JP2008280515A - Additive and lubricant formulation for improving phosphorus retention property - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method and a composition to lubricate a surface by a lubricating oil having high phosphorus retention. <P>SOLUTION: A lubrication surface includes a lubricant composition including a base oil of a lubrication viscosity, a certain quantity of a phosphorus including compound and a certain quantity of a titanium compound which is soluble in at least one hydrocarbon and is more effective for increasing the phosphorus retention of the lubricant composition than for increasing the phosphorus retention of a lubricant composition which lacks a titanium compound to be soluble in a hydrocarbon. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The examples described herein are effective in reducing the deactivation of exhaust gas catalysts, and in particular the use of such metal additives in certain oil-soluble metal additives and lubricating oil formulations, Related to soluble titanium additives used to improve the phosphorus retention of lubricant formulations.

  For over 50 years, car engine oils have been formulated with zinc dialkyldithiophosphate (ZDDP), resulting in low levels of wear, oxidation, and corrosion. This additive is everywhere and is found in almost all modern engine oils. ZDDP is multifunctional in the areas of wear resistance, antioxidant resistance, and corrosion resistance, and is unmistakably the most cost-effective additive commonly used by engine oil manufacturers and marketers one of.

  However, there is a concern that phosphorus from engine oil volatilizes and passes through the combustion chamber, which can cause phosphorus element to accumulate in the catalyst system and cause loss of catalyst efficiency. ZDDP is a source of phosphorus that can cause significant problems for exhaust gas catalytic converters and oxygen sensors when forming an impervious glaze that causes phosphorus from the burned oil to cover the precious metal catalyst portion. It is known. As a result, the amount of phosphorus-containing compounds used in engine oils is controlled and promoted to extend the life of converters and oxygen sensors, and to reduce the manufacturer's initial cost by lowering the precious metal content of the converter. There is pressure from automakers that must be reduced.

  Although reducing the phosphorus content of the lubricating oil may improve the life or efficiency of the catalytic converter, additives that do not contain phosphorus advantageously benefit from the phosphorus additive for friction control and wear protection It cannot be obtained equally. Accordingly, there is a need for contradictory additives and methods that allow for the protection of catalysis without significantly reducing the total phosphorus content of the lubricating oil composition.

  In one embodiment of the present specification, the lubricant is more than an increase in the phosphorus retention of a lubricant composition lacking a lubricating viscosity base oil, an amount of phosphorus-containing compound, and a hydrocarbon-soluble titanium compound. Lubricating surfaces containing a lubricant composition comprising an effective amount of at least one hydrocarbon soluble titanium compound to increase the phosphorus retention of the composition are presented.

  In another embodiment, a vehicle is provided that includes a moving part and includes a lubricant that lubricates the moving part. This lubricant has a higher phosphorus retention in the lubricant composition than the lubricant composition lacking the oil of lubricating viscosity, at least one phosphorus-containing compound, and a hydrocarbon-soluble titanium compound. An effective amount of at least one hydrocarbon soluble titanium compound is included to increase retention.

  In another embodiment, the lubricant composition has more than an increase in phosphorus retention of a lubricant composition lacking a lubricating viscosity base oil component, at least one phosphorus-containing compound, and a hydrocarbon-soluble titanium compound. A fully formulated lubricant composition comprising an amount of a hydrocarbon soluble titanium-containing agent effective to increase phosphorus retention is provided, wherein Such titanium-containing agents are substantially devoid of sulfur and phosphorus atoms.

  Further embodiments of the present disclosure provide a method for increasing phosphorus retention in an engine lubricant composition during engine operation, wherein the phosphorus retention is sufficient to reduce catalyst poisoning. It is. In this method, engine parts are used to increase the lubricant retention above a lubricant composition lacking a lubricating viscosity base oil, at least one phosphorus-containing compound, and a hydrocarbon-soluble titanium compound. Contacting a lubricant composition containing an effective amount of a hydrocarbon soluble titanium compound to increase the phosphorus retention of the composition is included.

  As briefly described above, the embodiments of the present disclosure are soluble in hydrocarbons that significantly improve phosphorus retention in the lubricating oil, thereby reducing the catalytic poisoning effect of phosphorus on the catalytic converter. A titanium additive is provided. This additive is mixed with an oily fluid applied to the surface between the movable parts. In another aspect, the additive is provided in a fully formulated lubricant composition. The additive is specifically aimed at meeting the currently proposed GF-5 standard for passenger car motor oils and PC-10 standard for heavy duty diesel engine oils, and also future passenger car and diesel engine oil specifications. This additive is particularly useful to allow vehicles to meet the more stringent Tier-II, BIN2 120,000 mile catalytic efficiency standards.

  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.

  The major component of the additives and concentrates provided for the lubricant compositions described in this disclosure are titanium compounds that are soluble in hydrocarbons. The term “hydrocarbon soluble” means that the compound is substantially suspended or dissolved in the hydrocarbon material by reaction or complexation of the reactive metal 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 non-hydrocarbon groups such as halo (especially chloro and fluoro), hydroxy, which do not change substituents that are predominantly hydrocarbons in the context of the present invention. Substituents including alkoxy, mercapto, alkylmercapto, nitro, nitroso, and sulfoxy);
(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.

式中ｎは２、３、および４の中から選択される整数、またＲは炭素数が約５から約２４のヒドロカルビル基である。またこの反応生成物は、次の化学式によって表されることもある：

式中Ｒ^１、Ｒ^２、Ｒ^３、およびＲ^４はそれぞれ、同一あるいは異なったものであり、炭素数が約５から約２５のヒドロカルビル基の中から選択される。上述の化学式の化合物は、実質的にリンおよびイオウを欠いている。 Hydrocarbon soluble titanium compounds suitable for use in the present invention, such as phosphorus retention agents, are provided by reaction products of titanium alkoxides with about C ₆ to about C ₂₅ carboxylic acids. This reaction product may be represented by the following chemical formula:

In the formula, n is an integer selected from 2, 3, and 4, and R is a hydrocarbyl group having about 5 to about 24 carbon atoms. The reaction product may also be represented by the following chemical formula:

Wherein R ¹ , R ² , R ³ , and R ⁴ are the same or different and are selected from hydrocarbyl groups having from about 5 to about 25 carbon atoms. The compounds of the above chemical formula are substantially devoid of phosphorus and sulfur.

  In some embodiments, the hydrocarbon soluble titanium compound is substantially or essentially devoid of sulfur and phosphorus atoms, and the lubricant or formulated lubricant package includes the hydrocarbon soluble titanium compound. Contains about 0.7% or less sulfur and about 0.12% or less phosphorus.

  In another example, the hydrocarbon soluble titanium compound may be substantially free of active sulfur. “Active” sulfur refers to sulfur that is not fully oxidized. Active sulfur is further oxidized, making it more acidic in oil during use.

  In yet another embodiment, the hydrocarbon soluble titanium compound is substantially free of any sulfur. In a further embodiment, the hydrocarbon soluble titanium compound is substantially free of any phosphorus.

  In yet a further embodiment, the hydrocarbon soluble titanium compound is substantially free of all sulfur and phosphorus. For example, a base oil in which a titanium compound is dissolved may have a relatively small amount, such as less than about 0.5% by weight in one embodiment and less than about 0.03% by weight in another embodiment. In yet another embodiment, the amount of sulfur and / or phosphorus is such that the finished oil in the base oil is the amount of sulfur and / or phosphorus in the motor oil. , Limited to an amount that allows the appropriate specification to be implemented for a given period of time.

  Examples of titanium / carboxylic acid products are essentially caproic acid, caprylic acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, oleic acid, erucic acid, linoleic acid, linolenic acid, cyclohexanecarboxylic acid. Examples include, but are not limited to, reaction products of an acid selected from the group consisting of acid, phenylacetic acid, benzoic acid, neodecanoic acid and the like and titanium. Methods for producing such titanium / carboxylic acid products are described, for example, in US Pat. No. 5,260,466, the description of which is incorporated herein by reference.

The hydrocarbon soluble titanium compounds of the examples described herein are effectively incorporated into the lubricant composition. Therefore, this hydrocarbon soluble titanium compound can be added directly to the lubricating oil composition. However, in one embodiment, the hydrocarbon-soluble titanium compound is a mineral oil, synthetic oil (eg, an ester of a dicarboxylic acid), naphtha, alkylated (eg, a C ₁₀ -C ₁₃ alkyl) benzene, toluene, or xylene. Diluted with a substantially inert, normally liquid organic diluent, to form a titanium additive concentrate. Titanium based additive concentrates typically contain from about 0% to about 99% by weight diluent oil.

  In the preparation of lubricating oil formulations, a common method is to use a titanium additive in the form of a 1% to 99% by weight concentrate active ingredient in a hydrocarbon such as a mineral lubricating oil or other suitable solvent. Concentrate is added. Typically these concentrates are lubricated with a DI additive package and a viscosity index (VI) improver containing 0.01 to 50 parts by weight of lubricating oil per part by weight of dispersant / inhibitor (DI) package. Added to the agent to form a finished lubricant, such as a crankcase motor oil. Suitable DI packages are described, for example, in US Pat. Nos. 5,204,012 and 6,034,040. The types of additives included in this DI additive package include cleaning agents, dispersants, antiwear agents, friction modifiers, seal expansion agents, antioxidants, antifoaming agents, lubricants, rust inhibitors, There are corrosion inhibitors, demulsifiers, viscosity index improvers and the like. Some of these ingredients are well known to those skilled in the art and are desirably used in the usual amounts with the additives and compositions described herein.

  In another example, the titanium additive concentrate may be top treated to a fully formulated motor oil or finished lubricant. The purpose of the titanium additive concentrate and DI package is, of course, to make the processing of various materials easier and easier to handle, and to facilitate dissolution or dispersion in the final blend. Typical DI packages include dispersants, antioxidants, cleaning agents, antiwear agents, antifoaming agents, pour point depressants, and optionally VI improvers, and seal expansion agents.

  Examples described herein provide lubricating oils having a relatively low content of hydrocarbon-soluble titanium compounds that provide the finished lubricant composition with about 1 ppm to about 1500 ppm titanium as elemental titanium, and A lubricant formulation is provided. In one embodiment, the titanium compound is present in the lubricating oil composition in an amount sufficient to provide about 50 ppm to about 1000 ppm titanium, and in further embodiments about 50 ppm to about 500 ppm titanium.

  Lubricant compositions made with the above-described hydrocarbon soluble titanium additives are used in a wide variety of applications. For compression ignition and spark ignition engines, it is desirable that the lubricant composition meet or exceed published GF-4 or API-CI-4 standards. Lubricant compositions according to the aforementioned GF-4 or API-CI-4 standards include base oils, DI additive packages, and / or VI improvers to provide a fully formulated lubricant. . The lubricant base oil of the lubricating oil according to the present disclosure is an oil of lubricating viscosity selected from among natural lubricating oils, synthetic lubricating oils, and mixtures thereof. Such base oils include those conventionally used as crankcase lubricants for spark added and compression ignition internal combustion engines, such as automobile and truck engines, marine and train diesel engines, and the like. .

Another component of the phosphorus-containing compound lubricant composition is a phosphorus-containing compound such as ZDDP. Suitable ZDDPs are made from specific amounts of primary and secondary alcohols. For example, the alcohols are combined in a primary alcohol to secondary alcohol ratio of about 100: 0 to about 0: 100. In yet a further example, the alcohols are combined at a primary alcohol to secondary alcohol ratio of about 60:40. Examples of suitable ZDDPs include reaction products obtained by combining the following (1) to (4): (1) about 50 mol% to about 100 mol%, about C ₁ to about C ₁₈ primary alcohols; (2) up to about 50 mol% of about C ₃ to about C ₁₈ secondary alcohols (3) phosphorus-containing components; and (4) zinc-containing components. As a further example, the primary alcohol is from about C ₁ mixture of alcohol about C _18. As yet a further example, the primary alcohol is a mixture of C ₄ and C ₈ alcohols. The secondary alcohol can also be a mixture of alcohols. As an example, the secondary alcohol may include a C ₃ alcohol. In addition, the alcohol may contain any one of branched chain, cyclic, and straight chain. ZDDP includes a combination of about 60 mol% primary alcohol and about 40 mol% secondary alcohol. Alternatively, ZDDP contains 100 mol% secondary alcohol, or 100 mol% primary alcohol.

  The phosphorus-containing component of the phosphorus-containing compound includes any suitable phosphorus-containing component such as, but not limited to, phosphorus sulfide. Suitable phosphorus sulfides include diphosphorus pentasulfide or tetraphosphorus trisulfide.

  Zinc-containing components include any suitable zinc-containing component such as, but not limited to, zinc oxide, zinc hydroxide, zinc carbonate, zinc proprate, zinc chloride, zinc propionate, or zinc acetate. It is.

  The reaction product includes the resulting mixture, component, or mixture of components. The reaction product may or may not include unreacted reactants, chemically bonded components, products, or polar bonded components.

  The ZDDP or ash-containing phosphorus compound is present in an amount sufficient to provide from about 0.03% to about 0.15% phosphorus by weight in the lubricant composition.

  In addition, or alternatively, an ashless phosphorus compound may be included in the mixture of phosphorus-containing compounds. The ashless phosphorus compound is selected from phosphoric acid, phosphorous acid, or organic esters of their amine salts. For example, the ashless phosphorus-containing compound includes dihydrocarbyl phosphite, trihydrocarbyl phosphite, monohydrocarbyl phosphate, dihydrocarbyl phosphate, trihydrocarbyl phosphate, any sulfur analog thereof, and any amine salt thereof. One or more of these. As a further example, the ashless phosphorus-containing compound includes at least one amine salt of monohydrocarbyl phosphate and dihydrocarbyl phosphate, or a mixture thereof. For example, the phosphate of amyl acid can be a mixture of phosphate of monoamyl acid and phosphate of diamyl acid.

  The weight ratio of phosphorus obtained from the ash-containing phosphorus compound to phosphorus obtained from the ashless phosphorus compound in the lubricating oil composition is from about 3: 1 to about 1: 3. Another mixture of phosphorus compounds used was obtained from about 0.5 to about 2.0 parts by weight phosphorus obtained from ash-containing phosphorus compounds and about 1 part by weight ashless phosphorus compounds. Contains phosphorus. Yet another phosphorus compound mixture contains substantially the same parts by weight of phosphorus obtained from the ash-containing phosphorus compound and phosphorus obtained from the ashless phosphorus compound. Examples of mixtures of phosphorus obtained from ash-containing phosphorus compounds and phosphorus obtained from ashless phosphorus compounds are shown in the table below.

  The mixture of phosphorus-containing compounds in the lubricating oil formulation is present in the lubricating oil formulation in an amount sufficient to provide a total of about 300 ppm to about 1200 ppm by weight of phosphorus. In a further example, the mixture of phosphorus-containing compounds is present in the lubricating oil formulation in an amount sufficient to provide a total of about 500 ppm to about 800 ppm by weight of phosphorus.

  The mixture of phosphorus-containing compound and titanium compound described herein is used in combination with other additives. This additive is generally incorporated into the base oil in an amount that is capable of providing the desired effect. Representative effective amounts of phosphorus-containing and titanium compound mixtures and additives when used in a crankcase lubricant are shown in Table 1 below. All numerical values in the table represent the weight percentage of the active ingredient.

Dispersant component The dispersant contained in the DI package includes, but is not limited to, an oil-soluble polymer hydrocarbon backbone having functional groups that can bind to the dispersed particles. In general, dispersants include, but are not limited to, amines, alcohols, amides, or polar moieties of esters often attached to the polymer backbone through cross-linking groups. The dispersant is, for example, a Mannich dispersant described in US Pat. Nos. 3,697,574 and 3,736,357; an ashless succinic acid described in US Pat. Nos. 4,234,435 and 4,636,322. Acid imide dispersants; amine dispersants as described in US Pat. Nos. 3,219,666, 3,565,804, and 5,633,326; US Pat. Nos. 5,936,041, 5,643 859, and Koch dispersants described in 5,627,259, and polyalkylene succinimides described in US Pat. Nos. 5,851,965, 5,853,434, and 5,792,729 It is selected from among dispersants.

Antioxidant components Antioxidants or antioxidants reduce the tendency of the base stock to deteriorate during use, but such degradation produces oxidatives such as sludge and varnish deposits on metal surfaces. Can be demonstrated by an increase in the viscosity of the product and the finished lubricant. Such oxidation inhibitors include hindered phenols, sulfurized hindered phenols, alkaline earth metal salts of alkylphenolthioesters C ₅ having an alkyl side chain of C _12, alkyl phenol sulfide, either sulfurized alkylphenol or non sulfurized alkylphenol Metal salts, such as calcium nonylphenol sulfide, ashless oil-soluble phenates and sulfurized phenates, phosphorylated and sulfurized hydrocarbons or sulfurized hydrocarbons, phosphorus esters, metal thiocarbamates, and US Pat. No. 4,867,890 The oil-soluble copper compound described in 1 is included.

  Other antioxidants used in combination with hydrocarbon soluble titanium compounds include sterically complex phenols and diallylamines, alkylated phenothiazines, sulfurized compounds, and ashless dialkyldithiocarbamates. Non-limiting examples of sterically complicated phenols include 2,6-di-t-butylphenol, 2,6 di-t-butylmethylphenol, 4-ethyl-2,6-di-t-butylphenol, 4-propyl-2,6-di-t-butylphenol, 4-butyl-2,6-di-t-butylphenol, 4-pentyl-2,6-di-t-butylphenol, 4-hexyl-2,6- Di-t-butylphenol, 4-heptyl-2,6-di-t-butylphenol, 4- (2-ethylhexyl) -2,6-di-t-butylphenol, 4-octyl-2,6-di-t- Butylphenol, 4-nonyl-2,6-di-t-butylphenol, 4-decyl-2,6-di-t-butylphenol, 4-undecyl-2,6-di-t-butylphenol, 4-do Decyl-2,6-di-t-butylphenol, 4,4-methylenebis (6-t-butyl-o-cresol), 4,4-methylenebis (2-t-amyl-o-cresol), 2, 2-methylenebis (4-methyl-6 t-butylphenol, 4,4-methylene-bis (2,6-di-t-butylphenol) and mixtures thereof as described in US Patent Publication No. 2004/0266630, and the like, Non-limiting examples include, but are not limited to, methylene bridged sterically complex phenols.

式中、Ｒ’およびＲ’’はそれぞれに、置換されたまたは置換されていない、炭素数が６から３０のアリル基を表す。このアリル基に対する例証的な置換基には、炭素数が１から３０のアルキル、ヒドロキシル基、ハロゲンラジカル、カルボン酸基あるいはエステル基、またはニトロ基のような、脂肪族炭化水素基が含まれる。 Diallylamine antioxidants include, but are not limited to, diallylamine represented by the following chemical formula:

In the formula, R ′ and R ″ each represent a substituted or unsubstituted allyl group having 6 to 30 carbon atoms. Illustrative substituents for this allyl group include aliphatic hydrocarbon groups such as alkyls having 1 to 30 carbon atoms, hydroxyl groups, halogen radicals, carboxylic acid groups or ester groups, or nitro groups.

  The allyl group is preferably substituted or unsubstituted phenyl or naphthyl, especially when one or both allyl groups are at least one 4 to 30, preferably 4 to 18, most preferably 4 to 9 carbons. Is substituted with an alkyl group having Desirably, one or both allyl groups are substituted with, for example, monoalkylated diphenylamine, dialkylated diphenylamine, or a mixture of monoalkylated diphenylamine and dialkylated diphenylamine.

  Diallylamine has a structure containing one or more nitrogen atoms in the molecule. Therefore, this diallylamine contains at least two nitrogen atoms. At this time, for example, in the case of various diamines having secondary nitrogen atoms, of which two allyls are bonded to one nitrogen atom. Thus, two allyl groups are bonded to at least one nitrogen atom.

  Examples of diallylamine used include diphenylamine; various alkylated diphenylamines; 3-hydroxydiphenylamine; N-phenyl-1,2-phenylenediamine; N-phenyl-1,4-phenylenediamine; monobutyldiphenylamine; Dioctyl diphenylamine; dioctyl diphenylamine; monononyl diphenylamine; dinonyl diphenylamine; monotetradecyl diphenylamine; ditetradecyl diphenylamine; phenyl-alpha-naphthylamine; monooctylphenyl-alpha-naphthylamine; phenyl-beta-naphthylamine; monoheptyldiphenylamine; -Diphenylamine; p-oriented styrenated diphenylamine; mixed butyloctyl Diphenylamine; and mixed octyl styryl diphenylamine, but it is not limited to.

式中、Ｒ_１はＣ_１からＣ_２４の線状あるいは分岐アルキル、アリル、ヘテロアルキルあるいはアルキルアリル基であり、Ｒ_２は水素、またはＣ_１からＣ_２４の線状あるいは分岐アルキル、ヘテロアルキル、あるいはアルキルアリル基である。アルキル化フェノチアジンは、モノテトラデシルフェノチアジン、ジテトラデシルフェノチアジン、モノデシルフェノチアジン、ジデシルフェノチアジン、モノノニルフェノチアジン、ジノニルフェノチアジン、モノオクチル−フェノチアジン、ジオクチルフェノチアジン、モノブチルフェノチアジン、ジブチルフェノチアジン、モノスチリルフェノチアジン、ジスチリルフェノチアジン、ブチルオクチルフェノチアジン、およびスチリルオクチルフェノチアジンからなる群の中から選択される。 Another class of amine antioxidants includes phenothiazines or alkylated phenothiazines represented by the following chemical formula:

Wherein R ₁ is a C ₁ to C ₂₄ linear or branched alkyl, allyl, heteroalkyl or alkylallyl group, R ₂ is hydrogen, or a C ₁ to C ₂₄ linear or branched alkyl, heteroalkyl, Or it is an alkylallyl group. Alkylated phenothiazines are monotetradecylphenothiazine, ditetradecylphenothiazine, monodecylphenothiazine, didecylphenothiazine, monononylphenothiazine, dinonylphenothiazine, monooctyl-phenothiazine, dioctylphenothiazine, monobutylphenothiazine, dibutylphenothiazine, monostyrylphenothiazine, It is selected from the group consisting of distyrylphenothiazine, butyloctylphenothiazine, and styryloctylphenothiazine.

  Sulfur-containing antioxidants include, but are not limited to, sulfurized olefins characterized by the type of olefin used to produce it and the final sulfur content of the antioxidant. High molecular weight olefins, that is, olefins having an average molecular weight of 168 g / mole to 351 g / mole are desirable. Examples of olefins used include alpha olefins, isomerized alpha olefins, branched olefins, cyclic olefins, and combinations thereof.

Alpha olefins include, but are not limited to, any C ₄ to C ₂₅ alpha olefin. Alpha olefins are isomerized prior to or during the sulfurization reaction. Alpha olefin structures and / or conformers may also be used that contain internal double bonds and / or branched chains. For example, isobutylene is the branched olefin counterpart of alpha olefin 1-butene.

  Sources of sulfur used in olefin sulfurization reactions include elemental sulfur, sulfur monochloride, sulfur dichloride, sodium sulfide, sodium polysulfide, and these added together or at different stages of the sulfurization process A mixture is included.

  Unsaturated oils are unsaturated and are therefore sulfurized and may be used as antioxidants. Examples of oils or fats used include corn oil, canola oil, cottonseed oil, grape seed oil, olive oil, coconut oil, peanut oil, coconut oil, rapeseed oil, safflower oil, safflower seed oil, sesame oil, soybean oil, sunflower Oil, tallow, and combinations thereof.

  The amount of sulfurized olefin or sulfurized fatty oil supplied to the finished lubricant depends on the sulfur content of the sulfurized olefin or fatty oil and the desired amount of sulfur supplied to the finished lubricant. For example, a sulfurized fatty oil or olefin containing 20% by weight sulfur, when supplied to a finished lubricant at a treat level of 1.0% by weight, provides 2000 ppm sulfur to the finished lubricant. A sulfurized fatty oil or olefin containing 10% by weight sulfur provides 1000 ppm sulfur to the finished lubricant when fed to the finished lubricant at a treat level of 1.0% by weight. It is desirable to add sulfurized olefins or sulfurized fatty oils to provide between 200 ppm and 2000 ppm sulfur to the finished lubricant. Such amine-based phenothiazines and sulfur-containing antioxidants are described, for example, in US Pat. No. 6,599,865.

  Ashless dialkyldithiocarbamates used as antioxidants include compounds that are soluble or dispersible in the additive package. The ashless dialkyldithiocarbamate is desirably low in volatility, desirably having a molecular weight of 250 daltons or more, and most desirably having a molecular weight of 400 daltons or more. Examples of ashless dithiocarbamates used include methylene bis (dialkyldithiocarbamate), ethylene bis (dialkyldithiocarbamate), isobutyl disulfide-2,2′-bis (dialkyldithiocarbamate), hydroxyalkyl substituted dialkyldithiocarbamates, Examples include, but are not limited to, dithiocarbamates produced from unsaturated compounds, dithiocarbamates produced from norbornylene, and dithiocarbamates produced from epoxides. At this time, the alkyl group of the dialkyldithiocarbamate preferably has 1 to 16 carbon atoms. Examples of dialkyldithiocarbamates used are US Pat. Nos. 5,693,598, 4,876,375, 4,927,552, 4,957,643, 4,885,365, 5, 789,357, 5,686,397, 5,902,776, 2,786,866, 2,710,872, 2,384,577, 2,897,152, 3,407 222, 3,867,359, and 4,758,362.

  Examples of suitable ashless dithiocarbamates include methylenebis- (dibutyldithiocarbamate), ethylenebis (dibutyldithiocarbamate), isobutyldisulfide-2,2'-bis (dibutyldithiocarbamate), dibutyl succinate N, N-dibutyl (Dithiocarbamyl), 2-hydroxypropyldibutyldithiocarbamate, butyl acetate (dibutyldithiocarbamyl), and S-carbomethoxy-ethyl-N, N-dibutyldithiocarbamate. The most preferred ashless dithiocarbamate is methylenebis (dibutyldithiocarbamate).

  A compound containing organic molybdenum used as a friction modifier may exhibit an antioxidant effect. US Pat. No. 6,797,677 describes a combination of an organomolybdenum compound, an alkylphenothidine and an alkyldiphenylamine for use in the finished lubricant composition. Suitable examples of friction modifiers containing molybdenum are described in the friction modifier section below.

Friction modifier component An organic molybdenum compound containing no sulfur and phosphorus used as a friction modifier is obtained by reacting a sulfur source containing no sulfur and phosphorus with an organic compound containing an amino group and / or an alcohol group. Generated by. Examples of molybdenum sources that do not contain sulfur and phosphorus include molybdenum trioxide, ammonium molybdate, sodium molybdate, and potassium molybdate. The amino group can be a monoamine, diamine, or polyamine. The alcohol group may be a monosubstituted alcohol, diol, bisalcohol, or polyalcohol. In one example, the reaction of a diamine with a fatty oil produces a product containing both amino and alcohol groups that can react with a sulfur and phosphorus free molybdenum source.

  Examples of organomolybdenum compounds that do not contain sulfur and phosphorus include U.S. Pat. Nos. 4,259,195, 4,261,843, 4,164,473, 4,266,945, 4,889,647. Nos. 5,137,647, 4,692,256, 5,412,130, 6,509,303, and 6,528,463.

Molybdenum compounds produced by reacting fatty oils, diethanolamine, and molybdenum sources as described in US Pat. No. 4,889,647 are often represented by the following chemical formula: The exact chemical composition of these materials is not fully known and may actually be a mixture of multiple components of several organomolybdenum compounds, where R is a fatty alkyl chain .

Sulfur-containing organomolybdenum compounds are sometimes used, but these are produced in various ways. One method involves reacting a sulfur and phosphorus-free molybdenum source with an amino group and one or more sulfur sources. Sulfur sources include, but are not limited to, for example, carbon disulfide, hydrogen sulfide, sodium sulfide, and elemental sulfur. On the other hand, sulfur-containing molybdenum compounds are produced by reacting a sulfur-containing molybdenum source with an amino group or thiuram group and optionally a second sulfur source. Examples of sulfur and phosphorus free molybdenum sources include molybdenum trioxide, ammonium molybdate, sodium molybdate, potassium molybdate, and molybdenum halides. The amino group is a monoamine, diamine, or polyamine. As an example, the reaction of molybdenum trioxide with secondary amines and carbon disulfide produces molybdenum dithiocarbamate. On the other hand, the reaction of (NH ₄ ) ₂ Mo ₃ S ₁₃ ^* n (H ₂ O) in which n changes between 0 and 2 and tetraalkylchiurum disulfide produces sulfur-containing trinuclear molybdenum dithiocarbamate. Is done.

  Examples of organic molybdenum compounds containing sulfur include U.S. Pat. Nos. 3,509,051, 3,356,702, 4,098,705, 4,178,258, 4,263,152, 4,265,773, 4,272,387, 4,285,822, 4,369,119, 4,395,343, 4,283,295, 4,362,633, 4, 402,840, 4,466,901, 4,765,918, 4,966,719, 4,978,464, 4,990,271, 4,995,996, 6, 232,276, 6,103,674, and 6,117,826 are included.

式中、各ＲはそれぞれにＨおよびＣ（Ｏ）Ｒ’からなる群の中から選択され、Ｒ’は炭素数が３から２３の、飽和あるいは不飽和アルキル基である。使用されるグリセリドの例としては、モノラウリン酸グリセロール、モノミリスチン酸グリセロール、モノパルミチン酸グリセロール、モノステアリン酸グリセロール、およびココナッツ酸、獣脂酸、オレイン酸、リノール酸、およびリノレン酸から得られたモノ−グリセリドなどが挙げられる。一般的な市販のモノグリセリドには、相当量の対応するジグリセリドおよびトリグリセリドが含まれている。これらの物質は、モリブデン化合物の生成に害をおよぼすことはなく、事実上より活性化させるものである。モノグリセリド対ジグリセリドのいかなる比率を用いてもかまわないが、３０％から７０％の有効部分が遊離ヒドロキシル基を含有することが望ましい（すなわち上述の化学式で表される、３０％から７０％のグリセリドの総合Ｒ基は、水素である）。好適なグリセリドは、モノオレイン酸グリセロールであり、通常は、オレイン酸から得られるモノグリセリド、ジグリセリド、およびトリグリセリドと、グリセロールとの混合物である。 Glycerides may be used alone or in combination with other friction modifiers. Suitable glycerides include glycerides of the following formula:

Wherein each R is individually selected from the group consisting of H and C (O) R ′, where R ′ is a saturated or unsaturated alkyl group having 3 to 23 carbon atoms. Examples of glycerides used include glycerol monolaurate, glycerol monomyristate, glycerol monopalmitate, glycerol monostearate, and mono-derived from coconut acid, tallow acid, oleic acid, linoleic acid, and linolenic acid. Examples include glycerides. Typical commercial monoglycerides contain a substantial amount of the corresponding diglycerides and triglycerides. These substances do not harm the production of molybdenum compounds and are more active. Any ratio of monoglyceride to diglyceride may be used, but it is desirable that 30% to 70% of the active moiety contains free hydroxyl groups (ie 30% to 70% glyceride represented by the above formula). The overall R group is hydrogen). A suitable glyceride is glycerol monooleate, usually a mixture of monoglycerides, diglycerides and triglycerides obtained from oleic acid and glycerol.

Other Additives Rust inhibitors selected from the group consisting of nonionic polyoxyalkylene polyols and esters thereof, polyoxyalkylene phenols, and anionic alkyl sulfonates may be used.

  A small amount of a demulsifying component is used. Suitable demulsifying components are described in EP 330,522. Such an emulsification-breaking component can be obtained by reacting alkylene oxide with an addition compound obtained by reacting a bisepoxide and a polyhydric alcohol. This demulsifier must be used at a level where the active ingredient does not exceed 0.1% by weight. The treat rate of the active ingredient is conveniently from 0.001% to 0.05% by weight.

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.

  Foam control is accomplished by a number of compounds including, for example, silicone oils or polysiloxane antifoams such as polydimethylsiloxane.

  Seal expanders such as those described in US Pat. Nos. 3,794,081 and 4,029,587 may also be used.

  Viscosity modifiers (VM) 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, styrene / butadiene, and isoprene / butadiene copolymers, and partially hydrogenated butadiene / isoprene / isoprene / divinylbenzene homopolymers.

  Functionalized olefin copolymers used include ethylene and propylene interpolymers grafted with an active monomer such as maleic anhydride and then derivatized with an alcohol or amine. Other such copolymers include ethylene and propylene copolymers grafted with nitrogen compounds.

  Each of the above-described additives is used in a functionally effective amount in use and provides the desired properties to the lubricant. Thus, for example, when the additive is a corrosion inhibitor, a functionally effective amount of the corrosion inhibitor is an amount sufficient to provide the desired corrosion protection to the lubricant. Typically, when these additives are used, the respective concentrations are about 20% by weight or more based on the weight of the lubricating oil composition, and in one embodiment about 0.001% to about 20% by weight, In one embodiment, it is about 0.01% to about 10% by weight.

A hydrocarbon soluble titanium additive may be 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 a liquid organic diluent. These concentrates usually contain about 1% to about 100% by weight, and in one embodiment about 10% to about 90% by weight of the titanium compound.

Base oils 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 alkyl esters of dicarboxylic acids, polyglycols and alcohols, and polybutenes, alkylbenzenes, organic esters of phosphoric acid, and polyalphaolefins including polysilicon oils, as well as alkylene oxide polymers, interpolymers, copolymers, In this case, the terminal hydroxyl group is modified by esterification or etherification.

  Natural base oils include animal and vegetable oils (for example, castor oil and lard oil), liquid petroleum, and hydrorefined, solvent-treated or acid-treated, paraffinic, naphthenic, and paraffin-naphthene mixed mineral lubricants. Such as oil. Oils of lubricating viscosity obtained from coal or shale are also useful base oils. The viscosity of the base oil at 100 ° C. is generally from about 2.5 cSt to about 15 cSt, and desirably from about 2.5 cSt to about 11 cSt.

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

Example 1
Titanium neodecanoate Neodecanoic acid (about 600 grams) was placed in a reaction vessel equipped with a condenser, a Dean-Stark trap, a thermometer, a thermocouple, and a gas inlet. A nitrogen bubble was placed in the acid. While stirring vigorously, titanium isopropoxide (about 245 grams) was slowly added to the reaction vessel. The reaction was heated to about 140 ° C. and stirred for 1 hour. The overhead and condensate obtained from the reaction were collected in a trap. The reaction vessel was depressurized and the reactants were stirred for an additional 2 hours until the reaction was complete. Analysis of the product showed that the product had a kinematic viscosity at 100 ° C. of about 14.3 cSt and a titanium content of about 6.4 weight percent.

  Comparative fluid phosphorus retention (PR) values and fluid phosphorus retention (PR) values based on exemplary embodiments of the present disclosure were measured using the Afton Catalyst Test (hereinafter “ACT”). ACT is a catalyst aging test for combustion engines developed by Afton Chemical Company to evaluate the impact related to lubricant volatility on catalyst deactivation. The ACT uses a 2001MY Ford 4.6 L SOHC V8 engine connected to an eddy current dynamometer and operated for 240 hours. Test operating conditions are selected to correspond to steady state highway travel of about 50,000 km, with the exception of exhaust gas, engine oil and engine coolant operating temperatures. In order to minimize the heat-related effects on catalyst deactivation, engine exhaust temperature is kept below 750 ° C. where such effects are known to occur. In order to maximize the effect of oil and oil chemical volatility on catalyst deactivation, engine oil and coolant temperatures are controlled to the highest practical levels, ie, 145 ° C. and 122 ° C. in sequence. Oil consumption is accurately determined by measuring the difference in mass removed from the amount added into the engine. Table 2 shows the operating conditions of ACT.

  Take an oil sample for analysis at each oil change during the test. Element concentration and viscosity characteristics are measured by using an inductively coupled plasma mass spectrometer (ICP-MS) and a kinematic viscometer. Oil consumption and elemental concentration data represent the amount of oil consumed by volatilization versus the amount consumed by a large oil change. This data also allows calculation of the amount of phosphorus throughput and phosphorus retention.

As the oil ages in the engine, a portion of the base stock evaporates or distills, leaving the additive components behind. The rate of increase in calcium concentration is directly proportional to the rate of decrease in base stock due to volatilization. Phosphorus also concentrates in the oil used, but the degree is low because certain types of phosphorus obtained from ZDDP tend to volatilize at high temperatures. Phosphorus retention (PR) in the used oil is expressed by the following equation: rate of change in calcium concentration (new oil / used oil) and change in phosphorus concentration (used oil / new oil) ) Multiplied by:

PR = (Ca in fresh oil / used oil Ca) X
(Oil P used / P in new oil) X 100

Since calcium is not volatile in the lubricant composition, calcium is used to calculate phosphorus retention to measure the increase in phosphorus concentration due to base oil volatilization.

  The performance of the catalyst is measured before and after the 240 hour aging process by running a conversion efficiency (CE) test. In the CE evaluation, the engine is operated under steady-state conditions while controlling the exhaust gas temperature to maintain a constant catalyst suction temperature. The exhaust suction temperature was measured from 200 ° C. to 440 ° C. while measuring the release of hydrocarbons (HC), carbon monoxide (CO), and nitrogen oxides (NOx) through probes inserted before and after the catalyst. Raised every ℃. A curve is drawn from this data to indicate the “T50” value or temperature when 50% conversion occurred for each exhaust type. By comparing the T50 values before and after aging, the relative amount of catalyst degradation is determined and compared to aging oil. The 240 hour oil aging process generally results in an increase in all T50 values except when the oil contains additives that do not contain phosphorus.

Example 2
A 100,000 mile New York taxi field test was performed on a conventional lubricant composition and a lubricant composition containing an amount of titanium neodecanoate sufficient to provide 500 ppm of titanium metal to the lubricant composition. It was. The results and statistical comparison are shown in Table 3. All cars started testing with a new engine and changed oil at intervals of 5000 miles or 10,000 miles. Four cars were operated with a lubricant composition containing 500-ppm titanium and three cars with the same lubricant composition without titanium.

  Consistent with the Sequence IIIG test, the phosphorus retention of the vehicle driven with the lubricant containing the titanium-containing compound was 92.2% PR, the baseline indicated by the vehicle driven with the lubricant lacking titanium. It was higher than 87.4PR.

Example 4
An experimental design (DOE) was performed on a fully formulated oil containing various concentrations of titanium obtained from titanium neodecanoate (TND). This composition and ingredients are shown in Table 4. Another variable included in this DOE was phosphorus level. A total of 15 separate blends were evaluated by the sequence IIIG engine test, which was conducted at an oil temperature of 150 ° C for 100 hours. As part of the IIIG test, oil samples were taken every 20 hours and analyzed by inductively coupled plasma mass spectrometry (ICP-MS) to determine changes in element concentration due to aging. Using this data, the phosphorus retention (PR,%) after 20 hours of aging was calculated according to the above formula.

  Statistical linear regression analysis of DOE data concluded that increasing titanium concentration has a significantly positive effect on improving PR%. The oil containing 100 ppm titanium obtained from TND showed an average 4.25 PR% (p-value 0.008) improvement.

  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, this example is not intended to be limited to the specific illustrations described above. Rather, the described 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. More than increasing the phosphorus retention of a lubricant composition lacking a lubricating viscosity base oil, at least one phosphorus-containing compound, and a hydrocarbon soluble titanium compound, to increase the phosphorus retention of the lubricant composition A lubricating surface comprising a lubricant composition containing an effective amount of at least one hydrocarbon soluble titanium compound.

2. 2. The lubricated surface according to 1 above, wherein the lubricated surface includes an engine drive train.

3. 2. The lubricating surface according to 1 above, wherein the lubricating surface contains an internal surface or component of an internal combustion engine.

4). 2. The lubricated surface according to 1 above, wherein the lubricated surface contains an inner surface or component of a compression ignition engine.

5. The lubricating surface of claim 1, wherein the amount of hydrocarbon soluble titanium compound is an amount that provides about 50 ppm to about 1000 ppm of titanium to the lubricant composition.

6). The lubricating surface of claim 1, wherein the amount of the hydrocarbon soluble titanium compound is an amount that provides about 100 ppm to about 500 ppm titanium to the lubricant composition.

7. The lubricating surface of claim 1, wherein the amount of hydrocarbon soluble titanium compound is an amount that provides about 50 ppm to about 300 ppm of titanium to the lubricant composition.

8). The lubricating surface according to 1 above, wherein the hydrocarbon-soluble titanium compound contains titanium neodecanoate.

9. An automobile including the lubricating surface according to 1 above.

10. 10. The vehicle of claim 9 wherein the amount of hydrocarbon soluble titanium compound is an amount that provides about 1 ppm to about 1000 ppm titanium to the lubricant.

11. A vehicle having a movable part and including a lubricant for lubricating the movable part, the lubricant lacking oil of lubricating viscosity, at least one phosphorus-containing compound, and a titanium compound soluble in hydrocarbons. More than the increase in phosphorus retention of the lubricant composition, the vehicle includes an amount of at least one hydrocarbon soluble titanium compound effective to increase the phosphorus retention of the lubricant composition.

12 The vehicle according to 11 above, wherein titanium neodecanoate is contained in a hydrocarbon-soluble titanium compound.

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

14 12. The vehicle of claim 11, wherein the amount of hydrocarbon soluble titanium compound is an amount that provides about 50 ppm to about 1000 ppm titanium to the lubricant composition.

15. 12. The vehicle of claim 11, wherein the amount of hydrocarbon soluble titanium compound is an amount that provides about 100 ppm to about 500 ppm titanium to the lubricant composition.

16. 12. The vehicle of claim 11, wherein the amount of the hydrocarbon soluble titanium compound is an amount that provides about 50 ppm to about 300 ppm titanium to the lubricant composition.

17. A fully formulated lubricant composition, wherein the lubricant retention of the lubricant composition lacks a lubricating viscosity base oil component, at least one phosphorus-containing compound, and a hydrocarbon-soluble titanium-containing agent. More than an increase, it includes an effective amount of a hydrocarbon-soluble titanium-containing agent to increase the phosphorus retention of the lubricant composition, wherein the titanium-containing agent is substantially devoid of sulfur and phosphorus atoms. A fully formulated lubricant composition.

18. 18. The lubricant composition of claim 17, wherein the lubricant composition comprises a low ash, low sulfur, and low phosphorus content lubricant composition suitable for a compression ignition engine.

19. 18. The lubricant composition according to 17 above, wherein titanium neodecanoate is contained in a hydrocarbon-soluble titanium-containing agent.

20. 18. The lubricant composition of claim 17, wherein the amount of hydrocarbon-soluble titanium-containing agent is an amount that provides about 50 ppm to about 1000 ppm titanium to the lubricant composition.

21. 18. The lubricant composition of claim 17, wherein the amount of hydrocarbon soluble titanium compound is an amount that provides about 100 ppm to about 500 ppm titanium to the lubricant composition.

22. 18. The lubricant composition of claim 17, wherein the amount of hydrocarbon soluble titanium compound is an amount that provides about 50 ppm to about 300 ppm titanium to the lubricant composition.

23. More than an increase in phosphorus retention of a lubricant composition that lacks a lubricating viscosity base oil, at least one phosphorus-containing compound, and a hydrocarbon-soluble titanium compound during engine operation. A lubricant composition comprising an amount of a hydrocarbon-soluble titanium compound effective to increase the phosphorus retention of the lubricant composition in contact with an engine part. A method for increasing phosphorus retention in a lubricant composition, wherein phosphorus retention is sufficient to reduce catalyst poisoning.

24. 24. The method of claim 23, wherein the engine comprises a heavy duty diesel engine.

25. 24. The method according to 23, wherein the titanium-soluble agent soluble in hydrocarbon contains titanium neodecanoate.

26. 24. The method of claim 23, wherein the amount of hydrocarbon-soluble titanium-containing agent is an amount that provides about 50 ppm to about 1000 ppm of titanium to the lubricant composition.

27. 24. The method of claim 23, wherein the amount of the titanium compound that is soluble in the hydrocarbon is an amount that provides from about 100 ppm to about 500 ppm titanium to the lubricant composition.

28. 24. The method of claim 23, wherein the amount of the titanium compound that is soluble in the hydrocarbon is an amount that provides about 50 ppm to about 300 ppm of titanium to the lubricant composition.

Claims (9)

  More than increasing the phosphorus retention of a lubricant composition lacking a lubricating viscosity base oil, at least one phosphorus-containing compound, and a hydrocarbon soluble titanium compound, to increase the phosphorus retention of the lubricant composition A lubricating surface comprising a lubricant composition containing an effective amount of at least one hydrocarbon soluble titanium compound.   The lubricated surface of claim 1, wherein the lubricated surface includes an engine drive train.   The lubricating surface of claim 1, wherein the amount of hydrocarbon soluble titanium compound is an amount that provides from about 50 ppm to about 1000 ppm titanium to the lubricant composition.   A vehicle having a movable part and including a lubricant for lubricating the movable part, the lubricant lacking lubricating oil, at least one phosphorus-containing compound, and a hydrocarbon-soluble titanium compound. More than the increase in phosphorus retention of the lubricant composition, the vehicle includes an amount of at least one hydrocarbon soluble titanium compound effective to increase the phosphorus retention of the lubricant composition.   The vehicle according to claim 4, wherein the movable part includes a heavy duty diesel engine.   The vehicle of claim 4, wherein the amount of the titanium compound that is soluble in the hydrocarbon is an amount that provides from about 50 ppm to about 300 ppm titanium to the lubricant composition.   A fully formulated lubricant composition, wherein the lubricant retention of the lubricant composition lacks a lubricating viscosity base oil component, at least one phosphorus-containing compound, and a hydrocarbon-soluble titanium-containing agent. More than an increase, it includes an effective amount of a hydrocarbon-soluble titanium-containing agent to increase the phosphorus retention of the lubricant composition, wherein the titanium-containing agent is substantially devoid of sulfur and phosphorus atoms. A fully formulated lubricant composition.   The lubricant composition of claim 7, wherein the lubricant composition comprises a low ash, low sulfur, and low phosphorus content lubricant composition suitable for a compression ignition engine.   More than an increase in phosphorus retention of a lubricant composition that lacks a lubricating viscosity base oil, at least one phosphorus-containing compound, and a hydrocarbon-soluble titanium compound during engine operation. A lubricant composition comprising an amount of a hydrocarbon-soluble titanium compound effective to increase the phosphorus retention of the lubricant composition in contact with an engine part. A method for increasing phosphorus retention in a lubricant composition, wherein phosphorus retention is sufficient to reduce catalyst poisoning.