CN103201364B - Lubricant oil composite - Google Patents

Abstract

The present invention generally relates to reduce the method for inlet valve deposits in direct injection spark-ignited engine, the method includes making electromotor work with lubricant oil composite, and described lubricant oil composite comprises: (a) major amount of lubrication viscosity oil；(b) selected from silicone oil, polysiloxanes, polyacrylate and at least one foam in hibitors of polymethacrylates；Wherein said foam in hibitors is not poly-(phenyl methyl) siloxanes；And the amount of foam in hibitors described in other wherein said lubricant oil composite be in the inlet valve deposits that realizes in described direct injection spark-ignited engine make the work of described electromotor with the described lubricant oil composite without any foam in hibitors compared with reduce at least 10% valid density.

Description

lubricating oil composition

field of invention

The present invention generally relates to methods for reducing intake valve deposits in direct injection spark ignition (DISI) engines. Also provided is a method of reducing intake valve deposits in a DISI engine by top treating an oil of lubricating viscosity with a lubricating oil additive concentrate.

Background of the invention

Many automotive engine manufacturers have recently introduced direct injection spark ignition (DISI) engines for gasoline. Such engines inject gasoline directly into the combustion chamber of the engine, rather than introducing gasoline indirectly through the intake manifold by means of, for example, carburetors or orifice fuel injectors. Because the gasoline is injected directly into the combustion chamber, it is possible to precisely control the amount of fuel burned and the timing of the injection. However, one disadvantage of this approach is that the intake valves of DISI engines may form a large amount of intake valve deposits (hereinafter "IVD") because there is no gasoline at the intake valve position to provide deposit control additives to prevent (combat ) deposits or deposit precursors. These valve deposits interfere with the operation of the valves, reduce the efficiency of the engine and have a negative impact on drivability.

Several patent documents disclose solving the problem of intake valve deposits in direct injection spark ignition engines by using lubricant formulations.

Japanese Patent Publication No. 2003-155492 by Konishi discloses lubricants containing polybutenyl succinimide, zinc dithiophosphate, phenolic and/or amine ashless antioxidants, and alkaline earth metal detergents, and It contains no viscosity index improvers.

U.S. Patent Application Publication No. 2004/0198614 to Calder discloses a method of reducing intake valve deposits in a direct injection engine comprising lubricating the engine with a lubricating oil composition comprising a base oil blend comprising and (ii) Synthetic ester oils combining (i) Group III oils, Group IV oils or mixtures thereof, the weight ratio of (i) to (ii) is from about 0.2:1 to about 6:1.

U.S. Patent Application Publication No. 2004/0231632 to Colucci et al. discloses the reduction of intake manifold deposits (such as valves including intake valves) and in internal combustion engines by delivering an organic molybdenum source from the gas phase of the engine lubricant into the combustion chamber. Methods of formation of exhaust valve deposits and combustion systems.

U.S. Patent Application Publication No. 2005/0236301 to Adams et al. discloses a process for the preparation of heavy and light lubricating base oils from partially isomerized Fischer-Tropsch derived feedstocks having a temperature below 400°C by the following steps: initial boiling point and final boiling point above 600°C by: (a) separating the fraction by distillation into a light base oil precursor fraction and a heavy base oil precursor fraction; (b) reducing each fraction by dewaxing the pour point of a separate base oil precursor fraction; and (c) isolating the desired base oil product from the dewaxed oil fraction obtained in step (b).

U.S. Patent Application Publication No. 2006/0052252 to Wedlock discloses a lubricant composition containing a mixture of at least two Fischer-Tropsch derived base oils and one or more additives, one of which is - Tropsch derived base oil (low viscosity component) has a kinematic viscosity of less than 7 cSt at 100°C, a second Fischer-Tropsch derived base oil (high viscosity component) has a kinematic viscosity of greater than 18 cSt at 100°C.

U.S. Patent Application Publication No. 2007/0197406 to Locke et al. discloses reducing intake valve deposits in direct injection internal combustion engines by lubricating the engine with a lubricant that is substantially free of ashless organic friction modifiers and Its base oil has a Noack volatility of less than 12% by mass.

A number of patent documents disclose the use of foam suppressors in a general manner in gasoline direct injection engines. These include: US Patent Application Publication Nos. 2008/0234153, 2008/0248981, and 2008/0110799; and Japanese Patent Publication Nos. 2008-120908, 2001-262172, 2008-231192, and 2008-231191.

As noted above, intake valve deposits are believed to be a problem in DISI engines. Various attempts have been made to alleviate the problem of reducing intake valve deposits in DISI engines.

Summary of the invention

One embodiment of the present invention is directed to a method of reducing intake valve deposits in a direct injection spark ignition engine, the method comprising operating the engine with a lubricating oil composition comprising:

(a) a major quantity of oil of lubricating viscosity; and

(b) at least one foam inhibitor selected from silicone oils, polysiloxanes, polyacrylates and polymethacrylates;

wherein the foam suppressor is not a poly(phenylmethyl)siloxane; and further wherein the amount of the foam suppressor in the lubricating oil composition is such that the intake valve in the direct injection spark ignition engine Deposits are reduced at an effective concentration of at least 10% compared to operating the engine with the lubricating oil composition without any foam inhibitor.

Another embodiment of the present invention is directed to a method of reducing intake valve deposits in a direct injection spark ignition engine comprising:

(a) operating said engine with lubricating oil; and

(b) finishing the lubricating oil composition with a lubricating oil concentrate comprising silicone oil, polysiloxane, polyacrylate and at least one foam inhibitor of polymethacrylate;

wherein the suds suppressor is not poly(phenyl-methyl)siloxane; and further wherein the amount of the suds suppressor in the finishing lubricating oil composition is such that the direct injection spark ignition is achieved Intake valve deposits in the engine are reduced to an effective concentration of at least 10% compared to operating said engine with the lubricating oil of step (a) without any final treatment.

In another embodiment, the lubricating oil composition disclosed herein further comprises antioxidants, antiwear agents, detergents, rust inhibitors, demulsifiers, friction modifiers, extreme pressure agents, viscosity index improvers, At least one additive of a pour point agent, a dispersant, a corrosion inhibitor, and combinations thereof.

definition

The term "finishing" refers to the addition of the lubricating oil concentrates described herein to the crankcase oil already present in a DISI engine.

Detailed description of the invention

The present invention is based, among other factors, on the surprising discovery that the addition of a greater than usual amount of foam suppressor to a lubricant used to lubricate a direct injection gasoline engine can substantially reduce the amount of intake valve deposits in said engine . Typical amounts of suds suppressors used in many lubricants are from about 5 to about 30 ppmw. The increased amount of added foam suppressor is relatively small, but enables the use of expensive specialty lubricants or base oils such as polyalphaolefin (group IV) or ester (group V) lubricants. Greatly reduces IVD deposits. This discovery also enables the aftermarket addition of small amounts of foam inhibitor boosters in gasoline direct injection engines lubricated with conventional lubricants.

According to one embodiment of the present invention, there is provided herein a method of reducing intake valve deposits in a direct injection spark ignition engine, the method comprising operating the engine with a lubricating oil composition comprising:

(a) a major quantity of oil of lubricating viscosity; and

(b) at least one foam inhibitor selected from silicone oils, polysiloxanes, polyacrylates and polymethacrylates;

wherein the foam suppressor is not a poly(phenylmethyl)siloxane; and further wherein the amount of the foam suppressor in the lubricating oil composition is such that the intake valve in the direct injection spark ignition engine Deposits are reduced at an effective concentration of at least 10% compared to operating the engine with the lubricating oil composition without any foam inhibitor.

According to another embodiment of the present invention, there is provided herein a method of reducing intake valve deposits in a direct injection spark ignition engine, the method comprising:

(a) operating said engine with lubricating oil; and

(b) finishing the lubricating oil composition with a lubricating oil concentrate comprising silicone oil, polysiloxane, polyacrylate and at least one foam inhibitor of polymethacrylate;

wherein the suds suppressor is not poly(phenyl-methyl)siloxane; and further wherein the amount of the suds suppressor in the finishing lubricating oil composition is such that the direct injection spark ignition is achieved Intake valve deposits in the engine are reduced to an effective concentration of at least 10% compared to operating said engine with the lubricating oil of step (a) without any final treatment.

In one embodiment of the invention, the direct injection spark ignition engine is an engine equipped with positive crankcase ventilation. Positive crankcase ventilation is a method used to reduce engine emissions in which combustion gases escaping from the combustion chamber past the pistons and piston rings into the crankcase (often referred to as "blow-by") are returned through the intake manifold to the combustor where the recycled hydrocarbons are combusted.

Oil of Lubricating Viscosity:

The oil of lubricating viscosity (also referred to as base oil) used in the lubricating oil composition of the present invention is typically greater than 50 wt.%, preferably greater than about 70 wt.%, more preferably about 80- It is present therein in an amount of about 99.5 wt.% and most preferably from about 85 to about 98 wt.%. As used herein, the term "base stock" should be understood to mean a base stock or base stock blend produced by a single manufacturer to the same specification (regardless of the origin of the raw material or the location of the manufacturer), meeting the specifications of the same manufacturer and Lubricant components identified by unique formulation, product identification number, or both.

The base oil used herein may be any base oil of lubricating viscosity now known or later discovered for use in formulating lubricating oil compositions for any and all such applications, such as engine oils, marine cylinder oils, functional fluids such as Hydraulic oil, gear oil, transmission oil, etc. A specific base oil is selected based on the intended use of the oil and the presence of other additives. For example, oils of lubricating viscosity useful in the practice of this invention may range in viscosity from light distillate mineral oils to heavy lubricating oils such as gasoline engine oils, mineral lubricating oils, and heavy-duty diesel oils. In addition, the base oils used herein may optionally contain viscosity index improvers such as polymerized alkyl methacrylates, olefin copolymers such as ethylene-propylene copolymers or styrene-butadiene copolymers, and the like, and mixtures thereof. The lubricating oil compositions of the present invention can be prepared by conventional techniques by mixing appropriate amounts of the suds suppressor compound as an additive concentrate with an oil of lubricating viscosity and conventional lubricating oil additives.

As one skilled in the art can readily appreciate, the viscosity of the base oil depends on the application. Accordingly, the base oils employed herein typically have viscosities in the range of about 2 to about 2000 centistokes (cSt) at 100°C. Generally, specific to base oils for use as engine lubricating oils, their kinematic viscosities at 100° C. range from about 2 to about 30 cSt, preferably from about 3 to about 16 cSt and most preferably from about 4 to about 12 cSt, and depending on the intended end use and The additives in the finished oil are selected or blended to obtain the desired grade of engine lubricating oil, for example, with SAE viscosity grades 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, 10W-50, 15W, 15W-20, 15W-30, or 15W-40 lubricating oil composition. Oils used as gear oils have viscosities ranging from about 2 cSt to about 2000 cSt at 100°C.

Base stocks can be manufactured using a variety of different methods including, but not limited to, distillation, solvent refining, hydrogen treatment, oligomerization, esterification, and re-refining. The re-refined base should be substantially free of substances introduced through production, contamination and prior use. The base oil of the lubricating oil compositions of the present invention may be any natural or synthetic lubricating base oil. Suitable hydrocarbon synthetic oils include, but are not limited to, oils prepared from the polymerization of ethylene or from polymers of 1-olefins to provide polymers such as polyalphaolefins or PAO oils, or from hydrocarbon synthesis processes using carbon monoxide and hydrogen, such as by the Fischer-Tropsch process prepared oil. For example, a suitable base oil is one that contains little, if any, heavy fractions; eg few, if any, fractions of lubricating oils having viscosities above 20 cSt at 100°C.

Base oils may be derived from natural lubricating oils, synthetic lubricating oils, or mixtures thereof. Suitable base stocks include those obtained by isomerization of synthetic and slack waxes, and those produced by hydrocracking (rather than solvent extraction) the aromatic and polar components of the crude product Cracking base material. Suitable base oils include those in all API classes, ie, I, II, III, IV and V, as defined in API Publication 1509, 14th Edition, Addendum I, Dec. 1998. Group IV base oils are polyalphaolefins (PAO). Group V base oils include all other base oils not included in Groups I, II, III or IV.

As demonstrated herein, one advantage of the present invention is that low volumes of IVD can be obtained without the use of large quantities of expensive Type IV or Type V base stocks. Thus, in one embodiment of the invention the oil of lubricating viscosity comprises at least 50 wt% of Group III base stock. In another embodiment of the present invention, the oil of lubricating viscosity comprises at least 50% by weight of an API Group II base stock. In a further embodiment of the present invention, the oil of lubricating viscosity comprises at least 50% by weight of a mixture of Group II and Group III base stocks. In one embodiment of the invention, the oil of lubricating viscosity is free of Group IV or V base stocks. In one embodiment of the invention, the base oil is a mixture of Group II, Group III and Group IV base stocks.

Natural oils may also be used, including mineral lubricating oils such as liquid petroleum, solvent-treated or acid-treated mineral lubricating oils of the paraffinic, naphthenic or mixed paraffinic-naphthenic type, derived from coal or shale oils, animal oils, vegetable oils (such as rapeseed oil, castor oil and refined lard), etc.

Synthetic lubricating oils may also be used, including but not limited to hydrocarbon oils and halogen-substituted hydrocarbon oils, such as polymerized and interpolymerized olefins such as polybutene, polypropylene, propylene-isobutylene copolymers, chlorinated polybutene, poly( 1-hexene), poly(1-octene), poly(1-decene), and their analogs and mixtures; alkylbenzenes such as dodecylbenzene, tetradecylbenzene, dinonylbenzene, Bis(2-ethylhexyl)-benzene, etc.; polyphenylenes such as biphenyl, terphenyl, alkylated polyphenylene, etc.; alkylated diphenyl ethers and alkylated diphenyl sulfides and their derivatives , analogues and homologues, etc.

Other synthetic lubricating oils used include, but are not limited to, oils prepared by polymerizing olefins of less than 5 carbon atoms, such as ethylene, propylene, butene, isobutylene, pentene, and mixtures thereof. Methods of preparing such polymer oils are well known to those skilled in the art.

Additional synthetic hydrocarbon oils used include liquid polymers of alpha olefins of suitable viscosity. Particularly useful synthetic hydrocarbon oils are hydrogenated liquid oligomers of C ₆ -C ₁₂ alpha olefins, such as 1-decene trimer.

Another class of synthetic lubricating oils includes, but is not limited to, alkylene oxide polymers, ie, homopolymers, copolymers and derivatives thereof, in which the terminal hydroxyl groups are modified by, for example, esterification or etherification. These oils are exemplified by oils prepared by polymerization of ethylene oxide or propylene oxide, alkyl and phenyl ethers of polyoxyalkylene polymers (e.g. methyl polypropylene glycol ether having an average molecular weight of 1,000, having a molecular weight of 500-1000 Diphenyl ether of polyethylene glycol with a molecular weight of 1,000-1,500, diethyl ether of polypropylene glycol with a molecular weight of 1,000-1,500, etc.) or their mono- and polycarboxylates such as acetates, mixed C ₃ -C ₈ fatty acid esters, or C ₁₃ oxyacid diesters of tetraethylene glycol.

Yet another class of synthetic lubricating oils includes, but is not limited to, esters of dicarboxylic acids such as phthalic acid, succinic acid, alkyl succinic acid, alkenyl succinic acid, maleic acid, azelaic acid, and various alcohols. acid, suberic acid, sebacic acid, fumaric acid, adipic acid, linoleic acid dimer, malonic acid, alkylmalonic acid, alkenylmalonic acid, etc., the alcohols such as butanol, hexanoic acid Alcohol, lauryl alcohol, 2-ethylhexanol, ethylene glycol, diethylene glycol monoether, propylene glycol, etc. Specific examples of these esters include dibutyl adipate, di(2-ethylhexyl) sebacate, di-n-hexyl fumarate, dioctyl sebacate, diisooctyl azelate , Diisodecyl azelate, Dioctyl phthalate, Didecyl phthalate, Dieicosyl sebacate, 2-Ethylhexyl linoleic acid dimer Diesters, complex esters formed by reacting 1 mole of sebacic acid with 2 moles of tetraethylene glycol and 2 moles of 2-ethylhexanoic acid, and the like.

Esters can also be used as synthetic oils and include, but are not limited to, carboxylic acids having from about 5 to about 12 carbon atoms with alcohols such as methanol, ethanol, etc., polyols and polyol ethers such as neopentyl glycol, trimethylolpropane, Those esters prepared from pentaerythritol, dipentaerythritol, tripentaerythritol, and the like.

Silicone-based oils, such as polyalkyl-, polyaryl-, polyalkoxy- or polyaryloxy-siloxane oils and silicate oils, constitute another class of synthetic lubricating oils that may be used in the present invention. Specific examples of these include, but are not limited to, tetraethyl silicate, tetraisopropyl silicate, tetra(2-ethylhexyl) silicate, tetra-(4-methyl-hexyl) silicate, tetra (p-tert-butylphenyl)ester, hexyl-(4-methyl-2-pentyloxy)disiloxane, poly(methyl)siloxane, poly(methylphenyl)siloxane, and the like.

Lubricating oils may be derived from unrefined, refined, and re-refined oils, and may be natural, synthetic, or a mixture of any two or more of these types disclosed above. Unrefined oils are those obtained directly from natural or synthetic sources such as coal, shale or tar sands bitumen without further purification or treatment. Examples of unrefined oils include, but are not limited to, shale oils obtained directly from retorting operations, petroleum oils obtained directly from distillation, or ester oils obtained directly from esterification processes, all of which are used without further treatment. Refined oils are similar to unrefined oils except that they have been further treated in one or more purification steps to improve one or more properties. These purification techniques are well known to those skilled in the art and include, for example, solvent extraction, secondary distillation, acid or base extraction, filtration, permeation, hydrotreatment, dewaxing, and the like. Refined oils are obtained by treating used oils in a process similar to that used to obtain refined oils. Such re-refined oils are also known as reclaimed or reprocessed oils and are often additionally processed by techniques involving the removal of spent additives and oil breakdown products.

Lubricating oil base stocks derived from wax hydroisomerization may also be used alone or in combination with the natural and/or synthetic base stocks described above. Such wax isomerized oils are produced by hydroisomerizing natural or synthetic waxes or mixtures thereof over a hydroisomerization catalyst.

Natural waxes are typically loose waxes recovered by solvent dewaxing of mineral oils; synthetic waxes are typically waxes produced by the Fischer-Tropsch process.

Foam inhibitor

Foam suppressors are lubricant additives that, when added to lubricants in small amounts, inhibit foam formation, accelerate foam collapse, or both. At least one foam suppressor or a mixture thereof is used in the lubricating oil composition as claimed in the present invention. The foam suppressor used is selected from silicone oils, polysiloxanes, polyacrylates, polymethacrylates and combinations thereof, with the proviso that the foam suppressor may not be poly(phenyl-methyl)siloxane .

In one embodiment, the suds suppressor is polydimethylsiloxane.

In one embodiment, the suds suppressor is poly(dimethyl,phenyl-methyl)siloxane. In one embodiment, the suds suppressor is a mixture of polydimethylsiloxane and poly(dimethyl,phenyl-methyl)siloxane.

In one embodiment, the suds suppressor is polymethacrylate.

In one embodiment, the suds suppressor is poly(trifluoropropylmethyl)siloxane.

In one embodiment, the amount of the foam inhibitor in the lubricating oil composition may be from about 30 to about 500 ppmw, or from about 50 to about 500 ppmw, or from about 75 to about 500 ppmw, based on the total weight of the lubricating oil composition, or From about 100 to about 500 ppmw, or from about 150 to about 500 ppmw, or from about 200 ppmw to about 400 ppmw.

In one embodiment, the reduction in intake valve deposits is at least 10%, or at least 20%, or at least 30%, compared to operating the engine with the lubricating oil composition without any foam suppressor. Or at least 40%, or at least 50%.

In one embodiment, the amount of suds suppressor in the lubricating oil concentrate may be from about 0.01 wt.% to about 1 wt.%, from about 0.02 wt.% to about 0.8 wt.%, based on the total weight of the lubricating oil concentrate. From about 0.03wt.% to about 0.7wt.%, or from about 0.04wt.% to about 0.6wt.%. The suds suppressor may conveniently be added to the lubricating oil concentrate in the form of a suds suppressor concentrate comprising a suds suppressor and at least one solvent.

Additional lubricant additives:

The lubricating oil compositions of the present invention may also contain other conventional additives for providing auxiliary functions to produce finished lubricating oil compositions in which these additives are dispersed or dissolved. For example, lubricating oil compositions can be blended with: antioxidants, ashless dispersants, detergents, rust inhibitors, cloud removers, demulsifiers, metal passivators, friction modifiers, pour point depressants, co- Solvents, package compatibilisers, corrosion inhibitors, ashless dispersants, dyes, extreme pressure agents, and the like and mixtures thereof. Various additives are well known and commercially available. The lubricating oil composition of the present invention can be prepared using these additives or their analogous compounds by a general blending method.

Examples of antioxidants include, but are not limited to, aminic type antioxidants such as diphenylamine, phenyl-α-naphthylamine, N,N-di(alkylphenyl)amine, and alkylated phenylenediamine, Phenolic antioxidants such as BHT, sterically hindered phenolic alkylphenols such as 2,6-di-tert-butylphenol, 2,6-di-tert-butyl-p-cresol and 2,6-di-tert-butyl-4- (2-octyl-3-propionyl)phenol and mixtures thereof.

Examples of anti-wear agents include, but are not limited to, zinc dialkyl dithiophosphates and zinc diaryl dithiophosphates, such as described in Born et al., Lubrication Science 4-2, January 1992, entitled "Relationship between Chemical Structure and Effectiveness of Some Metallic Dialkyl-and Diaryl-dithiophosphates in Different Lubricated Mechanisms" (see e.g. pages 97-100); aryl phosphates and phosphites, sulfur-containing esters, phosphorus-sulfur compounds, metallic or ashless Dithiocarbamates, xanthates, alkyl sulfides, etc. and mixtures thereof.

Representative examples of ashless dispersants include, but are not limited to, amines, alcohols, amides, or ester polar moieties attached to the polymer backbone via bridging groups. The ashless dispersants of the present invention may, for example, be selected from oil-soluble salts, esters, amino-esters, amides, imides and oxazolines of long-chain hydrocarbon-substituted mono- and dicarboxylic acids or their anhydrides; long-chain hydrocarbons, Thiocarboxylate derivatives of long-chain aliphatic hydrocarbons having polyamines directly attached thereto; and Mannich condensation products resulting from the condensation of long-chain substituted phenols with formaldehyde and polyalkylene polyamines.

Carboxylic acid-type dispersants are carboxylic acid-type acylating agents (acids, anhydrides, esters, etc.) containing at least about 34 and preferably at least about 54 carbon atoms in combination with nitrogen-containing compounds (such as amines), organic hydroxyl compounds (such as aliphatic compounds including alcohols and polyols, or aromatic compounds including phenols and naphthols), and/or basic inorganic substances. These reaction products include imides, amides and esters.

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

Succinic acid based dispersants come in a variety of chemical structures. One class of succinic acid-based dispersants can be represented by the formula:

Wherein, each R ¹ is independently a hydrocarbon group, such as a polyolefin-derived group. Typically the hydrocarbyl group is an alkyl group such as polyisobutyl. Alternatively expressed, the R1 group may contain from ^about 40 to about 500 carbon atoms, which atoms may be present in aliphatic form. R ² is an alkylene group, typically ethylene (C ₂ H ₄ ). Examples of succinimide dispersants include those described in, for example, US Patent Nos. 3,172,892, 4,234,435, and 6,165,235.

The polyolefins from which the substituents are derived are generally homopolymers and copolymers of polymerizable olefinic monomers of 2 to about 16 carbon atoms and usually 2 to 6 carbon atoms. The amine that reacts with the succinic acylating agent to form the carboxyl-containing dispersant composition can be a monoamine or a polyamine.

Succinimide dispersants are so called because they generally contain nitrogen mostly in the form of imide functionality, although the amide functionality can be in the form of amine salts, amides, imidazolines, and mixtures thereof. To prepare succinimide dispersants, one or more succinic acid generating compounds and one or more amines are heated, optionally in the presence of a substantially inert organic liquid solvent/diluent and typically remove water. The reaction temperature generally ranges from about 80°C up to the decomposition temperature of the mixture or the product, which typically ranges from about 100 to about 300°C. Additional details and examples of methods of preparing the succinimide dispersants of the present invention include those described, for example, in US Patent Nos.

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

Suitable ashless dispersants may also include "Mannich dispersants", which are alkylphenols with aldehydes (especially formaldehyde) and amines (especially polyalkylenepolyamines) in which the alkyl group contains at least about 30 carbon atoms. reaction product. Examples of such dispersants include those described in, for example, US Patent Nos. 3,036,003, 3,586,629, 3,591,598, and 3,980,569.

Suitable ashless dispersants may also include post-treated ashless dispersants such as post-treated succinimides, such as those disclosed in U.S. Patent Nos. 4,612,132 and 4,746,446 involving borate and ethylene carbonate, among others. post-processing method. Carbonate-treated alkenyl succinimides are derived from compounds having a molecular weight of from about 450 to about 3000, preferably from about 900 to about 2500, more preferably from about 1300 to about 2400, most preferably from about 2000 to about 2400, and mixtures of these molecular weights. Polybutene succinimide of polybutene. Preferably, it is prepared by reacting a polybutene succinic acid derivative, an unsaturated acidic agent, an unsaturated acidic agent copolymer of an olefin, and a mixture of polyamines under reactive conditions, such as described in U.S. Patent No. 5,716,912 published, the contents of which are incorporated herein by reference.

Suitable ashless dispersants may also be polymeric, which are copolymers of oil-soluble monomers such as decyl methacrylate, vinyl decyl ether and high molecular weight olefins with monomers containing polar substituents. Examples of polymeric dispersants include those described in, for example, US Patent Nos. 3,329,658, 3,449,250, and 3,666,730.

In a preferred embodiment of the present invention, the ashless dispersants for lubricating oil compositions are disuccinimides derived from polyisobutylene groups having a number average molecular weight of from about 700 to about 2300. Dispersants for use in the lubricating oil compositions of the present invention are preferably non-polymeric (eg, mono- or disuccinimides).

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

Representative examples of metal detergents include sulfonates, alkylphenates, sulfurized alkylphenates, carboxylates, salicylates, phosphonates, and hypophosphites. Commercially available products are generally referred to as neutral or overbased species. Usually by reacting with a mixture of hydrocarbons, detergent acids such as sulfonic acids, alkylphenols, carboxylates, etc., metal oxides or hydroxides (such as calcium oxide or calcium hydroxide), and accelerators such as xylene, methanol and water Carbonation to prepare overbased metal detergents. For example, to prepare overbased calcium sulfonate, in carbonation, calcium oxide or hydroxide is reacted with gaseous carbon dioxide to form calcium carbonate. The sulfonic acid is neutralized with an excess of CaO or Ca(OH) ₂ to form the sulfonate.

Metal-containing or ash-forming detergents act as detergents to reduce or remove deposits and act as acid neutralizers or rust inhibitors, reducing wear and corrosion and extending engine life. Detergents generally contain a polar head with a long hydrophobic tail. The polar head comprises a metal salt of an acidic organic compound. The salts may contain substantially stoichiometric amounts of the metal, in which case they are often referred to as normal or neutral salts, and the salts generally have a total base number or TBN (as determined by ASTM D2896 measurement). Large amounts of metal bases can be incorporated by reacting excess metal compounds such as oxides or hydroxides with acid gases such as carbon dioxide. The resulting overbased detergent contains the neutralized detergent as the outer layer of the metal base (eg carbonate) micelles. Such overbased detergents can have a TBN of about 150 or greater, and typically can have a TBN of about 250 to about 450 or greater.

Detergents which may be used include oil-soluble neutral and overbased sulfonates, phenates, sulfurized phenates, thiophosphates, salicylates and naphthenates and metals, especially alkali or alkaline earth metals Other oil-soluble carboxylates such as barium, sodium, potassium, lithium, calcium and magnesium. The most commonly used metals are calcium and magnesium (which can both be present in detergents used in lubricants), and mixtures of calcium and/or magnesium with sodium. Particularly suitable metal detergents are neutral and overbased calcium sulfonates with a TBN of from about 20 to about 450, neutral and overbased calcium phenates and sulfurized phenates of calcium with a TBN of from about 50 to about 450, and neutral and overbased magnesium or calcium salicylates having a TBN of about 20 to about 450. Combinations of detergents, whether overbased or neutral or both, can be used.

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

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

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

In another embodiment, the olefin is a branched olefinic propylene oligomer or mixture thereof having from about 20 to about 80 carbon atoms, ie, a branched olefin derived from the polymerization of propylene. The alkenes may also be substituted with other functional groups such as hydroxyl groups, carboxylic acid groups, heteroatoms, and the like. In one embodiment, the branched olefinic propylene oligomers or mixtures thereof have from about 20 to about 60 carbon atoms. In one embodiment, the branched olefinic propylene oligomers or mixtures thereof have from about 20 to about 40 carbon atoms.

In one embodiment, at least about 75 moles of the alkyl group in the alkali metal or alkaline earth metal salt of an alkyl-substituted hydroxyaromatic carboxylic acid (for example, the alkyl group of an alkaline earth metal salt of an alkyl-substituted hydroxybenzoic acid detergent) % (eg, at least about 80 mol%, at least about 85 mol%, at least about 90 mol%, at least about 95 mol%, or at least about 99 mol%) is _C20 or more. In another embodiment, the alkali metal or alkaline earth metal salt of an alkyl-substituted hydroxyaromatic carboxylic acid is an alkali metal or alkaline earth metal salt of an alkyl-substituted hydroxybenzoic acid derived from an alkyl-substituted hydroxybenzoic acid, wherein The alkyl group is a normal alpha olefin residue containing at least 75 mol% of C ₂₀ or higher normal alpha olefins.

In another embodiment, at least About 50 mol%, such as at least about 60 mol%, at least about 70 mol%, at least about 80 mol%, at least about 85 mol%, at least about 90 mol%, at least about 95 mol%, or at least about 99 mol%, is about _C14 to about _C18 .

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

The alkali metal or alkaline earth metal salts of the alkyl-substituted hydroxyaromatic carboxylic acids can be neutral or overbased. Typically, overbased alkali metal or alkaline earth metal salts of alkyl-substituted hydroxyaromatic carboxylic acids are those in which the alkyl substitution is increased by, for example, addition of an alkali source such as lime and an acidic overbased compound such as carbon dioxide. Substances of BN of alkali metal or alkaline earth metal salts of hydroxyaromatic carboxylic acids.

The overbased salt can be a low overbased salt, such as an overbased salt with a BN of less than about 100. In one embodiment, the low overbased salt may have a BN of from about 5 to about 50. In another embodiment, the low overbased salt may have a BN of from about 10 to about 30. In yet another embodiment, the low overbased salt may have a BN of from about 15 to about 20.

The overbased detergent can be a moderately overbased, such as an overbased salt with a BN of about 100 to about 250. In one embodiment, the BN of the medium overbased salt may range from about 100 to about 200. In another embodiment, the BN of the medium overbased salt can be from about 125 to about 175.

Overbased detergents can be highly overbased, such as overbased salts with a BN greater than about 250. In one embodiment, the overbased salt may have a BN of about 250 to about 450.

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

Oil-soluble sulfonates or alkylarylsulfonic acids can be treated with metal oxides, hydroxides, alkoxides, carbonates, carboxylates, sulfides, hydrosulfides, nitrates, borates or ethers. neutralize. The amount of metal compound is selected according to the desired TBN of the final product, but is typically from about 100 to about 220 wt.% (preferably at least about 125 wt.%) of the stoichiometrically required amount.

Metal salts of phenols and sulfurized phenols are prepared by reaction with suitable metal compounds such as oxides or hydroxides and neutral or overbased products can be obtained by methods well known in the art. Sulfurized phenols can be prepared by reacting phenols with sulfur or sulfur-containing compounds such as hydrogen sulfide, sulfur monohalides, or sulfur dihalides to produce products, usually in which two or more phenols are bonded via sulfur-containing bridges. Mixture of bridging compounds.

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

Examples of rust inhibitors include, but are not limited to, nonionic polyoxyalkylene agents such as polyoxyethylene lauryl ether, polyoxyethylene higher alcohol ether, polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene octylphenyl ether, Oxyethylene octylstearyl ether, polyoxyethylene oleyl ether, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan monooleate, and polyethylene glycol monooleate; stearin fatty acids and other fatty acids; dicarboxylic acids; metal soaps; fatty acid amine salts; metal salts of heavy sulfonic acids; metacarboxylates of polyhydric alcohols; phosphoric acid esters; (short-chain) alkenylsuccinic acids; Nitrogen derivatives; synthetic alkaryl sulfonates such as metal dinonylnaphthalene sulfonate; and analogs and mixtures thereof.

Examples of friction modifiers include, but are not limited to, alkoxylated fatty amines; borated fatty epoxides; fatty phosphites, fatty epoxides, fatty amines, borated alkoxylated Fatty amines, metal salts of fatty acids, fatty acid amides, glycerides, borated glycerides; and fatty imidazolines disclosed in U.S. Patent No. 6,372,696, the contents of which are incorporated herein by reference; friction modifiers Obtained from the reaction product of C ₄ -C ₇₅ , preferably C ₆ -C ₂₄ , most preferably C ₆ -C ₂₀ fatty acid esters, and nitrogen-containing compounds selected from ammonia, alkanolamines and their analogs and mixtures.

Examples of pour point depressants include, but are not limited to, polymethacrylates, alkyl acrylate polymers, alkyl methacrylate polymers, bis(tetraparaffinphenol) phthalates, tetraparaffinphenol Condensates of chlorinated alkanes and naphthalene, and combinations thereof. In one embodiment, the pour point depressant comprises ethylene-vinyl acetate copolymers, condensates of chlorinated paraffins and phenols, polyalkylstyrenes, and the like, and combinations thereof. The amount of pour point depressant may be from about 0.01 wt.% to about 10 wt.%.

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

Examples of corrosion inhibitors include, but are not limited to, half esters or amides of dodecylsuccinic acid, phosphoric acid esters, phosphorothioate esters, alkylimidazolines, sarcosine, and the like, and combinations thereof. The amount of corrosion inhibitor can be from about 0.01 wt.% to about 5 wt.%.

Examples of extreme pressure agents include, but are not limited to, sulfurized animal or vegetable fats or oils, sulfurized animal or vegetable fatty acid esters, fully or partially esterified esters of trivalent or pentavalent acids of phosphorus, sulfurized olefins, dihydrocarbyl poly Sulfides, sulfurized Diels-Alder adducts, sulfurized dicyclopentadiene, sulfurized or co-sulfurized mixtures of fatty acid esters and monounsaturated olefins, co-sulfurized blends of fatty acids, fatty acid esters and alpha-olefins , functionally substituted dihydrocarbyl polysulfides, thioaldehydes, thioketones, episulfide compounds, sulfur-containing acetal derivatives, cosulfidation blends of terpenes and acyclic olefins, polysulfide olefin products , amine salts of phosphoric acid esters or phosphorothioate esters, etc., and combinations thereof. The amount of extreme pressure agent may be from about 0.01 wt.% to about 5 wt.%.

Each of the foregoing additives, when used, is used in a functionally effective amount to impart desired properties to the lubricant. Thus, for example, if the additive is a friction modifier, a functionally effective amount of the friction modifier would be an amount sufficient to impart the desired friction modifying properties to the lubricant. Generally, unless otherwise specified, each of these additives may be used at a concentration of from about 0.001 wt.% to about 20 wt.%, and in one embodiment from about 0.01 wt.% to about 10wt.%.

In another embodiment of the present invention, the lubricating oil additives of the present invention may be provided in the form of an additive package or concentrate wherein the additive is added to a substantially inert, conventional liquid organic diluent such as mineral oil, naphtha, Benzene, toluene or xylene to form additive concentrates.

Concentrates and Diluents:

Lubricant oil concentrates are also contemplated herein. These concentrates generally include at least about 90 wt.% to about 10 wt.%, or about 80 wt.% to about 20 wt.%, or about 70 wt.% to about 30 wt.%, or about 60 wt.% to about 40 wt.% of the diluted Oil, and about 10wt.% to about 90wt.%, or about 20wt.% to about 80wt.%, or about 30wt.% to about 70wt.%, or about 40wt.% to about 60wt.% of the lubricating oil combination of the present invention The foam suppressor described in the article, or their combination. Typically, the concentrates contain sufficient diluent to render them easy to handle during shipping and storage. Suitable diluents for the concentrate include any inert diluent, preferably an oil of lubricating viscosity, so that the concentrate can be readily mixed with a lubricating oil to prepare a lubricating oil composition. Suitable lubricating oils useful as diluents typically have a viscosity of from about 35 to about 500 Saybolt Universal Seconds (SUS) at 100°F (38°C), although oils of any lubricating viscosity may be used.

Other additives may be blended with the foregoing lubricating oil concentrates to enhance performance, if desired. Examples of such additives include, but are not limited to, antioxidants, antiwear agents, detergents, rust inhibitors, demulsifiers, friction modifiers, extreme pressure agents, viscosity index improvers, pour point depressants, agent, dispersant, corrosion inhibitor, etc.

It is also contemplated that the foam suppressors of the present invention, together with other additional additives described herein, may be used as a finishing treatment for crankcase lubricants used in DISI engines. When so used, the finishing lubricating oil concentrate may be added to the oil at about 0.01 to 5 wt. %, or about 0.5 to about 2 wt. %, based on the total weight of the lubricant composition.

In another embodiment, the final finishing treatment of the lubricating oil concentrate is added to the initial DISI engine lubricating oil composition.

In one embodiment, the addition of the finishing lubricating oil concentrate reduces the IVD by at least 10% compared to operating the engine with the lubricating oil without any finishing lubricating oil concentrate.

In one embodiment, the addition of the finishing lubricating oil concentrate reduces the IVD by at least 20% compared to operating the engine with the lubricating oil without any finishing lubricating oil concentrate.

In one embodiment, the addition of the finishing lubricating oil concentrate reduces the IVD by at least 30% compared to operating the engine with the lubricating oil without any finishing lubricating oil concentrate.

In one embodiment, the addition of the finishing lubricating oil concentrate reduces the IVD by at least 40% compared to operating the engine with the lubricating oil without any finishing lubricating oil concentrate.

In one embodiment, the addition of the finishing lubricating oil concentrate reduces the IVD by at least 50% compared to operating the engine with the lubricating oil without any finishing lubricating oil concentrate.

Performance Testing

The lubricating oil compositions of Examples 1 and 2 below were evaluated using the 2001 Mitsubishi 1.8L DISI 212 Hour Intake Valve Deposit Test ("Mitsubishi IVD Test") described below. A 2001 Mitsubishi 1.8L DISI engine used in this procedure was mounted on an engine stand and connected to a dynamometer with load and speed control. The MitsubishiDISI engine is a wall-guided engine capable of operating homogeneous and lean-stratified combustion. For the tests described herein, the engine was operated in lean-stratified combustion mode.

The engine was first flushed with the oil to be tested, refilled with test oil, and then operated on a test cycle for 30 minutes. The engine was then stopped, the oil was drained, and a fresh sample of the test oil was added to the engine. A 212-hour test was then started, consisting of approximately 636 repeated test cycles. In this test cycle, the engine was operated at idle speed (750+-150 rpm) and no load for 1 minute, followed by 19 minutes at low load (20.0 N/m) and low speed (1400+-10 rpm). At 106 hours the engine was stopped and the oil level was checked and if necessary additional test oil was added to the full mark.

After 212 hours, the engine heads were removed and the intake valves and combustion chambers were rated for deposit weight. Eight intake valves in the engine (two per cylinder) were flushed with hexane and weighed. The intake valves were weighed before and after the test, and the difference in weight represented the weight of deposits accumulated during the test.

Example

The following non-limiting examples illustrate the invention. The efficacy of using a high concentration foam suppressor crankcase lubricant on a direct injection spark ignition engine was demonstrated by the 2001 Mitsubishi 1.8L DISI 2 12 Hour Intake Valve Deposit Test ("Mitsubishi IVD Test") described above. All lubricants tested contained the same amount of "baseline additive package" additives including dispersants, detergents, zinc dialkyl dithiophosphates, aminic antioxidants, friction modifiers , polymethacrylate pour point depressant and olefin copolymer viscosity index improver, but no foam suppressor.

Type III lubricants containing polysiloxane foam inhibitors

Mitsubishi IVD tests were performed on lubricants containing a baseline additive package in approximately 75 wt-% Yubase 4 Group III base oil, and various active ingredient concentrations of different foam inhibitors. Foam inhibitor A is poly(phenyl-methyl)siloxane; B is a mixture of polydimethylsiloxane and poly(dimethyl,phenyl-methyl)siloxane; C is polymethylsiloxane acrylate; D is poly(trifluoropropylmethyl)siloxane; and E is poly(dimethyl,phenyl-methyl)siloxane. The results are shown in Table 1 below.

The results in Table 1 show the surprising effectiveness of different foam suppressors in reducing intake valve deposits in Group III lubricants.

Type II/III/IV Lubricants Containing Silicone Foam Inhibitors

The Mitsubishi IVD test was performed on lubricants containing the baseline additive package at about 75 wt-% in the mixture below, and the various active ingredient concentrations from above for Foam Inhibitor B. The mixture contained (1) 50 wt-% PT100D Group II base oil, (2) 30 wt-% Yubase6 Group III base oil, and (3) 20 wt-% PAO8 Group IV base oil. The results are shown in Table 2 below.

Table 2

Example 7 Example 8 Foam inhibitor B B Foam inhibitor concentration, ppmw 30 150 IVD, mean mg 38 26

The results in Table 2 show that blended Type II/III/IV lubricants containing the foam suppressor of the present invention also exhibit low levels of intake valve deposits.

BMW 5W30 lubricants finished with foam inhibitor:

The Mitsubishi IVD test was performed on a commercial 5W30 lubricating oil finished with Foam Inhibitor B at an active ingredient concentration of 350 ppm from above. The results are shown in Table 3 below.

table 3

The results in Table 3 show the surprising effectiveness of finishing lubricating oils with concentrates containing foam suppressors in reducing intake valve deposits.

Claims (28)

1. for reducing the method for inlet valve deposits, the party in direct injection spark-ignited engine Method includes making electromotor work with lubricant oil composite, and described lubricant oil composite comprises:

(a) major amount of lubrication viscosity oil；With

B () is selected from polysiloxanes, polyacrylate and at least one foam of polymethacrylates Inhibitor；

Wherein said foam in hibitors is not poly-(methyl phenyl siloxane)；And wherein institute State the amount of foam in hibitors described in lubricant oil composite to be in and realize described direct-injection spark-ignition Inlet valve deposits in electromotor with the described lubricant oil composite without any foam in hibitors The work of described electromotor is made to compare the concentration of the 30-500ppmw reducing at least 10%.

2. the process of claim 1 wherein that described foam in hibitors is selected from polysiloxanes and poly-first Base acrylate.

3. the method for claim 1 or 2, wherein said foam in hibitors is selected from: poly dimethyl Siloxanes, poly-(trifluoro propyl methylsiloxane).

4. the method for claim 1 or 2, described in wherein said lubricant oil composite, foam presses down The concentration of preparation is 100-500ppmw.

5. the method for claim 1 or 2, the slip of wherein said inlet valve deposits be to Few 20%.

6. the method for claim 1 or 2, wherein said lubricant oil composite also comprise selected from Under at least one additive: detersive, dispersant, antioxidant, antiwear agents, antirust Agent, remove clouding agent, demulsifier, matal deactivator, friction modifiers, pour point depressant, altogether the most molten Agent, bag compatilizer, corrosion inhibitor, dyestuff, extreme pressure agent and their mixture.

7. the method for claim 1 or 2, wherein said lubrication viscosity oil comprises at least 50wt% API II class or Group III basestocks or their mixture.

8. for reducing the method for inlet valve deposits, the party in direct injection spark-ignited engine Method includes:

A () makes described electromotor work with lubricating oil；And

(b) with lubricant oil concentrate, described lubricant oil composite carried out finally completes process thus Thering is provided the lubricant oil composite through finally completing process, described lubricant oil concentrate comprises selected from silicon At least one foam in hibitors of oil, polysiloxanes, polyacrylate and polymethacrylates；

Wherein said foam in hibitors is not poly-(methyl phenyl siloxane)；And wherein institute The amount of foam in hibitors described in the lubricant oil composite through finally completing process of stating is in and realizes institute State inlet valve deposits in direct injection spark-ignited engine and any finally complete place with not having The lubricating oil of the step (a) of reason makes the work of described electromotor compare the 30-500 reducing at least 10% Ppmw concentration, wherein said finally completing processes the lubricant oil concentrate addition referred to described In DISI electromotor in already present crankcase oils.

9. the method for claim 8, wherein said foam in hibitors is selected from polysiloxanes and poly-first Base acrylate.

10. the method for claim 8 or 9, wherein said foam in hibitors is selected from: poly-diformazan Radical siloxane, poly-(trifluoro propyl methylsiloxane).

The method of 11. claim 8 or 9, foam described in wherein said lubricant oil concentrate The concentration of inhibitor is 0.01-1.0wt%.

The method of 12. claim 8 or 9, the wherein said lubricating oil through finally completing process The ultimate density of foam in hibitors described in compositions is 100-500ppmw.

The method of 13. claim 8 or 9, the slip of wherein said inlet valve deposits is At least 20%.

The method of 14. claim 8 or 9, the wherein said lubricating oil through finally completing process Compositions also comprises selected from least one following additive: detersive, dispersant, antioxidation Agent, antiwear agents, antirust agent, remove clouding agent, demulsifier, matal deactivator, friction modified Agent, pour point depressant, cosolvent, bag compatilizer, corrosion inhibitor, dyestuff, extreme pressure agent and it Mixture.

The method of 15. claim 8 or 9, wherein said lubricating oil comprises at least 50wt%'s API II class or Group III basestocks or their mixture.

The method of 16. claim 1 or 2, foam described in wherein said lubricant oil composite The concentration of inhibitor is 150-500ppmw.

The method of 17. claim 1 or 2, foam described in wherein said lubricant oil composite The concentration of inhibitor is 200-400ppmw.

The method of 18. claim 1 or 2, the slip of wherein said inlet valve deposits is At least 30%.

The method of 19. claim 1 or 2, the slip of wherein said inlet valve deposits is At least 40%.

The method of 20. claim 1 or 2, the slip of wherein said inlet valve deposits is At least 50%.

The method of 21. claim 8 or 9, foam described in wherein said lubricant oil concentrate The concentration of inhibitor is 0.02-0.8wt%.

The method of 22. claim 8 or 9, foam described in wherein said lubricant oil concentrate The concentration of inhibitor is 0.03-0.7wt%.

The method of 23. claim 8 or 9, foam described in wherein said lubricant oil concentrate The concentration of inhibitor is 0.04-0.6wt%.

The method of 24. claim 8 or 9, the wherein said lubricating oil through finally completing process The ultimate density of foam in hibitors described in compositions is 150-500ppmw.

The method of 25. claim 8 or 9, the wherein said lubricating oil through finally completing process The ultimate density of foam in hibitors described in compositions is 200-400ppmw.

The method of 26. claim 8 or 9, the slip of wherein said inlet valve deposits is At least 30%.

The method of 27. claim 8 or 9, the slip of wherein said inlet valve deposits is At least 40%.

The method of 28. claim 8 or 9, the slip of wherein said inlet valve deposits is At least 50%.