believed to produce products with reduced volatility compared to products prepared from shorter chain alcohols. It is also contemplated that the use of alcohols having at least one branch will promote solubility of the product in the oil. Thus, certain embodiments of the invention are prepared using branched alcohols having 6 or more carbon atoms, such as branched C _6-12 or C _6-10 alcohols or branched C _8-10 alcohols, either alone or as a mixture. Use one product. Such branched alcohols can provide maximum solubility and compatibility with oils. Embodiments include 2-ethylhexanol and isotridecyl alcohol, the latter may be a mixture of various isomers that are commercially available. In addition, certain embodiments of the present invention utilize products prepared using linear alcohols having six or more carbon atoms, such as linear C _6-12 or C _6-10 alcohols or linear C _8-10 alcohols, alone or as a mixture. Such linear alcohols can provide the optimum friction performance for the oil.

The tartrate of the present invention can be conveniently prepared by reacting tartaric acid or a reactive equivalent of this tartaric acid (eg, esters, acid halides or anhydrides) with one or more of the corresponding alcohols in accordance with known condensation methods.

Likewise, the alkyl groups of the amines can similarly be linear or branched.

The tartaric acid used in the preparation of the tartrate of the invention may be of commercially available type (obtained from Sargent Welch), which is one or more isomeric forms, such as often from sources (natural) or synthetic methods (e.g. from maleic acid). ) May be present as d -tartaric acid, l -tartaric acid or mesotartaric acid. Such derivatives may also be prepared from functional equivalents to diacids which are readily apparent to those skilled in the art, such as esters, acid chlorides, anhydrides and the like.

The tartrate of the present invention may be solid, semisolid or oil, depending on the particular alcohol used to prepare the tartrate. For use as an additive in oily compositions comprising a lubricating composition and a fuel composition, tartrate is advantageously soluble and / or stable dispersible in the oily composition. That is, a composition intended to be used, for example, in oils is generally oil-soluble and / or stable dispersibility in the oil in which the composition is used. The term "solubility" as used herein and in the claims that follow does not necessarily mean that all of the compositions in question are miscible or soluble in all proportions in all oils. Rather, it is intended to indicate that the composition is soluble in oils (mineral oils, synthetic oils, etc.) in that the solution functions to exhibit one or more desired properties. Similarly, this "solution" need not be a true solution in the strict physical or chemical sense. Instead, it may be a microemulsion or colloidal dispersion that exhibits properties close enough to true solutions for alternative purposes in the context of the present invention for practical purposes.

As indicated above, the tartrate compositions of the present invention are useful as additives for lubricants in that they can function as rust and corrosion inhibitors, friction modifiers, antiwear agents and anti-emulsifiers. The compositions can be used in a variety of lubricants based on various oils of lubricity viscosity, including natural and synthetic lubricants and mixtures thereof. Such lubricants include crankcase lubricants for spark and compression ignition internal combustion engines, including automotive and truck engines, two-stroke engines, aviation piston engines, ships and railway diesel engines. It can also be used in gas engines, stationary power engines and turbines. In addition, automotive transmission fluids, transaxle lubricants, gear lubricants, metalworking lubricants, hydraulic oils, and other lubricants and grease compositions may also benefit from the addition of the compositions of the present invention.

Other friction modifiers may be present in the lubricant of the invention, such as esters of polyols such as glycerol monooleate; Oleyl amides; Diethanol fatty acid amines and mixtures thereof. A useful list of friction modifiers is included in US Pat. No. 4,792,410.

Esters of polyols include fatty acid esters of glycerol. Esters of polyols can be prepared by a variety of methods known in the art. Many esters, such as glycerol monooleate and glycerol monotallowate, are produced on a commercial scale. Esters useful in the present invention are oil soluble and are preferably prepared from C ₈ to C ₂₂ fatty acids or mixtures thereof as found in natural products. Fatty acids may be saturated or unsaturated. Certain compounds found in acids of natural origin may include licanic acid containing one keto group. Useful C ₈ to C ₂₂ fatty acids are those represented by the formula R-COOH, wherein R is alkyl or alkenyl.

Fatty acid monoesters of glycerol are useful. Mixtures of monoesters and diesters may also be used. The mixture of monoesters and diesters may comprise at least about 40% monoesters. Mixtures of monoesters and diesters of glycerol containing from about 40% to about 60% by weight monoesters can be used. For example, glycerol monooleate containing a mixture of commercially available 45 to 55% by weight monoester and 55 to 45% by weight diester can be used.

Useful fatty acids are derived from oleic acid, stearic acid, isostearic acid, palmitic acid, myristic acid, palmitoleic acid, linoleic acid, lauric acid, linolenic acid and eleostearic acid, and natural products, tallow, palm oil, olive oil and peanut oil. It's a mountain.

Although esters of tartrate and polyols, such as glycerol monooleate, may seem similar in appearance to molecular structures, it is observed that certain combinations of these materials can actually provide better performance, such as wear protection than when used alone.

Fatty acid amides are discussed in detail in US Pat. No. 4,280,916. Suitable amides are C ₈ -C ₂₄ aliphatic monocarboxylic amides and are known. The reaction of fatty acid base compounds with ammonia produces fatty acid amides. Fatty acids and amides derived therefrom may be saturated or unsaturated. Important fatty acids include lauric acid C ₁₂ , palmitic acid C ₁₆ and stearic acid C ₁₈ . Other important unsaturated fatty acids include oleic acid, linoleic acid and linolenic acid, all of which are C ₁₈ . In one embodiment, the fatty acid amides of the invention are derived from C ₁₈ unsaturated fatty acids.

Fatty acid amines and diethoxylated long chain amines such as N, N-bis- (2-hydroxyethyl) -tallowamine per se are generally useful as components of the present invention. These two types of amines are commercially available. Fatty acid amines and ethoxylated fatty acid amines are described in more detail in US Pat. No. 4,741,848.

Etc

Antioxidants (ie, antioxidants) are hindered phenolic antioxidants such as 2,6-di-t-butylphenol and hindered phenolic esters such as those represented by the formula:

According to a specific embodiment, it includes:

Wherein R ³ is a straight or branched chain alkyl group containing 2 to 10 carbon atoms, in one embodiment 2 to 4 and in another embodiment 4. In one embodiment, R ³ is an n-butyl group. In another embodiment, R ³ may have 8 carbon atoms as found in the Shiva product Irganox L-135 ™. Methods for preparing such antioxidants can be found in Patent 6,559,105.

Still other antioxidants include secondary aromatic amine antioxidants such as dialkyl (eg dinonyl) diphenylamines, sulfurized phenolic antioxidants, oil soluble copper compounds, phosphorus antioxidants, molybdenum compounds such as Mo dithiocarbamate , Organic sulfides, disulfides and polysulfides (eg, sulfide dies alder adducts of butadiene and butyl acrylate). A diverse list of antioxidants can be found in US Pat. No. 6,251,840.

EP agents / abrasion resistant agents used in connection with the present invention are generally in the form of zinc dialkyldithiophosphates. There are a very large number of different antiwear agents that can be used in connection with the functional fluids of interest, but the inventors have found that zinc dialkyldithiophosphate type antiwear agents are particularly associated with other components to obtain the desired properties. It worked well. In one embodiment, at least 50% of the alkyl groups (derived from alcohol) present in the dialkyldithiophosphates are secondary groups, ie groups derived from secondary alcohols. In another embodiment, at least 50% of the alkyl groups are groups derived from isopropyl alcohol.

Ashless detergents and dispersants may produce nonvolatile materials, such as boron oxide or phosphorus pentoxide, upon combustion, depending on the composition. However, ashless detergents and dispersants usually do not contain metal and do not produce metal containing ash upon combustion. Ashless dispersants are well known in the art for many types. Such materials may bind metal ions from other sources within the system but are generally referred to as "ash-free".

(1) "carboxyl dispersants" are nitrogen-containing compounds (e.g., amines), organic hydroxy compounds (e.g., aliphatic compounds, including monohydric and polyhydric alcohols, or aromatic compounds, including phenols and naphthols), and / or basic Reaction products of carboxyl acylating agents (acids, anhydrides, esters, etc.) containing at least 34, preferably at least 54 carbon atoms, which react with inorganic materials. Such reaction products include imides, amides and ester reaction products of carboxyl ester dispersants.

Carboxylic acylating agents include fatty acids, isoaliphatic acids (e.g. 8-methyl-octadecanoic acid), dimer acids, added dicarboxylic acids (4 + 2 and 2 + 2 adducts of unsaturated carboxyl reagents and unsaturated fatty acids), trimers Body acids, added tricarboxylic acids (Empol ^® 1040, Hystrene ^® 5460 and Unidyme ^® 60) and hydrocarbyl substituted carboxyl acylating agents (derived from olefins and / or polyalkenes). In one embodiment, the carboxyl acylating agent is a fatty acid. Fatty acids generally contain up to 8 to 30 carbon atoms, or up to 12 to 24 carbon atoms. Carboxylic acylating agents are taught in US Pat. Nos. 2,444,328, 3,219,666, 4,234,435 and 6,077,909.

The amines can be monoamines or polyamines. Monoamines generally have one or more hydrocarbyl groups containing 1 to 24 carbon atoms, or 1 to 12 carbon atoms. Examples of monoamines include fatty (C8-30) amine (Armeens ™), primary ether amines (SURFAM ^® amines), tertiary-aliphatic primary amines (Primenes ™), hydroxyl amine (primary, secondary, or 3 Primary alkanol amines), ether N- (hydroxyhydrocarbyl) amines and hydroxy-hydrocarbyl amines (Ethomeens ™ and Propomeens ™). The polyamines are alkoxylated diamines (Ethoduomeens ™), fatty acid diamines (Duomeens ™), alkylenepolyamines (ethylenepolyamines), hydroxy containing polyamines, polyoxyalkylene polyamines (Jeffamines ™), condensed polyamines (at least one primary or Condensation reactions between at least one polyamine reactant containing a secondary amino group and at least one hydroxy compound) and heterocyclic polyamines. Useful amines include those disclosed in US Pat. Nos. 4,234,435 (Meinhart) and 5,230,714 (Steckel).

Polyamines from which the dispersant is derived mostly comprise alkylene amines according to the general formula:

Wherein t is usually an integer less than 10, A is hydrogen or a hydrocarbyl group, typically of up to 30 carbon atoms, and the alkylene group is typically an alkylene group of less than 8 carbon atoms. Alkylene amines mainly include methylene amine, ethylene amine, hexylene amine, heptylene amine, octylene amine, other polymethylene amines. Specific examples include ethylene diamine, diethylene triamine, triethylene tetraamine, propylene diamine, decamethylene diamine, octamethylene diamine, di (heptamethylene) triamine, tripropylene tetramine, tetraethylene pentamine, trimethylene diamine, Pentaethylene hexamine, di (-trimethylene) triamine. Also useful are higher homologues such as those obtained by condensing two or more of the alkylene amines exemplified above. Tetraethylene pentamine is particularly useful.

Especially useful are ethylene amines, also called polyethylene polyamines. A more detailed description is given in the book Encyclopedia of Chemical Technology, Kirk and Othmer, Vol. 5, pp. 898-905, Interscience Publishers, New York (1950), under the heading "ethylene amine."

Also useful are hydroxyalkyl substituted alkylene amines, ie alkylene amines having one or more hydroxyalkyl substituents on the nitrogen atom. Examples of such amines include N- (2-hydroxyethyl) ethylene diamine, N, N'-bis (2-hydroxyethyl) -ethylene diamine, 1- (2-hydroxyethyl) piperazine, monohydroxypropyl Piperazine, di-hydroxypropyl substituted tetraethylene pentamine, N- (3-hydroxypropyl) -tetra-methylene diamine and 2-heptadecyl-1- (2-hydroxyethyl) -imidazoline Included.

Also useful are higher homologues such as those obtained by condensation via amino radicals or hydroxy radicals of the alkylene amines or hydroxy alkyl substituted alkylene amines exemplified above. Condensed polyamines are formed by condensation reactions between at least one polyamine reactant containing at least one primary or secondary amino group and at least one hydroxy compound and are described in US Pat. Nos. 5,230,714 and 5,296,154 (Steckel).

Examples of such “carboxy clock dispersants” are British Patents 1,306,529 and a number of US patents, such as 3,219,666, 3,316,177, 3,340,281, 3,351,552, 3,381,022, 3,433,744, 3,444,170, 3,467,668, 3,501,405, 3,542,680, 3,576,909, 3,576, 909, 3,576, 909, 3,576, 909, 6,574, 743, 6,574, 743, 6,576, 743, 6, 574, 743, 6, 574, 743, 6, 574, 743, 6, 574, 743, 6, 574, 743, 6, 574, 743, 6, 574, 743, 6, 574, 743, 6, 574, 743, 6, 574, 743, 6, 574, 743, 6, 574, 743, 6, 574, 743, 6, 574, 743 6 It is.

(2) The succinimide dispersant is a kind of carboxyl dispersant. This dispersant is a reaction product of an organic hydroxy compound or an amine containing at least one hydrogen attached to a nitrogen atom, or a mixture of said hydroxy compound and amine with a hydrocarbyl substituted succinic acylating agent. The term "succinic acylating agent" includes hydrocarbon substituted succinic or succinic acid producing compounds, which term may also include the acid itself. Such materials generally include hydrocarbyl substituted succinic acids, anhydrides, esters (including half esters) and halides.

Succinic dispersants vary in chemical structure, but generally include the following structures:

이 500 또는 700 내지 10,000인 폴리올레핀계 기이다. 일반적으로, 하이드로카르빌 기는 알킬 기, 흔히 분자량이 500 또는 700 내지 5000 또는 대안적으로 1500 또는 2000 내지 5000인 폴리이소부틸 기이다. 달리 표현하면, R¹ 기는 40 내지 500개의 탄소원자, 예컨대 적어도 50개, 예컨대 50 내지 300개의 탄소원자, 예컨대 지방족 탄소원자를 포함할 수 있다. R²는 알킬렌 기, 일반적으로 에틸렌(C₂H₄) 기이다. 이러한 분자는 일반적으로 폴리아민과 알케닐 아실화제의 반응으로부터 유래되고, 위에 제시된 간단한 이미드 구조 외에, 다양한 아미드 및 4차 암모늄 염을 비롯한 두 모이어티 사이의 다양한 결합도 가능하다. 석신이미드 분산제는 미국 특허 4,234,435, 3,172,892 및 6,165,235에 더욱 상세하게 설명되어 있다.In this structure, each R ¹ is independently a hydrocarbyl group, such as

And 500 or 700 to 10,000 polyolefin group. Generally, hydrocarbyl groups are alkyl groups, often polyisobutyl groups having a molecular weight of 500 or 700 to 5000 or alternatively 1500 or 2000 to 5000. In other words, the R ¹ group may comprise 40 to 500 carbon atoms, such as at least 50, such as 50 to 300 carbon atoms, such as aliphatic carbon atoms. R ² is an alkylene group, generally an ethylene (C ₂ H ₄ ) group. Such molecules are generally derived from the reaction of polyamines with alkenyl acylating agents, and in addition to the simple imide structures shown above, various bonds between two moieties, including various amide and quaternary ammonium salts, are possible. Succinimide dispersants are described in more detail in US Pat. Nos. 4,234,435, 3,172,892 and 6,165,235.

Polyalkenes from which substituents are derived are generally homopolymers and interpolymers of polymerizable olefin monomers having 2 to 16, usually 2 to 6 carbon atoms. The amines that react with the succinic acylating agents to form the carboxyl dispersant composition may be monoamines or polyamines as described above.

Succinimide dispersants may be in the form of amine salts, amides, imidazolines as well as mixtures thereof, but are called as such because they usually contain nitrogen mainly in the form of imide functional groups. In order to prepare the succinimide dispersant, at least one succinic acid producing compound and at least one amine are usually mixed at 80 ° C. to a mixture, usually in the presence of water, optionally in the presence of a liquid, a substantially inert organic liquid solvent / diluent. Or heated to a temperature range below the decomposition point of the product, generally from 100 ° C to 300 ° C.

Further details and examples of procedures for preparing the succinimide dispersants of the present invention are included in US Pat. Nos. 3,172,892, 3,219,666, 3,272,746, 4,234,435, 6,440,905 and 6,165,235.

(3) An "amine dispersant" is a reaction product of a relatively high molecular weight aliphatic halide and an amine, preferably a polyalkylene polyamine. Examples thereof are described in US Pat. Nos. 3,275,554, 3,438,757, 3,454,555 and 3,565,804.

(4) "Mannich dispersants" are reaction products of alkyl phenols in which the alkyl group contains at least 30 carbon atoms with aldehydes (especially formaldehyde) and amines (especially polyalkylene polyamines). Examples of this material are described in US Pat. Nos. 3,036,003, 3,236,770, 3,414,347, 3,448,047, 3,461,172, 3,539,633, 3,586,629, 3,591,598, 3,634,515, 3,725,480, 3,726,882 and 3,980,569.

(5) Post-treated dispersants include carboxyl, amine or Mannich dispersants with dimercaptothiadiazole, urea, thiourea, carbon disulfide, aldehydes, ketones, carboxylic acids, hydrocarbon-substituted succinic anhydrides, nitrile epoxides, boron compounds It is obtained by reacting with a reagent such as phosphorus compound. Examples of materials of this kind are described in the following U.S. patents: 3,200,107, 3,282,955, 3,367,943, 3,513,093, 3,639,242, 3,649,659, 3,442,808, 3,455,832, 3,579,450, 3,600,372, 3,702,757 and 3,708,422.

(6) Polymeric dispersants include oil-soluble monomers such as decyl methacrylate, vinyl decyl ether and high molecular weight olefins and polar substituent-containing monomers such as aminoalkyl acrylates or acrylamides and poly- (oxyethylene) -substituted acrylates. Of interpolymers. Examples of these polymer dispersants are disclosed in the following US patents: 3,329,658, 3,449,250, 3,519,656, 3,666,730, 3,687,849 and 3,702,300.

The composition may also contain one or more detergents which are usually salts, in particular overbased salts. Overbased salts or overbased materials are single phase homogeneous Newtonian systems characterized by metal contents in excess of the amounts that may be present depending on the stoichiometry of the metal and the specific acidic organic compound reacting with the metal. Overbased materials contain acidic materials (typically inorganic or lower carboxylic acids, preferably carbon dioxide) containing acidic organic compounds, at least one inert organic solvent (e.g. mineral oil, naphtha, toluene, xylene) for these acidic organic materials. Prepared by reaction with a reaction medium, a mixture containing a stoichiometric excess of metal base and promoter.

Acidic organic compounds useful in the preparation of overbased compositions of the present invention include carboxylic acids, sulfonic acids, phosphorus acids, phenols or mixtures thereof. Preferably, the acidic organic compound is a carboxylic acid or a sulfonic acid (eg hydrocarbyl substituted benzenesulfonic acid) and a hydrocarbyl substituted salicylic acid bearing a sulfonic or thiosulfone group. Another class of compounds useful for preparing the overbased compositions of the present invention is salixarate. A description of salixarates useful in the present invention can be found in WO 04/04850 publication.

Metal compounds useful for the preparation of overbased salts are generally any Group 1 or Group 2 metal compound (CAS version of the Periodic Table of Elements). Group 1 metals of the metal compounds include Group 1a alkali metals (eg sodium, potassium, lithium) as well as Group 1b metals such as copper. Group 1 metals are preferably sodium, potassium, lithium and copper, more preferably sodium or potassium, and more preferably sodium. Group 2 metals of the metal base include Group 2a alkaline earth metals (eg magnesium, calcium, strontium, barium) as well as Group 2b metals such as zinc or cadmium. Preferably, the Group 2 metal is magnesium, calcium, barium or zinc, preferably magnesium or calcium, more preferably calcium.

Examples of overbased detergents of the present invention include, but are not limited to, calcium sulfonates, calcium phenates, calcium salicylates, calcium salicylates, and mixtures thereof.

The amount of overbased material, ie, detergent, if present, is, according to one embodiment, between 0.05 and 3 weight percent or 0.1 to 3 weight percent, or 0.1 to 1.5 weight percent, or 0.15 to 1.5 weight percent of the composition.

Defoamers used to reduce or prevent the formation of stable foams include silicones and organic polymers. Examples of such antifoam compositions and other antifoam compositions are described in "Foam Control Agents", by Henry T. Kerner (Noyes Data Corporation, 1976), pages 125-162.

The composition of the present invention is used as a real lubricant by supplying lubricant to an internal combustion engine (eg, a fixed gas powered internal combustion engine) in such a way that the lubricant is delivered to critical parts of the engine to lubricate the engine during operation of the engine.

As used herein, "hydrocarbyl substituent" or "hydrocarbyl group" is used in its conventional meaning known to those skilled in the art. Specifically, it refers to a group in which a carbon atom is directly attached to the rest of the molecule and mainly exhibits hydrocarbon properties. Examples of hydrocarbyl groups are hydrocarbon substituents, ie aliphatic (eg alkyl or alkenyl), aliphatic ring (eg cycloalkyl, cycloalkenyl) substituents and aromatic-, aliphatic- and aliphatic ring-substituted aromatic substituents, as well as But also cyclic substituents in which the ring is completed through another part of the molecule (eg, two substituents together form a ring); Substituted hydrocarbon substituents, ie, non-hydrocarbon groups that do not primarily alter the hydrocarbon nature of the substituents in the context of the invention (eg halo (especially chloro and fluoro), hydroxy, alkoxy, mercapto, alkylmercapto, nitro, nitro) Bovine and sulfoxy); Hetero substituents, that is, substituents which possess primarily hydrocarbon properties in the context of the present invention but contain atoms other than carbon in rings or chains composed of carbon atoms. Heteroatoms include sulfur, oxygen, nitrogen and include substituents such as pyridyl, furyl, thienyl and imidazolyl. Generally, up to 2, preferably up to 1 non-hydrocarbon substituents will be present for every 10 carbon atoms of the hydrocarbyl group; Typically there will be no non-hydrocarbon substituents in the hydrocarbyl group.

It is known that some of the foregoing materials may interact in the final formulation, such that the components of the final formulation may be different from the initial one added. For example, metal ions (eg, metal ions of a detergent) may migrate to other acidic or anionic sites of other molecules. The products thus formed, such as the products formed when using the compositions of the present invention for their intended use, may not be readily described. Nevertheless, all such modifications and reaction products are included in the scope of the present invention, and the present invention also includes a composition prepared by mixing the aforementioned components.

The present invention will be described in more detail with reference to the following examples describing particularly advantageous embodiments. These examples are intended to illustrate the invention and are not intended to limit the invention.

Lubricants were evaluated by HFRR 1% CHP (High Frequency Reciprocating Rig 1% cumene hydroperoxide) test and the Cameron-Plint High Temperature Reciprocating Wear test for wear and friction reduction.

The HFRR 1% CHP test is used to evaluate the friction and wear performance of lubricants containing reduced levels of phosphorus and sulfur. The percentage of abrasion defect diameter and film thickness using a reciprocating steel ball bearing sliding against a steel plate is measured. This test is performed using 1% cumene hydroperoxide (CHP) in conjunction with a high speed reciprocating suitability tester, part of the commercial tribological testing equipment.

Cameron-Flint high temperature reciprocating wear tests are used to evaluate the friction and wear performance of lubricants. The percentage of wear scar diameter and film thickness is measured using reciprocating steel ball bearings that slide against steel plates. This test is carried out using the Cameron-Flint reciprocating wear test, which is part of the commercial tribological testing equipment.

Formulations of the following formulations are prepared in oils of lubricious viscosity: where the content of the additive components is by weight unless otherwise indicated: 0.15% pour point inhibitor (including about 35% dilution oil), 8% viscosity index improver ( About 91% dilution oil), 0.89% dilution oil, 5.1% succinimide dispersant (including about 47% dilution oil), 0.48% zinc dialkyldithiophosphate (excluding 0.98% C1) About 9% diluted oil), 1.53% overbased calciumsulfonate detergent (containing about 42% diluted oil), 0.1% glycerol monooleate (containing about 0% diluted oil), 3.44% antioxidant (about 5% Diluent oil), commercially available antifoaming agent of 90 to 100 ppm and base oil of the remaining content.

The formulation is added with the components as shown in the table below and subjected to the HFRR 1% CHP test and the Cameron-Flint high temperature reciprocating wear test. The results are shown in the table below.

Table 1

C1 0.1% P C2 0.05% P Ex. 1 0.05% P Ex. 2 0.05% P Ex. 3 0.05% P Ex. 4 0.05% P Additional Ingredients: Ingredient 1 One% Component 2 One% Ingredient 3 One% Ingredient 4 One% inspection: 1. HFRR 1% CHP inspection Wear crack diameter (㎛) 161, 185 285, 295 225 228 214 214 Film thickness (%) 94,83 23,1 98 82 98 93 2. Cameron-Flint High Temperature Reciprocating Wear Test Wear crack diameter (㎛) 339 661 361 323 324 345 Film thickness (%) 100 62 58 58 79 5.7

Component 1: (DL) tartaric acid / C8-10 alcohol / 2-ethylhexyl alcohol (50:50) (water removal)

Component 2: (DL) tartaric acid / C8-10 alcohol / tridecyl alcohol (50:50) (water removal)

Component 3: (DL) tartaric acid / C12-14 alcohol / 2-ethylhexyl alcohol (50:50) (water removal)

Component 4: ethylhexyl tartrate

The result is a low sulfur, low ash and low phosphorus lubricant containing 0.05 wt% of phosphorus delivered to the composition (C2) containing tartrate of the present invention (Ex. 1-4) without tartrate. It shows reduced wear compared to SAPS formulations. The formulation also provides equivalent wear protection as compared to the conventional GF-3 formulations (C1), which are high in phosphorus.

In addition, the lubricant is evaluated by the HFRR Low PS test. The HFRR Low PS test is used to evaluate the friction and wear performance of lubricants containing reduced phosphorus and sulfur levels. The percentage of abrasion defect diameter and film thickness using a reciprocating steel ball bearing sliding against a steel plate is measured. This test is carried out using 1% cumene hydroperoxide (CHP) in conjunction with a high speed reciprocating suitability tester which is part of the commercial tribological testing equipment.

Formulations of the following formulations are prepared in oils of lubricious viscosity: where the content of the additive components is by weight unless otherwise indicated: 0.15% pour point inhibitor (including about 35% dilution oil), 8% viscosity index improver ( About 91% dilution oil), 0.41% dilution oil, 5.0% succinimide dispersant (including about 47% dilution oil), 0.63% zinc dialkyldithiophosphate (each about 9% dilution oil) ), 1.53% overbased calcium sulfonate detergent (including about 42% diluent oil), 2.2% antioxidant (including about 5% diluent oil), 90 to 100 ppm commercial antifoaming agent and the rest of the base oil.

The formulation is added with ingredients as set out in the table below and subjected to the HFRR Low PS test. The results are shown in the table below.

TABLE 2

C3 0.05% P C4 0.05% P C5 0.05% P Ex. 5 0.05% P Ex. 6 0.05% P Additional ingredients Ingredient 5 0.5 1.0 Ingredient 6 0.5 1.0 1. HFRR Low PS Inspection Wear crack diameter (㎛) 337 318 241 219 223 Film thickness (%) 38 37 61 87 90

Component 5: 50:50 mixture of GMO: SNFO

Ingredient 6: C8-10 Tartrate

The results show that the formulation with the tartrate of the present invention (Ex. 5-6) in a low sulfur, low ash and low phosphorus lubricant contained 0.05% by weight of phosphorus delivered to the composition (C3-5) containing no tartrate. It shows reduced wear compared to a lower SAPS formulation.

Each document mentioned above is incorporated by reference in the present invention. Except for the examples, or unless expressly indicated otherwise, all numerical contents that specify the amount of material, reaction conditions, molecular weight, number of carbon atoms, etc. herein are understood to be modified by the word "about." Should be. Unless otherwise indicated, each chemical or composition referred to herein is to be construed as being a commercial grade material that may include isomers, by-products, derivatives, and other materials commonly understood to be present in the commercial grade. However, the amount of each chemical component is the amount shown, except for any solvents or diluent oils that may normally be present in the commercial material, unless otherwise noted. It is to be understood that the upper and lower limits, ranges, and ratio limits set forth herein may be combined independently. Likewise, the ranges and amounts of each component of the present invention may be used with the ranges or amounts of all other components. As used herein, the expression “consisting essentially of” allows for the inclusion of materials that do not substantially affect the basic and novel properties of the composition under consideration.

Claims (20)

(a) oils of lubricity viscosity, and (b) a low sulfur, low phosphorus, low ash lubricant composition suitable for use in an internal combustion engine comprising a condensation product of a substance represented by formula (I) with an alcohol of 6 to 12 carbon atoms, wherein the ash value is less than or equal to about 1.0; Lubricant compositions having a phosphorus content of about 0.08% or less and a sulfur content of about 0.4% or less: Formula I

[Wherein R is each independently H or a hydrocarbyl group or R groups together form a ring and when R is H the condensation product is optionally further functionalized by reaction with an acylation or boron compound do.] The lubricant composition of claim 1 wherein the alcohol is linear, branched, or a mixture thereof. The lubricant composition of claim 1 wherein the alcohol has about 8 to 10 carbon atoms. The lubricant composition of claim 1 wherein the condensation product (b) is a linear C _8-10 alkyl tartrate ester. The lubricant composition of claim 1 wherein the amount of condensation product is from about 0.05 to about 5.0 weight percent. 6. The lubricant composition of claim 5 wherein the amount of condensation product is from about 0.1 to about 2.0 weight percent. The lubricant composition of claim 6 wherein the amount of condensation product is from about 0.25 to about 1.25 weight percent. The lubricant composition of claim 1 further comprising a metal dialkyldithiophosphate. The lubricant composition of claim 1 wherein the metal dialkyldithiophosphate is zinc dialkyldithiophosphate wherein at least about 50% of the alkyl groups are secondary alkyl groups. The lubricant composition of claim 1 further comprising a dispersant. The lubricant composition of claim 10 wherein the dispersant is succinimide. The lubricant composition of claim 1 further comprising at least one calcium overbased detergent. 13. The lubricant composition of claim 12 wherein the calcium overbased detergent is selected from the group consisting of calcium sulfonates, calcium phenates, calcium salicylates, calcium salixates, and mixtures thereof. The lubricant composition of claim 1 further comprising at least one antioxidant. 15. The lubricant composition of claim 14 wherein the antioxidant is selected from the group consisting of hindered phenols, aryl amines, and mixtures thereof. The lubricant composition of claim 1 further comprising other additional friction modifiers in addition to (b). 17. The lubricant composition of claim 16 wherein the further friction modifier is selected from the group consisting of glycerol monooleate, oleyl amide, diethanol fatty acid amines and mixtures thereof. The lubricant composition of claim 1 further comprising an antifoaming agent. Supplying an oil of lubricating viscosity and a condensation product of a substance represented by the following formula (I) with an alcohol having 6 to 12 carbon atoms to the internal combustion engine, wherein the lubricant composition has a sulfur content of about 1.0 or less, Method for lubricating internal combustion engines with phosphorus content up to about 0.08% by weight and sulfur content up to about 0.4% by weight: Formula I

[In this product, each R is independently H or a hydrocarbyl group, or R groups together form a ring, and when R is H, the hydroxy group obtained is optionally added by acylation or reaction with a boron compound. Is functionalized.] (a) blending an oil of lubricity viscosity and a condensation product of an alcohol having from 6 to 12 carbon atoms with a substance represented by formula (I); A method for preparing a lubricant composition, comprising the steps of obtaining a lubricant composition having a sulfur content of about 1.0 or less, a phosphorus content of about 0.08% by weight or less, and a sulfur content of about 0.4% by weight or less: Formula I

[Wherein R is each independently H or a hydrocarbyl group, or R groups together form a ring, and when R is H, the hydroxy group obtained is further functionalized by an acylation or reaction with a boron compound .]