CN87100331A

CN87100331A - Be used to control the lubricant compositions that contains transition metal of viscosity

Info

Publication number: CN87100331A
Application number: CN87100331.7A
Authority: CN
Inventors: 戴维德·厄吉尼·里波
Original assignee: Lubrizol Corp
Current assignee: Lubrizol Corp
Priority date: 1986-01-21
Filing date: 1987-01-20
Publication date: 1987-09-16
Also published as: NO174347C; CN1013685B; AU6941087A; HK96694A; EP0290457A1; ZA87280B; DE3788345T2; IN167977B; BR8707574A; DE3788345D1; NO873690D0; WO1987004454A3; DK489487A; ES2003209A6; JPH01501396A; DK489487D0; FI883438A0; CA1290314C; NO174347B; EP0290457B1

Abstract

A kind of lubricant that contains certain oil soluble of trace or oil-dispersing property metallic compound, this compound can block the speed that lubricant viscosity increases in the environment that easily accumulates cigarette ash.

Description

Be used to control the lubricant compositions that contains transition metal of viscosity

The invention relates to lubricant compositions, specifically about controlling the viscosity of lubricant in the diesel engine.

Lubricant, the diesel lubrication agent in low speed, the running of high moment of torsion has the shortcoming that viscosity increases under long-time the use.The increase surface of this viscosity is that not only the interior lubricant viscosity of diesel engine begins to strengthen gradually, and the rate of growth of viscosity is quickened to increase in time.Finally, it is very high that viscosity becomes, thereby the mobile of oil of oil engine is restricted.

Second kind of factor is the lubricant not lubricate of retrogradation and change gradually in the oil groove.When the lubricant of thickening can not pass through oil pump nozzle, fault had just taken place in oil engine.

Therefore, the viscosity increase causes the unallowable wearing and tearing of oil engine, especially under the condition of cold.Avoid viscosity to increase that too fast to cause the main preventive measures of damage be the viscosity of discharging a spot of oil and maintenance lubricant from oil groove.So, problem becomes how to determine correct timed interval inspection oil cistern.Along with viscosity accelerated growth, check that the timed interval of lubricant viscosity must be littler, to guarantee that oil engine does not break down.

Be entitled as at one piece in the paper of " multiviscosisty of lubricating oil in Mack T-7 engine test " (Covitch, Humphrey and Ripple work) and point out, different compounds can be joined in the diesel fuel lubricity agent and limit thickening of lubricant.(Tulsa, Oklahoma read out on 1985.10.23) this piece paper in SAE fuel and lubricating oil meeting.It has told about how the cigarette ash (soot) as the not exclusively product generation of fuel enters in the lubricating oil in diesel engine.Exist cigarette ash relevant in the crankcase with the speed that the increase and the viscosity of lubricant viscosity increase.

In people's such as Koch application (September 24 1985 applying date, application number, U.S. attorney docket L-2226 B), advise that the mixture of Manny phase (Mannich) alkali of various transition metals can be used in the fuel.People such as Koch advise that also Schiff (Schiff) alkali can be introduced in its composition.People such as Dorer are in pending application (October 5 nineteen eighty-three applying date, application number, U.S. attorney docket L-2162 B) suggestion in, the mixture of manganiferous salt and copper bearing hydrocarbon dissolubility salt can be used as fuel dope, to reduce the burning-point of the useless particle that oil engine discharges.

In the U. S. application number (applicant Ripple, September 19 1985 applying date, U.S. attorney docket L-2238 R), described the diesel fuel lubricity agent of alkali metal containing salt as additive, it makes, and undesirable viscosity increase is reduced to minimum in the diesel engine.This application has further described the dispersion agent of the lubricating oil that is used for diesel engine crankcase.Disclosed the hydrocarbon dissolubility composition that contains the filtering metal element in the application (Application No., August 30 1984 applying date, U.S. attorney docket 2176B) of Tupa, it contains ashless dispersant and phenolic aldehyde antioxidant.

On June 6th, 1978, the U.S. of approval reissued patent 29, a kind of tentative composition has been described 661(applicant Hendrickson), it comprises the neutral treated oil (containing succinimide dispersants) of SAE, PHENOL 99.8 MIN ((CARBOLIC ACID)) calcium, and as the kerosin of a kind of metal ring alkyl salt of oxide catalyst, and the metal of being talked comprises copper, iron, tin, manganese and lead.In the Hendrickson patent, the purpose that comprises metal obviously is the oxidisability that improves oil for rapid, and its part as employed dispersion agent efficiency assay.

The United States Patent (USP) 4,529 of on July 16th, 1985 promulgation, 408(applicant Yan) suggestion can make burning of coal improve by a kind of metal that comprises several parts in per thousand parts of coals, and the ash corrosion is improved, and dirt and lime-ash obtain reducing.The additive that Yan proposes includes from Manganse Dioxide ferric oxide, manganese particle, a kind of material of selecting in sand and their mixture.

The United States Patent (USP) 4 of promulgation on October 25 nineteen eighty-three, 411,774(applicant Johnson) proposes, contain several parts of different metals in the waste oil in per 1,000,000 concentration, comprising tin, lead, copper, aluminium, iron, chromium, zinc, magnesium, nickel, barium, sodium, calcium, vanadium, molybdenum, boron and manganese.According to the saying of Johnson, also can contain silicon, phosphorus in the waste oil, also may contain silver.

The United States Patent (USP) 4,049 of on September 20th, 1977 promulgation, 562(applicant Hotten) propose, in the presence of a kind of solution of the naphthenate of cupric, iron, manganese, lead and chromium, but the anti-oxidant activity of test oil.This patent points out that further expection will be found the metal of distribution in exhausted diesel engine crankcase oil.

The United States Patent (USP) 4,122 of on October 24th, 1978 promulgation, 033(applicant Black) the various transition metals as oxidation retarder has been described.The United States Patent (USP) 3,652 of on March 28th, 1972 promulgation, 616(applicant Watson) the fuel and lubricant composition that contains metal such as zinc, manganese, chromium, copper, cobalt, vanadium, titanium, molybdenum, silver, cadmium, tungsten or mercury has been described.The European application 0024146(applicant Colelough that on February 25th, 1981 was announced) disclosed with copper as the antioxidant in the lubricant.

The present invention has been found that in diesel lubrication agent composition can oil-soluble form use more a spot of certain transition metal, with the relevant cigarette ash of speed (acceleration) that significantly reduces with viscosity increases and viscosity increases.Composition of the present invention is effective especially in being subjected to the diesel oil that viscosity strengthens harm rapidly.

In whole specification sheets and claims, all be by weight except that particularly pointing out per-cent and ratio, temperature is degree centigrade that pressure is to adopt kPa (Kpa) meter.Apply for that the reference of being quoted is applicable to the present invention, is incorporated herein by reference for this piece.

Feature of the present invention is a kind of lubricant compositions, and it comprises a kind of lubricant viscosity oil; A kind of dispersion agent; And the metallic compound of a kind of oil soluble of trace or oil-dispersing property, its consumption is to be enough to block the speed that is caused by cigarette ash, its viscosity increases when oil is used for diesel engine, and metallic compound wherein contains a kind of metal that is selected from manganese, titanium, cobalt, chromium, vanadium, nickel, tungsten, molybdenum and composition thereof.

Another embodiment of the invention is a kind of lubricant compositions, it mainly comprises a kind of lubricant viscosity oil and contains the about 30ppm～oil soluble of about 500ppm metal or the metallic compound of oil-dispersing property, when being used for diesel engine, the latter can block by cigarette ash and causes the speed that oil viscosity increases, wherein metallic compound contain a kind of be selected from manganese, titanium, cobalt, vanadium, nickel, tungsten, molybdenum, and composition thereof metal.

The present invention also described a kind of in being easy to accumulate the lubricating system of cigarette ash retardance cause the processing method of the speed that lubricant viscosity increases by cigarette ash, it comprises introduces step in a kind of lubricant to a kind of metallic compound, metal wherein be selected from manganese, titanium, cobalt, copper, vanadium, nickel, tungsten, chromium, molybdenum, and composition thereof, its consumption is enough to block the speed that viscosity increases.

Fundamentally, the present invention is a kind of composition that comprises a polyvalent metal compounds and a diesel fuel lubricity oil.Metallic compound comprise organic and inorganic form manganese, copper, nickel, vanadium, titanium, tungsten, cobalt, chromium, molybdenum, and composition thereof.Best, metallic compound contains manganese or titanium.At this, the carbolate of metal, salicylate, phosphoric acid salt, dithiocar-bamate and naphthenate also are effectively, and naphthenate is the metal compound species of recommending.

Mineral compound comprises as oxide compound, oxyhydroxide and carbonate.The present invention can also be with organic and mixture inorganic metal compound.The amount of employed metal should be enough to make the speed deceleration (Mack T-7 test) between 100～150 hours of viscosity increase.During 100～150 hours, the slope of the speed that viscosity increases should be less than 0.1, preferably less than 0.08.

The general salt of preferably at least a organic acid of organic compound that is used for metal component.When adopting the mixture of organic and inorganic metal component, very need to use a kind of organometallic compound to help metallic compound to be dispersed in the lubricant.

The organic acid that is used to prepare the salt of metallic compound can be a carboxylic acid, particularly contains the carboxylic acid of 1～30 carbon atom, for example carboxylicesters; Can also be sulfonic acid, especially contain the sulfonic acid that useful one or more alkyl (4～about 30 carbon atoms) replaces cyclophane structure (for example phenyl ring), for example certain sulphonate; Can also be the phosphoric acid that in its structure, contains one or more organic groups (contain 1～about 30 or more carbon atom).Organic acid is preferably used a kind of mixture of organic acid, and each carboxyl of the latter on average contains 7 carbon atoms at least, is advisable with about 4 to about 30, is preferably 6～30.

This carboxylic acid, sulfonic acid and phosphoric acid are well-known in the present technique field.Carboxylic acid can be monobasic or polycarboxylic acid (if the latter, representational is binary or tribasic carboxylic acid).

Monocarboxylic acid comprises C _1-7Lower acid (acetate, propionic acid etc.) and be higher than the higher acid (for example sad, capric acid etc.) of eight carbon atoms and the lipid acid of about 12～30 carbon atoms.New acids also is effective such as new sad and neodecanoic acid and analogue.

Lipid acid usually is the mixture of straight chain and branched acids, and for example it can contain 5%～about 30%(mole) straight-chain acid and about 70%～approximately 95%(mole) branched acids.Many fatty acid mixts that the ratio that contains straight-chain acid that other is commercially available is high also are effective.Can also use the mixture of the dimerization symphysis one-tenth of unsaturated fatty acids.

The high carboxylic acid comprises the di-carboxylic acid of having known that is made by the alkylation of maleic anhydride or derivatives thereof.The product of this reaction is the succsinic acid that hydrocarbon replaces, acid anhydrides etc.Also can use low-molecular-weight di-carboxylic acid as replacing succsinic acid such as tetrapropylene base succsinic acid and use about C with acid of polymethylene bridging (pentanedioic acid, hexanodioic acid, or the like) and lower molecular weight ₃₀The succsinic acid that replaces of homologue prepare salt of the present invention.

The high molecular substituted succinyl oxide, acid and the homologue that are used for preparing salt of the present invention appear at a large amount of patents, especially relate in the patent of making dispersion agent with the compound of acidylate at those being described.Typical high-molecular weight acid is those acid that make with polyisobutene component that has 30～400 carbon atoms (being generally 50～250) and maleic anhydride reaction.This class material was done to describe in following patent; United States Patent (USP) 3,172,892(applicant Le Suer etc. were issued March 9 nineteen sixty-five), United States Patent (USP) 3,219,666(applicant Norman etc. were issued November 23 nineteen sixty-five), United States Patent (USP) 3,272,746(applicant Le Suer etc. were issued on September 13rd, 1966).The monocarboxylic acid of other similar molecular weight can prepare by making vinylformic acid and derivative alkylation thereof.Also can use the mixture of this class acid.

Effective metallic compound of the present invention also can prepare from carboxylic acid even with acid oxy-compound such as alkylating phenol.This material is at United States Patent (USP) 4,100, and 082(applicant Clason etc. were issued on July 11st, 1978, particularly 15～17 the row) in done introduction.

The representational organic acid that is used to prepare salt of the present invention is a carboxylic acid, sulfonic acid, or its mixture, or contain the compound of these two kinds of acid functional groups.

The sulfonic acid that is used to form metallic compound comprises fat sulfonic acid class.The example of this sulfonic acid has mahogany acid, bright stock sulfonic acid; The sulfonic acid (the former Saybolt viscosity is about 100 seconds (37 ℃)～about 200 seconds (99 ℃)) that obtains from lubricating oil component; Vaseline sulfonic acid; Sulfonic acid and polybasic sulfoacid that benzene that single wax and many wax replaces, naphthalene, phenol, diphenyl ether, naphthyl disulfide, diphenylamine, thiophene, x-chloronaphthalene etc. are arranged; The sulfonic acid that also has other group to replace, alkyl benzene sulphonate (ABS) (wherein alkyl has 8 carbon atoms at least) for example, hexadecyl phenyl list thiosulfonic acid, dotriacontyl thianthrene disulfonic acid, dilauryl-beta-naphthalenesulfonic-acid, dioctyl nitro-naphthalene-monosulfonic acid, and an alkarylsulphonic acid, for example dodecylbenzene (bottoms) sulfonic acid.Dodecylbenzene (bottoms) mainly is the mixture of dodecylbenzene and two dodecylbenzenes.

Aliphatic sulfonic comprises paraffin sulfonic acid, unsaturated paraffin sulfonic acid, the paraffin sulfonic acid that hydroxyl replaces, six propene sulfonic acids, four amylene sulfonic acid, polyisobutylene sulphonic acid (wherein polyisobutene contain 20～7000 or more a plurality of carbon atom), chloro paraffin sulfonic acid, nitro paraffin sulfonic acid etc., alicyclic ring sulfonic acid such as petronaphthalene sulfonic acid, 12 cyclopentyl sulfonic acid, lauryl cyclohexyl sulfonic acid, two-(diisobutyl) cyclohexyl sulfonic acid, the cyclohexyl sulfonic acid that single wax or many wax replace etc.

Can in following United States Patent (USP), find about further specifying of the employed sulfonic acid of this paper:

Patent No. contriver issues the date

4 days November nineteen fifty-two of people such as 2,616,905 Asseff

People such as 3,027,325 Mc Millen on March 27th, 1962

People such as 3,312,618 Le Suer on April 4th, 1967

People such as 3,350,308 Mc Millen on October 31st, 1967

People such as 3,471,403 Le Suer on October 7th, 1969

People such as 3,488,284 Le Suer on January 6th, 1970

People such as 3,595,790 Norman on July 27th, 1971

3,798,012 Le Suer on March 19th, 1974

3,829,381 Le Suer on August 13rd, 1974

4,100,083 Ripple on August 22nd, 1978

4,326,972 27 days April nineteen eighty-two of Chamberlin

The useful salt of the present invention also can be produced from phosphoric acid, and this class phosphoric acid discloses in many United States Patent (USP)s and other document, and the example of this salt is at the United States Patent (USP) 4,191 of promulgation on March 4th, 1980,658(applicant Jahnke) in reveal phosphoric acid salt into following formula:

R ²（X ²）b

M is the metal of aforementioned metal compound or its mixture in the formula; R ¹And R ²It respectively is an alkyl; X ¹, X ², X ³And X ⁴Be oxygen or sulphur, a and b respectively are 0 or 1.

The salt of producing from organic acid can by make organic acid and metallics, preferably the manganese reaction prepares, this metallics is manganese oxide, manganous hydroxide, manganous carbonate, cupric oxide, copper hydroxide and copper carbonate for instance.

A kind of method that obtains the special recommendation of metallic compound is to adopt the form of overbasic salt.Overbasic salt is those organic acid salts that contain the excessive metal of the acid neutralization that is enough to make existence.In other words, overbasic salt is whenever the acidic part of amount contains metal more than the monovalent.This salt is being known in the art.About the disclosure of height alkalization, generally referring to United States Patent (USP) (applicant Piotrwski etc.) 3,827,979; United States Patent (USP) (applicant Le Suer etc.) was issued on April 4th, 1967) 3,312,618; United States Patent (USP) 2,616,904 and 2,616,905(applicant Asseff was issued November 4 nineteen fifty-two); United States Patent (USP) 2,595,790(applicant Norman etc.); With United States Patent (USP) 3,725,441(applicant Murphy etc. were issued on April 3rd, 1973).For the concrete disclosure of overbasic manganese of organic acid and mantoquita, referring to United States Patent (USP) 2,695,910(applicant Asseff etc. were issued on November 30th, 1954) and United States Patent (USP) 4,162,986(applicant Alratis etc. were issued on July 31st, 1979).

Specifically, the present invention relates to hydrocarbon dissolubility organic acid manganese salt.High alkaline manganese metal organic composite comprises a kind of mixture of oxide compound-oxyhydroxide-carboxylate salt of manganese, wherein contained metal in multi-nuclear metal oxide junction nucleus with the oxygen part of compounds, the then different monocarboxylic acid chemical combination of part with at least two kinds, or with one or more monocarboxylic acids with the mixture of the monobasic sulfonic acid that contains two carbon atoms at least with the form of hydroxyl-metal-carboxylate salt and hydroxyl-metal-sulfonate combination chemical combination mutually.For example, referring to United States Patent (USP) 4191658(Jahnke, issued) on March 4th, 1980.

Composition of the present invention is the hydrocarbon dissolubility preferably.In specification sheets and claims used term " hydrocarbon dissolubility " mean that this composition can dissolve or stable dispersion in common liquid hydrocarbon.Used term " energy stable dispersion " means composition and can be distributed to the degree that lubricant is worked with its predetermined way in lubricant in specification sheets and claims.Therefore, for instance, if composition can be suspended in the lubricating oil, and be enough to make oil to play the effect of lubricant, said composition is oil-soluble so.

The mixing of lubricating oil, metallic compound and dispersion agent can any mode easily be carried out.When using copper and manganese simultaneously, concerning the every grammeatom copper that is used for composition, adopt about 0.05～about 23 grammeatom manganese, the most handy about 2～about 23, best manganese with about 4～about 20 grammeatom.At this, also can use the mixture of manganese and titanium, manganese and cobalt and titanium and cobalt.The metal molar ratio of advising above-mentioned binary combination is about 15: 1～and 1: 15, preferably be about 10: 1～1: the ratio of first kind of metal of 10(and second kind of metal).

The present invention also considers to use other additive.For example, this class additive comprises detergent and the dispersion agent that produces ash or do not have the ash type.

The detergent that produces ash is the oily molten neutrality and the basic salt of alkali or alkaline-earth metal and following acid for example, described acid is sulfonic acid, carboxylic acid or is the organic phosphoric acid of feature with at least one direct C, for example those use phosphorization agent such as phosphorus trichloride, phosphorus heptasulfide, thiophosphoric anhydride, the tri-chlorination p and s, white phosphorus and fontanel sulphur, or sulfur subchloride phosphorus is handled the acid of olefin polymer (for example molecular weight is 1000 polyisobutene) preparation.The salt of the most frequently used this acid is sodium, potassium, lithium, calcium, magnesium, strontium, barium.

Term " subsalt " is used for representing following metal-salt, and wherein institute's containing metal has surpassed by the due amount of organic acidic group stoichiometric calculation.Preparing the general method of using of this subsalt is to heat together with certain metal neutralizing agent that surpasses stoichiometric quantity at about 50 ℃ of mineral oil solutions with a kind of acid, and filter the material of gained, described metal neutralizing agent for example is metal oxide oxyhydroxide, carbonate, hydrogen-carbonate or sulfide.

Know again, in neutralization procedure, use " promotor " can help to sneak into excessive a lot of metal.The example that is used as the compound of promotor has aldehydes matter, for example the product of phenol, naphthols, alkylphenol, thiophenol, sulphurized alkyl phenols and formaldehyde and certain aldehydes matter condensation; Also have alcohols, for example methyl alcohol, 2-propyl alcohol, octanol, cellosolvo, Trivalin SF, ethylene glycol, Stearyl alcohol, hexalin; Also have amine, for example aniline, phenylenediamine, thiodiphenylamine, Phenyl beta naphthylamine and amino dodecane.A kind of effective especially method for preparing subsalt comprises: a kind of acid and excessive certain basic alkaline earth metal neutralizing agent and at least a pure promotor one are reacted, and at high temperature (for example 60-200 ℃) with this mixture carbonating.

In burning, can not form generation a kind of non-volatile substance such as boron chloride or Vanadium Pentoxide in FLAKES though there is the ash dispersion agent according to it; But it does not generally contain metal, thereby burning the time do not produce metallic ash, is no ash detergent and dispersion agent so still call them.The ashless detergent and the dispersion agent of many types are known in the present technique field, and any of them all is applicable in the lubricant compositions of the present invention.Illustrate below:

(1) contain about at least 30, preferably the carboxylic acid of about at least 50 carbon atoms (or derivatives thereof) with nitrogenous compound as amine also just like phenol and the such organic hydroxide of alcohols, and/or the product that reacts of alkaline inorganic material one.The example of these " carboxylic dispersants " is in English Patent 1,306,529 and following many United States Patent (USP)s in description all arranged:

The patent inventor issues the date

3,163,603 Le Suer on December 29th, 1964

3，184，474

3,215,707 2 days November nineteen sixty-five of Rense

23 days November nineteen sixty-five of people such as 3,219,666 Norman

3,271,310 Le Suer on September 6th, 1966

People such as 3,272,746 Le Suer on September 13rd, 1966

3,281,357 Vogel on October 25th, 1966

3,306,908 Le Suer on February 28th, 1967

People such as 3,311,558 Prizer on March 28th, 1967

3,316,177 Dorer on April 25th, 1967

3,340,281 Brannen on September 5th, 1967

People such as 3,341,542 Le Suer on September 12nd, 1967

3,346,493 Le Suer on October 10th, 1967

3,351,552 Le Suer on November 7th, 1967

3,381,022 30 days April nineteen sixty-eight of Le Suer

3,399,141 27 days Augusts nineteen sixty-eight of Clemens

3,415,750 10 days December nineteen sixty-eight of Anzenberger

3,433,744 Le Suer on March 18th, 1969

People such as 3,444,170 Norman on May 13rd, 1969

3,448,048 Le Suer on June 3rd, 1969

People such as 3,448,049 Preuss on June 3rd, 1969

3,451,933 Leister on June 24th, 1969

3,454,607 Le Suer on July 8th, 1969

People such as 3,467,668 Gruber on September 16th, 1969

3,501,405 Willette on March 17th, 1970

3,522,179 Le Suer on July 28th, 1970

3,541,012 Stuebe on November 17th, 1970

3,542,680 Le Suer on November 24th, 1970

3，543，678

3,567,637 Sabol on March 2nd, 1971

3,574,101 Murphy on April 6th, 1971

People such as 3,576,743 Widmer on April 27th, 1971

People such as 3,630,904 Musser on February 28th, 1971

3,632,510 Le Suer on January 4th, 1972

3,632,511 Chien-Wei Liao on January 4th, 1972

3，697，428

3,725,441 Murphy on April 3rd, 1973

4,234,435 Meinhardt on November 18th, 1980

26,433 6 days Augusts nineteen sixty-eight of Le Suer of Re

(2) fat of higher molecular weight or alicyclic ring fontanelle compound and amine, the reaction product of polyalkylenepolyamines preferably.They are to be feature with " amine dispersion agent ", and the example is described in such as following United States Patent (USP):

The patent inventor issues the date

3，275，554

3，438，757

People such as 3,454,555 Vander Voort on July 8th, 1969

People such as 3,565,804 Honnen on February 23rd, 1971

(3) reaction product of alkylphenol and aldehyde (especially formaldehyde) and amine (especially polyalkylenepolyamines), wherein alkyl contains about 30 carbon atoms at least.This reaction product is to be feature with " Mannish dispersion agent ".This material is in following United States Patent (USP) illustrated:

The patent inventor issues the date

2,459,112 Oberright on January 11st, 1949

2,962,442 29 days November nineteen sixty of Andress

2,984,550 Chamot on May 16th, 1961

3,036,003 Verdol on May 27th, 1962

3，166，516

3,236,770 Matson on February 22nd, 1966

3,355,270 Amick on November 28th, 1967

3,368,972 13 days February nineteen sixty-eight of Otto

3,413,347 26 days November nineteen sixty-eight of Worrel

3,442,808 Traise on May 6th, 1969

3,448,047 Traise on June 3rd, 1969

3,454,497 Wittner on July 8th, 1969

3,459,661 Schlobohn on August 5th, 1969

3，461，172

People such as 3,493,520 Verdol on February 3rd, 1970

People such as 3,539,633 Piasek on November 10th, 1970

On January 26th, 1971 such as 3,558,743 Verdol

On June 22nd, 1971 such as 3,586,629 Otto

On July 6th, 1971 such as 3,591,598 Traise

On Augusts 17th, 1971 such as 3,600,5372 Udeihofen

On January 11st, 1972 such as 3,634,515 Piasek

3，649，229

On October 10th, 1972 such as 3,697,574 Piasek

3,725,277 Worrel on April 3rd, 1973

People such as 3,725,480 Traise on April 3rd, 1973

People such as 3,726,882 Traise on April 10th, 1973

People such as 3,980,569 Pindar on September 14th, 1976

(4) reagent aftertreatment carboxylic acid, amine or Mannich dispersion agent such as the succinyl oxide that replaces with urea, thiocarbamide, dithiocarbonic anhydride, aldehyde, ketone, carboxylic acid, hydrocarbon, nitrile, epoxide, boron compound, phosphorus compound and the product that obtains.This class examples of substances is described in following United States Patent (USP):

The patent inventor issues the date

3,036,003 Verdol on May 22nd, 1962

3,087,936 Le Suer on April 30th, 1963

3,200,107 10 days Augusts nineteen sixty-five of Le Suer

3,216,936 9 days November nineteen sixty-five of Le Suer

3,254,025 Le Suer on May 31st, 1966

3,256,185 Le Suer on June 14th, 1966

People such as 3,278,550 Norman on October 11st, 1966

3，280234

3,281,428 Le Suer on October 25th, 1966

3,282,955 Le Suer on November 1st, 1966

3,312,619 Dale on April 4th, 1967

30 days January nineteen sixty-eight of people such as 3,366,569 Norman

3，367，943

12 days March nineteen sixty-eight of people such as 3,373,111 Le Suer

3,403,102 24 days September nineteen sixty-eight of Le Suer

People such as 3,442,808 Traise on May 6th, 1969

3，455，831

3，455，832

People such as 3,493,520 Uerdol on February 3rd, 1970

3,503,677 Le Suer on March 24th, 1970

3,513,093 Le Suer on May 19th, 1970

3,533,945 Uogel on October 13rd, 1970

People such as 3,539,633 Piasek on November 10th, 1970

3,573,010 Mehmed basich on March 30th, 1971

3,579,450 Le Suer on May 18th, 1971

3,591,598 Traise on July 6th, 1971

3，600，372

3,639,242 Le Suer on February 1st, 1972

3，649，229

People such as 3,649,659 Otto on March 14th, 1972

3,658,836 Uineyard on April 25th, 1972

People such as 3,697,574 Piasek on October 10th, 1972

3，702，757

3，703，536

3，704，308

3,708,422 Swanson on January 2nd, 1973

(5) interpolymer of oil-soluble monomer (such as decyl-octyl methacrylate, vinyl ether in the last of the ten Heavenly stems and high molecular weight olefin) and the monomer that contains polar substituent (such as the acrylate of aminoalkyl acrylate or acrylamide and many-(oxygen ethyl) replacement).These are feature with " polymeric dispersant ", and its example is disclosed in following United States Patent (USP):

The patent inventor issues the date

3,329,658 Fields on July 4th, 1967

3，449，250

3,519,565 Coleman on July 7th, 1970

3,666,730 Coleman on May 30th, 1972

3,687,849 Abbott on August 29th, 1972

3,702,300 Coleman on November 7th, 1972

As previously mentioned, composition of the present invention is effective as the additive of diesel fuel lubricity agent.In general, these lubricant compositions comprise the lubricant viscosity oil of main amount and manganese or other metallic compound of the present invention of trace.

When the term of using in specification sheets and appended claims " trace " meant composition and contains the concrete material of " trace ", its content was lower than 50% of composition weight.

When the term of using in specification sheets and appended claims " main amount " meant composition and contains the concrete material of " main amount ", its content accounted for more than 50% of composition weight.

In general, the amount that joins the metallic compound in the present composition lubricating oil to make the metal that contains about 30ppm～500ppm in the handled lubricant compositions, with 30ppm～350ppm be advisable, preferably approximately 40ppm～approximately 150ppm(calculates by composition weight).

The lubricant viscosity oil that is used to prepare diesel fuel lubricity agent of the present invention can be natural oils, synthetic oils or its mixture as base oil.

Natural oils comprises animal oil and vegetables oil (for example Viscotrol C, lard) and mineral lubricating oils (for example petroleum liquid lubricating oil) and solvent treatment paraffin mineral lubricating oils that cross or acid treatment, cycloalkanes mineral lubricating oils or paraffin-cycloalkanes mixed type mineral lubricating oils.The lubricant viscosity oil that obtains from coal or shale also is effective.Ucon oil comprises that hydrocarbon ils and fontanel replace hydrocarbon ils, for example through the alkene (for example polybutene, polypropylene, propylene-isobutylene copolymers, chlorating polybutene etc.) of polymerization and copolymerization; Poly-(1-hexene), poly-(1-octene), poly-(1-decene) etc. and composition thereof; Alkylbenzene (for example dodecylbenzene, tetradecyl benzene, dinonyl benzene, two-(2-ethylhexyl) benzene etc.); Polyphenyl (for example biphenyl, terphenyl, alkylation polyphenyl etc.); Alkylation phenyl ether and alkylation diphenyl sulfide and derivative thereof, homologue, congener etc.

Alkylene oxide polymer and multipolymer and derivative thereof (wherein end group modification such as over-churning, etherificate) constitute another kind of known and operable ucon oil.These examples are by oxyethane or propylene oxide polymerization, by the alkyl of these polyoxyalkylene polymers and aryl ethers (the poly-Isopropanediol ether of the methyl of molecular-weight average about 1000 for example, the diphenyl ether of the polyoxyethylene glycol of molecular weight about 500～1000, the diethyl ether of the polypropylene glycol of molecular weight about 1000～1500, or the like) or its monobasic and multi-carboxylate (acetic ester for example, C ₃～C ₈Mixed aliphatic ester, or the C of Tetraglycol 99 ₁₃The oxygen acid diesters) oil of making.

Another kind of operable suitable lubricating oil comprises di-carboxylic acid (phthalic acid for example, succsinic acid, alkyl succinic acid, alkenyl succinic, toxilic acid, nonane diacid, suberic acid, sebacic acid, fumaric acid, hexanodioic acid, linoleic dimer, propanedioic acid, the alkyl propanedioic acid, the alkenyl propanedioic acid, or the like) with multiple alcohol (butanols for example, hexanol, lauryl alcohol, 2-Ethylhexyl Alcohol, ethylene glycol, monoalkyl ethers of diethylene glycol, propylene glycol, etc.) ester.The object lesson of this ester has Polycizer W 260, two (2-ethyl diethyldithiocarbamate) sebate, the just own ester of fumaric acid two, dioctyl sebacate, diisooctyl azelate, two different decayl esters of azelaic acid, dioctyl phthalate (DOP), didecyl phthalate, sebacic acid two-eicosane ester, dimeric two-(2-ethylhexyl) esters of linolenic acid, the complex ester that the Tetraglycol 99 of one mole sebacic acid and two moles forms with two moles reactions such as 2 ethyl hexanoic acid etc.

Ester as ucon oil also has those from C ₅～C ₁₂The ester that makes with many alcohol and many alcohol ethers (for example neopentyl glycol, TriMethylolPropane(TMP), tetramethylolmethane, Dipentaerythritol, tripentaerythritol etc.) of monocarboxylic acid.

The silica-based lubricating oil of poly-alkyl, poly-aryl, poly-alkoxyl group one class or poly-aryloxy-siloxane lubricant oil and silicon ester lubricating oil are another kind of useful synthetic lubricant (tetraethyl orthosilicates for example, silicic acid four isopropyl esters, four-(2-ethylhexyl) silicon ester, four-(4-methyl hexyl) silicon ester, four-(to tert-butyl-phenyl) silicon ester, hexyl (4-methyl-2-pentyloxy) sily oxide, poly-(methyl) siloxanes, poly-(aminomethyl phenyl) siloxanes etc.).Other ucon oil have liquid phosphorated acid ester (Tritolyl Phosphate for example, tricresyl phosphate hydroxy toluene ester, the diethyl ester of decane phosphoric acid, etc.) also have polytetrahydrofuran etc.

Refining, the refining and recovered oil of this class that discloses above is natural or synthetic (and they two or more mixture) arbitrarily all can be used in the enriched material of the present invention.Unpurified oil is that those directly obtain from natural or synthetic source, does not have the oil of further purification processes.For example, the direct shale oil that from the destructive distillation operation, obtains, direct petroleum oil or the direct esterised oil that obtains from esterification technique that obtains from primary distillation, they are not for further processing and just use, and such oil is unrefined oil.

Treated oil is similar to unrefined oil, and just they have done further processing to improve a kind of of it or some kinds of character in one or more purification step.It is that this area professional is known that this purification techniques has many, for example solvent extraction, and second distillation, hydrotreatment, hydrocracking, diafiltration etc. are filtered in acid or alkali extraction.

Recovered oil is to obtain by handle and the treated oil that acquisition treated oil similar methods is applied in the use again.This recovered oil is also referred to as and reclaims or reprocessed oils, they usually the metal of the product by directly removing remaining additive and oil breaking carry out other processing treatment.

At this, what recommended most is the oil of petroleum derivation with oil.In petroleum derived oils, chanced in this used keying action that various metal rose.

The influence that cigarette ash is produced in the speed that lubricant viscosity increases and the viscosity change is big can use the fresh lubricant of crossing according to metal treatment of the present invention to block by adding a part periodically.Thereby untreated at first (metal) lubricant can be by replacing original lubricating oil to be benefited with a kind of lubricant of handling in the middle of conversion lubricating oil.Metallic compound also can add in the crankcase in the presence of thinning oil, and wherein contained metallic compound and comparing of being found in oil are usually wanted excessive 1 to 25 times (with form of metal).In this method, contain and be low to moderate 1 liter additive by adding in the diesel engine crankcases of 20～25 liters of oil that are untreated and then can make metallic compound content reach requirement.

Generally be used for lubricating oil of the present invention, its consumption is the about 75%～99.5% of composition weight, is preferably about 80%～99% of weight.The thinning oil (lubricant) that exists with various additive forms is included in the above-mentioned amount.The consumption of dispersion agent as previously discussed generally is preferably the about 0.05%～20% of composition weight, is preferably 0.01%～15%.

At this used diesel fuel lubricity composition, preferably be substantially free of any type of lead, iron, aluminium or tin.Not having above-mentioned metal is ideal, and this is because they are antifriction metal (AFM) or the part material of normally forming oil engine.Fast in the analysis that shows (fleet owner), attrition resistant materials detect the wear problem that usually indicates oil engine, therefore attrition resistant materials does not wish to be included in the lubricant, because these materials have reduced the accuracy of this analytical procedure that is used to survey wearing and tearing.Do not wish that the described metal that exists also may play the oxide catalyst effect of oil, they can cause oily oxidation, thereby require oil to change prematurely.

The total basicnumber of diesel fuel lubricity agent is generally 0～25, preferably 1～15.This total basicnumber shows that lubricant is to stand to tend to the variation that acid increases.Acid increases and causes that corrosion increases, and high base number is represented acidproof increase.

In preferred embodiments, diesel fuel lubricity agent of the present invention also contain by at least a neutrality or alkalescence alkaline-earth metal form oil soluble metal salt with at least a acidic organic compound.The common name of this salt compound makes to contain the dispersion agent of ash, and acidic organic compound can be wherein a kind of of sulfuric acid, carboxylic acid, phosphoric acid, phenol, salicylate or its mixture at least.

Calcium, magnesium and vanadium are the alkaline-earth metal of being recommended, and also can use the salt of the mixture that contains two or more these alkaline-earth metal ions.

Effectively salt can be neutral or alkaline, and neutral salt contains a kind of alkaline-earth metal, and its amount just is enough to neutralize and is present in acidic-group in the salt anionic, and basic salt then contains excessive a kind of alkaline earth metal cation.

The amount that is included in the alkaline earth salt in the diesel fuel lubricity agent of the present invention also can in very large range change, and its significant quantity can be definite by the professional in present technique field at an easy rate.This salt plays a part auxiliary or additional detergent.The amount that is used for the alkaline earth salt of diesel fuel lubricity agent of the present invention can change to about 5% or higher from about 0% of composition weight, and preferably 0.5%～4%.

The present invention also considers to use other additive in diesel fuel lubricity agent composition of the present invention.These other additive comprises additive types commonly used, for example antioxidant, ultimate pressure agent, corrosion inhibitor, hectare select down the additive that depressant prescription, colour(ing)stabiliser, defoamer and other professional in the technical field of lubricant that makes up oil generally know that, when using antioxidant, the antioxidant of recommending is amine type, for example alkylation aromatic amine.Tertiary butyl hindered phenol preferably is not used in the present invention.If use, this hindered phenol should use with second kind of antioxidant.

Ultimate pressure agent and anticorrosive, examples of antioxidants have chlorinated aliphatic class such as chlorinated wax; Organic sulfide and polysulfide, for example dibenzyl disulfide ether, two (benzyl chloride base) two sulphur, dibutyl four sulphur, oleic sulfuration methyl ester, sulfenyl phenolate, sulfuration limonene and sulfuration terpenes; Also has phosphosulfurized hydrocarbon such as phosphoric sulfide product with turps or Witconol 2301 reaction; The phosphide that mainly comprises two hydrocarbon and three hydrocarbon phosphorous acid esters in addition, for example phenyl phosphites of the phenyl phosphites of dibutyl phosphorous acid ester, diheptyl phosphorous acid ester, dicyclohexyl phosphorous acid ester, amyl group phenyl sulfite, diamyl phenyl phosphites, three decyl sulfites, distearyl sulfite, dimethyl naphthyl phosphorous acid ester, oil base 4-amyl group phenyl phosphites, polypropylene (molecular weight 500) replacement, diisobutyl replacement; The thiocarbamate that also has metal, for example dioctyl zinc dithiocarbamate; The heptyl diamyl disulfide is for carboxylamine barium; The dithiophosphates that also has second main group metal, for example dicyclohexyl zinc dithiophosphate, dioctyl zinc dithiophosphate, two (heptyl phenyl)-phosphorodithioic acid barium, dinonyl phosphorodithioic acid cadmium, and by the zinc salt of thiophosphoric anhydride with the phosphorodithioic acid of the mixture reaction generation that waits mole Virahol and n-hexyl alcohol.

Many above-mentioned auxiliary ultimate pressure agent and corrosion one oxidation retarder also play the effect of anti-wear agent.The zinc dialkyl dithiophosphate compound is exactly an example of knowing.

Pour point reducer is the useful especially additive of a class, and it often is included in the lubricating oil described herein.Knowing in the art, using such pour point reducer in oil-based composition is in order to improve the cold property of oil-based composition.Example sees also " lubricant additive " (author: C.V.Smalheer and R.Kennedy Smith (Lezius-Hiles Co.publishers, Cleveland, Ohio, (1967)) the 8th page.

Effectively the example of pour point reducer is a polymethacrylate; Polyacrylic ester; Polyacrylamide, fontanel is for the condensation product of paraffin and aromatic substance; The polymkeric substance of vinyl carboxylates; And the terpolymer of dialkyl group fumarate, vinyl fatty ester and alkyl vinyl ether.Be used for the pour point reducer of the object of the invention and preparation thereof and use technology below United States Patent (USP) description is arranged.

The patent inventor issues the date

2，387，501

2，015，748

2，655，479

1，815，022

2,191,498 Reiff on February 27th, 1940

2，666，746

2，721，877

2，721，878

3,250,715 Wyman on May 10th, 1966

Defoamer is to be used for reducing or to prevent to form stable foam.Representational anti-pore forming material comprises siloxanes or organic polymer.Anti-foaming composition in addition Foam Control " (author: Henry T.Kerner(Noyes Data Corporation, 1976)) the 125th～162 page in description is arranged.

Viscosity modifier generally is to exist with about 5%～15% of composition weight.Viscosity modifier is used for keeping because lubricant temperature improves variation about viscosity.The example of viscosity activator is the multipolymer of hydrogenated styrene-isoprene; Maleic anhydride-styrene copolymers; Olefin copolymer, for example ethylene-propylene copolymer; Styrene-butadiene copolymer and homopolymer, for example polyhutadiene.

Below studying, only be used for illustrating embodiments of the invention, will understand further the present invention.As can be seen, other embodiment of the present invention can be conspicuous for present technique field professional from the research of following example.

Embodiment one

Prepare a kind of lubricant compositions that detailed prescription is arranged, it contains:

The composition umber

Mineral oil 92.45

Viscosity modifier 0.68

Basic alkylation Phenylsulfonic acid magnesium 0.77

Dispersion agent 3.48

Alkyl disulfide is for the zinc salt 1.43 of phosphoric acid

Wear-resistant detergent 1.11

Silicone antifoam agent 0.001

Antioxidant 0.08

Dialkyl benzene (alkylbenzene molecular weight

Average out to 300～380) sulfonic acid 50ppm

Manganese salt report is regarded the manganese metal as

The product of embodiment one obtains slope in operation in 100～150 hours be 0.018 Mack T-7 test-results.In current Mack T-7 test, qualified slope value is equal to or less than 0.04.The test-results that identical prescription (except that the manganese addition not) obtains is 0.16.

Embodiment two

The composition umber

Mineral oil 92.45

Viscosity modifier 0.68

Basic alkylation Phenylsulfonic acid magnesium 0.77

Dispersion agent 3.48

Alkyl disulfide is for the zinc salt 1.43 of phosphoric acid

Wear-resistant detergent 1.11

Silicone antifoam agent 0.001

Antioxidant 0.08

Manganese oxide, manganous hydroxide and

Manganese carboxylate (neodecanoate) is regarded manganese metal 40ppm as

It is 0.035 Mack T-7 test-results that this prescription has provided slope, and qualified be 0.04.The test-results of no manganese, slope value are 0.16.

Embodiment three

The composition umber

Mineral oil 92.45

Viscosity modifier 0.68

Basic alkylation Phenylsulfonic acid magnesium 0.77

Dispersion agent 3.48

Alkyl disulfide is for the zinc salt 1.43 of phosphoric acid

Wear-resistant detergent 1.11

Silicone antifoam agent 0.001

Antioxidant 0.08

Cobalt 50ppm as naphthenate

The slope value that contains the Mack T-7 test that the prescription of cobalt obtains is 0.068, and it shows with the prescription that does not contain cobalt compares, and result's improvement surpasses 50%.Crossed 100～150 hours interval, the lubricant viscosity under the no cobalt situation increases 58%.

Embodiment four

Prepare a kind of diesel fuel lubricity agent composition that detailed prescription is arranged, it contains:

The composition umber

Mineral oil 92.45

Viscosity modifier 0.68

Basic alkylation Phenylsulfonic acid magnesium 0.77

Dispersion agent 3.48

Alkyl disulfide is for the zinc salt 1.43 of phosphoric acid

Wear-resistant detergent 1.11

Silicone antifoam agent 0.001

Antioxidant 0.08

With the organic adducts 50ppm of different third titanium oxide

The titanium (regarding titanium metal as) that form exists

The Mack T-7 test-results of titanium compound, its slope is 0.026.When not using titanium, the oil body increase is 182%.

Embodiment five

The composition umber

Mineral oil 92.45

Viscosity modifier 0.68

Basic alkylation Phenylsulfonic acid magnesium 0.77

Dispersion agent 3.48

Alkyl disulfide is for the zinc salt 1.43 of phosphoric acid

Wear-resistant detergent 0.001

Silicone antifoam agent 0.08

This embodiment has used the PHENOL 99.8 MIN ((CARBOLIC ACID)) copper that contains 150ppm copper.Another change is to use the manganese salicylate that contains 450ppm manganese to replace PHENOL 99.8 MIN ((CARBOLIC ACID)) copper.

Embodiment six

Prepare a kind of lubricant compositions that detailed prescription is arranged

The composition umber

Mineral oil 92.45

Viscosity modifier 0.68

Basic alkylation Phenylsulfonic acid magnesium 0.77

Dispersion agent 3.48

Alkyl disulfide is for the zinc salt 1.43 of phosphoric acid

Wear-resistant detergent 1.11

Silicone antifoam agent 0.001

Antioxidant 0.08

With the manganic compound among the new octylate replacement embodiment one that contains the 100ppm vanadium.Another change is to use nickel, tungsten, molybdenum and the chromium of same amount to replace manganese.

Claims

1, a kind of lubricant compositions, it comprises a kind of lubricant oil; A kind of dispersion agent; With a kind of oil soluble of trace or the metallic compound of oil-dispersing property, its consumption is to be enough to block the speed that the oil viscosity that causes because of cigarette ash when being used for diesel engine increases, wherein metallic compound contain a kind of be selected from manganese, titanium, cobalt, copper, vanadium, nickel, tungsten, molybdenum, chromium, and composition thereof metal.

2, the lubricant compositions of claim 1, wherein lubricant viscosity oil accounts for about 75%～about 99.5% of composition weight.

3, the lubricant compositions of claim 1, wherein metallic compound calculates the about 30ppm～about 500ppm that accounts for composition by metal.

4, the lubricant compositions of claim 1, its total basicnumber are about 0～about 25.

5, the lubricant compositions of claim 1, unleaded basically.

6, the lubricant compositions of claim 1, wherein metallic compound is a kind of sulfonate.

7, the lubricant compositions of claim 1, wherein metallic compound is a kind of carboxylate salt.

8, the lubricant compositions of claim 1, wherein metallic compound is a kind of phosphoric acid salt.

9, the lubricant compositions of claim 1, wherein metallic compound is a kind of salicylate.

10, the lubricant compositions of claim 1, wherein metallic compound is a kind of carbolate.

11, the lubricant compositions of claim 1 contains a kind of about viscosity modifier of 5%～about 15% of composition weight that accounts for.

12, the lubricant compositions of claim 1, wherein metallic compound contain a kind of be selected from manganese, titanium, cobalt, and composition thereof integral part.

13, the lubricant compositions of claim 1, wherein metallic compound contain a kind of be selected from copper, chromium, and composition thereof integral part.

14, the lubricant compositions of claim 7, wherein carboxylate salt is the soap that a kind of each carboxyl has about 6～about 30 carbon atoms.

15, the lubricant compositions of claim 12, wherein metallic compound contains manganese.

16, the lubricant compositions of claim 12, wherein metallic compound contains titanium.

17, the lubricant compositions of claim 1, wherein dispersion agent is selected from the phosphorated olefin polymer, amine dispersion agent, Mannich dispersion agent, and the basic metal and the alkaline earth salt of carboxylic acid, sulfonic acid, organic phosphoric acid.

18, the lubricant compositions of claim 7, wherein carboxylic acid is to obtain from a kind of branched chain fatty acid.

19, the lubricant compositions of claim 17, wherein dispersion agent accounts for about 0.05～about 20% of composition weight.

20, the lubricant compositions of claim 1, wherein metallic compound is a kind of naphthenate.

21, the lubricant compositions of claim 1, wherein metallic compound is pressed metal calculating, accounts for about 35ppm～about 350ppm of composition.

22, the lubricant compositions of claim 1 also contains a kind of zn cpds.

23, a kind of lubricant compositions, it comprises a kind of lubricant viscosity oil of main amount and contains the oil soluble or the dispersed metallic compound of about 30ppm～about 500ppm metal, the latter can block the speed that is caused the oil viscosity increase when being used for diesel engine by the pharynx ash, and wherein metallic compound contains a kind of metal that is selected from manganese, titanium, cobalt, chromium, vanadium, nickel, tungsten, molybdenum and their mixture.

24, the lubricant compositions of claim 23, its total basicnumber are 0～about 25.

25, the lubricant compositions of claim 23 contains a kind of dispersion agent.

26, the lubricant compositions of claim 23, wherein metallic compound is a kind of carboxylate salt.

27, the lubricant compositions of claim 23, wherein metallic compound is a kind of phosphoric acid salt.

28, the lubricant compositions of claim 23, wherein metallic compound is a kind of salicylate.

29, the lubricant compositions of claim 23, wherein metallic compound is a kind of carbolate.

30, the lubricant compositions of claim 23 contains a kind of about viscosity modifier of 5%～about 15% that accounts for composition weight.

31, the lubricant compositions of claim 23, wherein metallic compound is a kind of metal that is selected from manganese, titanium, cobalt and compound thereof.

32, the lubricant compositions of claim 26, wherein carboxylate salt is the soap that a kind of each carboxyl has about 6～about 30 carbon atoms.

33, the lubricant compositions of claim 23, wherein metallic compound is a kind of naphthenate.

34, the lubricant compositions of claim 31, wherein metallic compound is a manganese.

35, the lubricant compositions of claim 26, wherein carboxylate salt is that a kind of branched chain fatty acid obtains.

36, the lubricant compositions of claim 23, wherein metallic compound is a kind of sulfonate.

37, the lubricant compositions of claim 23, wherein the metal in the metallic compound accounts for about 35ppm～about 350ppm of composition.

38, the lubricant compositions of claim 25, wherein dispersion agent accounts for about 0.1%～about 15% of composition weight.

39, the lubricant compositions of claim 23 is unleaded basically.

40, the lubricant compositions of claim 23 also contains a kind of zn cpds.

41, the lubricant compositions of claim 25, wherein dispersion agent is selected from the phosphorated olefin polymer, amine dispersion agent, Mannich dispersion agent, and the basic metal and the alkaline earth salt of carboxylic acid, sulfonic acid, organic phosphoric acid.

42, a kind of in being easy to accumulate the lubricant system of cigarette ash retardance cause the method for the speed that lubricant viscosity increases by cigarette ash, it comprises the step of a kind of metallic compound being introduced a kind of lubricant, wherein metal is selected from manganese, titanium, cobalt, copper, vanadium, nickel, tungsten, chromium, molybdenum and compound thereof, and its consumption is to be enough to block the speed that viscosity increases.

43, the method for claim 42, wherein the manganese metal that contains of metallic compound accounts for about 30ppm～500ppm of lubricant.

44, the method for claim 42, wherein metallic compound contains manganese.

45, the method for claim 42, wherein metallic compound contains titanium.

46, the method for claim 42, wherein metallic compound contains cobalt.