CN1020749C - Modified lubricant composition for saving fuel - Google Patents

Abstract

The present invention provides a lubricating oil composition for improved fuel economy comprising as major components an oil of lubricating viscosity and minor components: a mixture of (1) at least one overbased sulfonate or phenate and (2) at least one magnesium overbased sulfonate or phenate, (B) a mixture of (1) at least one zinc di-primary hydrocarbyl dithiophosphate and (2) at least one zinc di-primary hydrocarbyl dithiophosphate, (C) at least one ashless dispersant and (D) a copper carboxylate antioxidant.

Description

Improved lubricant compositions for enhanced fuel economy

The present invention relates to the obviously lubricating oil composition of fuel saving oil.Specifically, the present invention relates to except that containing dispersion agent and antioxidant addn, also contain the sulfonate of a spot of calcium and magnesium and the lubricating oil composition of primary and secondary zinc antiwear agents mixture.

Providing lubricating oil composition to make gasoline and diesel motor can obtain tangible improvement aspect fuel saving is an industrial big task.For this purpose, the project that is commonly referred to " additive for saving energy " develops, and its effect mainly is to improve the milimeter number or the mileage of per unit volume fuel.In recent years, the prescription of lubricating oil composition is very complicated, and the additive in this based composition must be complementary with other component wherein, and should not produce adverse influence to several other functions of traditional lubrication additive, and for example, dispersiveness, viscosity stability, anticorrosive and oxidation-resistance etc.

United States Patent (USP) 2911367 relates to the mineral oil composition that is used to prevent be exposed to the metallic surface corrosion of moisture, said composition contains main component mineral lubricating oils and the less added ingredients of amount, added ingredients is an an alkali metal salt, oil-soluble sulfonic acid, the alkyl-thio-phosphate of metal, each molecule has the polyvalent alcohol and the part ester that has the lipid acid of 8 carbon atoms at least of 3～6 carbon atoms and 3-6 hydroxyl, and the C of ethylene glycol ₆The side chain alkyl oxide.Said metal alkyl thiophosphate comprises the alkyl-thio-phosphate of magnesium, calcium, zinc, strontium, cadmium and barium, and wherein typical example is the dioctyl dithiophosphates of zinc and the octyl group hexyl dithiophosphates of zinc.Consumption by total composition sulfonate is 1～5%(weight), and metal alkyl sulphur, be 0.1～1.5%(weight for the preferable amount of phosphoric acid salt (comprising the dioctyl carbophenothion hydrochlorate of above-mentioned zinc and the octyl group hexyl carbophenothion hydrochlorate of zinc)).

United States Patent (USP) 3562159 relates to synthetic lubricant, the carboxylicesters that wherein contains the similar basic liquid of lubricant viscosity, as additive, also contain alkylation alkylene polyamines (about 5～30 weight parts), alkaline earth metal sulfonate (5～15 weight part), the di(2-ethylhexyl)phosphate sulfosalt of metal (5-70 weight part), the alkaline earth salt of phosphorylation hydrocarbon, hydrocarbon replaces the ester of succsinic acid, and alkylphenol sulphur alkaline earth salt.

United States Patent (USP) 3714042 relates to the high-alkali synthetics after the processing, and disclose this synthetics as additive at lubricating oil, be of great use in gasoline and other organic materials.Wherein the basic metal synthetics is selected from sulfonate, sulfonate-carboxylate salt and carboxylic acid synthetics, high in its amount of specified temperature condition to the total alkalescence that is equivalent to wherein, and used each carboxyl to contain the high molecular aliphatic anhydrides or the carboxylic acid of 25 aliphatic carbon atoms at least.But metal magnesium in the alkaline metal salt synthetics or calcium (the special metal example of quoting).Also other additive and said composition can be merged use, as the dithiophosphates of second main group metal, object lesson has dicyclohexyl zinc dithiophosphate and dioctyl zinc dithiophosphate.

United States Patent (USP) 3933659 relates to lubricating oil composition, wherein contain the main component oil of lubricant viscosity and the alkenyl succinimide of significant quantity, the II family metal-salt of dialkyl phosphorodithioic acid, alkalescence Sodium Sulphide earth metals alkyl phenate, and the compound that is selected from a certain fatty acid ester and fatty acid amide or amine.Wherein the amount of the II family metal-salt of dialkyl phosphorodithioic acid accounts for 0.5～1.5% of functional fluid weight, and the amount of alkaline Sodium Sulphide earth metals alkyl phenate accounts for 0.4～4%.

United States Patent (USP) 4308154 relates to the mixed metal salt (particularly zinc salt) of dialkyl dithiophosphoric acid and carboxylic acid, according to the document, these salt are of great use as antioxidant with the extreme-pressure additive that has improved thermostability for lubricant and functional fluid (as hydraulic fluid).Mixed metal salt in this invention also comprises I and II family metal-salt.

United States Patent (USP) 4417990 relates to mixed metal salt/phenol red salt composition, is used for lubricant and functional fluid as antioxidant and the improvement thermostability additive of anti-the extremely high pressure; United States Patent (USP) 4308154 disclosed contents have wherein been comprised.

For preparing required metal-salt, there is multiple scheme all to relate to the carbon content that occurs alkyl or aryl in the used dialkyl dithiophosphoric acid in the prior art, character and pattern.For example, mention in the United States Patent (USP) 2344393, think that in the past metal dithionite should have one or more chain alkyl for phosphoric acid salt, enough solubilities are arranged so that have the lubricating oil of actual application value; But it is oil-soluble for zinc phosphate that this patentee finds diamyl disulfide.Say in the United States Patent (USP) 3318808 that the alkyl that contains more (more than 4) carbon atom can increase oil soluble.Thus, this article is then said, use C capable of being combined ₄Alkyl and C ₅And C ₅Above than lower primary alcohols and/or secondary alcohol, each pure ratio should select to make consideration economically to coordinate mutually with the consideration on the solubility.

United States Patent (USP) 3190833 discloses oil soluble second family metal dithionite for phosphoric acid salt, and the dithiophosphates of wherein selecting calcium, barium, strontium, zinc and cadmium for use is good, is 7.6 aliphatic carbon atom and have overall mean in each phosphate radical at least.Be to improve the oil soluble of metal-salt, also make it with can be up to 0.75 mole epoxide reaction.

United States Patent (USP) 3000822 is that an another piece of writing relates to the preparation dithiophosphates, is used as the document of lubricant additive again.This article also mentions the mixture of zinc dialkyl dithiophosphate, and alkyl wherein comprises the lower molecular weight aliphatics uncle's alkyl that is less than 5 carbon atoms and has the mixture of the high molecular aliphatics uncle alkyl of 5 carbon atoms at least.The lower molecular weight alkyl is 1: 1～3: 1 to the ratio of high molecular alkyl in the zinc salt.

Multiple suggestion is arranged in the prior art in order to improve the practicality that on oil soluble, easily goes wrong than the low alkyl group dithiophosphates.United States Patent (USP) 4306984 discloses and has made non-oil soluble metal C ₂～C ₃Dialkyl dithiophosphate has oil-soluble method, and it is to make between dithiophosphates and alkenyl or alkyl list or the double amber imide to form title complex.Be used for the lubricated of such compositions of additives by can be used for the combustion engine crank case.In United States Patent (USP) 3843530, proposing another kind of preparation alkyl has the alkalescence of 1-13 carbon atom or the method for alkalescence and the non-crystallizable mixture of neutral blended zinc dialkyl dithiophosphate.In this alkalescence or alkalescence and the neutral zinc salt compound the individual different alkyl of 4-13 is arranged, average carbon atom content is 3.5-4.5, and contains 12%(weight at least) zinc.

United States Patent (USP) 4466895 also relates to lubricating oil composition; Wherein contain one or more dialkyl dithiophosphoric acid metal-salt; Wherein the 2-4 carbon atom to be arranged and have an alkyl at least be butyl to each alkyl, each phosphorus atom the total number of carbon atoms is less than 8, by mole wherein the alkyl of about 30-90% be that primary alkyl and the alkyl that 10-70% is arranged are secondary alkyl, metal-salt wherein is a zinc, copper or molysite, or its mixing salt, or the mixture of calcium salt and above-mentioned one or more salt; And when having only two alkyl, by the alkyl of the about 30-80% of mole be just-butyl, the alkyl of about 20-70% is a n-propyl.The patentee declares, decreases and antioxidant as lubrication oil antiwear, and these metal-salts are very useful.Document also mentions for example, and these lower dialkyl dithiophosphatess well are used in combination in the prescription in effect with the zinc dialkyl dithiophosphate of conventional more senior alkyl, also contain the sulfonated petroleum calcium salt of alkalescence and the mixture of magnesium salts in this prescription.

Prepared zinc dialkyl dithiophosphate up to now with the preparation of blended dialkyl dithiophosphoric acid.United States Patent (USP) 3293181 relates to at least two kinds of different branched-chain primary alcohol mixtures and prepares mixing salt, and wherein a kind of is isopropylcarbinol, and alcohol in addition contains 6 carbon atoms at least.

United States Patent (USP) 3397145 is open, but the alkyl straight or branched alkyl in the alkylthio phosphoric acid, alkyl the primary, the second month in a season and/or uncle's substituting group (identical or different alkyl).

United States Patent (USP) 3442804 relates to the zinc dithiophosphate that is used for lubricating composition, and alkyl wherein is primary alkyl and is made up of the mixture of harmonic component and macromolecule group.

United States Patent (USP) 4328111 relates to the high alkali sulfonate and the phenolate of modification, wherein the alkali compound with comprise organic carboxyl acid, organic carboxylic acid anhydride, phosphoric acid, phosphoric acid ester, the reaction of the acidic cpd of thiophosphatephosphorothioate or its mixture.

United States Patent (USP) 4614602 also relates to lubricant compositions, wherein contains the washing composition-dispersion agent lubricant additive of high alkali, contains the reaction product of the phenates and the alkyl benzene sulphonate (ABS) ammonium of alkaline-earth metal here; The patentee points out that also such additive can be used in combination with other traditional lubrication agent addition agent, comprises antiwear agents such as zinc dialkyl dithiophosphate.The abovementioned alkyl benzene sulfonate can comprise by alkaline-earth metal such as Ca, Mg, Ba, the sulfonate that its oxide compound or oxyhydroxide and their mixture derive out.For instance, the properties-correcting agent with high alkali sulfonic acid magnesium reaction can be 2-ethylhexyl phosphorodithioic acid.

United States Patent (USP) 4326972 discloses the method for improving the automotive fuel economic benefit, and it has adopted special lubricant compositions, and wherein neccessary composition is special vulcanising composition and basic metal sulfonate.

United States Patent (USP) 4362633 relates to lubricating oil additive, wherein contains the amination sulfide additive of molybdenum.The patentee points out, this additive can with the calcium phenates that contains high alkali, the compound of high alkali sulfonic acid magnesium and zinc dialkyl dithiophosphate is used in combination.

European patent 24146 relates to the lubricating oil composition that contains copper antioxidant; Contain the 400TBN sulfonic acid magnesium (magnesium that contains 9.2wt%) that also contains 1.0wt.% in the example of copper antioxidant in the lubricating oil composition, the 250TBN calcium phenates (calcium that contains 9.3wt.%) of 0.3wt.%, and alkyl zinc dithiophosphate; The mixture of the alkyl in the zinc dialkyl dithiophosphate wherein or this class group contains 4～5 carbon atoms, and uses P ₂S ₅With about 65% isopropylcarbinol and 35% amyl alcohol mixture prepared in reaction, making the phosphorus content in the lubricating oil composition is 1.0wt.%.

European patent application 92946 relates to the lubricating oil composition that improves fuel economy benefit, wherein contains glycerol part ester and oil soluble organocopper compound.The document has also been narrated the composition that contains aforesaid combination and be blended together with alkali metal detergent and antiwear agents.Document discloses, and desirable washing composition is common or the phenates of the calcium of high alkali or magnesium, sulfuration phenates and/or sulfonate; Also open, antiwear additive generally is oil soluble dialkyl zinc dithiophosphate and wherein the rarest 5 carbon atoms.

United States Patent (USP) 4394726 relates to the lubricating oil that contains the sulfur-bearing alkenediols that reduces the oil engine oil consumption.This patentee proposes, these fuel saving additives are in the oil for preparing fully, the high alkali alkyl trimagnesium phosphate that wherein contains 30 mmole/kilograms, the high alkali sulfuration polypropylene phenol calcium and the 18 mmoles/kilogram O of 20 mmole/kilograms, O-two (2-ethylhexyl)-zinc dithiophosphate.

United States Patent (USP) 4362636,4406803,4495088,4563293 and 4629576 all relate to the Saving Energy by Lubrication oil additive, and can for example understand every kind of additive with the form of full formula lubricating oil.

United States Patent (USP) 4104180 relates to the method for producing high alkali carbonate.In example 11, narrated and contained the neutral calcium phenylate of 1.2wt%, the lubricating oil of 1.2wt% zinc dialkyl dithiophosphate and 1.2wt% sulfonic acid magnesium.

People such as N.E.Gallopoulos (see ASLE Transactions Vol.14pp.1-7,1971) studied under the situation of the mixture ageing of sulfonate and zinc dialkyl dithiophosphate, and alkaline sulfonated petroleum calcium salt also works, reacting to each other between zinc dialkyl dithiophosphate and the lubricating oil dispersant; And reach a conclusion, chemical reaction is easy to take place.But the research report that does not have alkaline earth metal sulfonate mixture aspect.

People such as J.A.Mc Geehan (see SAE Daper 852133,1983, pps.879-892) have studied zinc dithiophosphate and the washing composition effect aspect the wearing and tearing of control dispersion agent.Conclusion is that aspect the wearing and tearing of control piston of gasoline engine, the diaryl zinc dithiophosphate is than the weak effect of zinc dialkyl dithiophosphate.The research of carrying out with multiple zinc dialkyl dithiophosphate and calcium or magnesium washing composition according to the author, reach a conclusion, in order to control the wearing and tearing of gasoline piston series, the wearing and tearing that diesel engine cylinder smooth finish difference band comes, and the wearing and tearing of the driven bronze pin of diesel oil arbor, the control engine scuffing need make the pattern match of zinc dithiophosphate and washing composition exactly.But do not point out the pattern of alkyl in the zinc dithiophosphate in the document, do not determine the effect of calcium magnesium detergent mixture yet.

Generally speaking, there is not one piece to disclose the relative quantity of controlling blending calcium/magnesium washing composition and mixing primary/secondary zinc dithiophosphate antiwear agents and can obtain actual benefit in the above-mentioned document.

Fig. 1 is the diagram that obtains data from example 1-27, the unexpected energy-saving effect that expression obtains with composition of the present invention.

The invention provides the lubricating oil composition that impels fuel saving, it comprises as the oil of the lubricant viscosity of principal constituent with as the fuel saving and the consumption of ancillary component and is able to improved following mixture:

(A) mixture of forming by high neutralizing treatment inhibitor of at least a calcium (1) and the high neutralizing treatment inhibitor of at least a magnesium (2);

(B) mixture of forming by at least a di-primary hydrocarbyl dithiophosphoric acid zinc (1) and at least a di-primary hydrocarbyl dithiophosphoric acid zinc (2);

(C) at least a ashless dispersant;

(D) carboxylate of at least a copper of anti-oxidant significant quantity;

Wherein, (A) in the amount of component (1) be expressed as 0.03～0.5wt% of lubricating composition with calcium; (A) amount of component (2) is expressed as the 0.01-0.25wt% of lubricating oil composition in magnesium; The amount of component (B) will be enough to provide the phosphorus of 0.05-0.15wt% to lubricating oil composition; And (A) (1) in the blended calcium magnesium washing inhibitor: (A) weight ratio of (2) is about 0.3: 1～6: 1, mixture (B) antiwear agents (B) (1): (B) weight ratio of (2) is between about 0.4: 1～9: 1.

Basis of the present invention is to be surprised to find that, wash inhibitor with blending calcium/magnesium in the crankcase lubricating oil composition and mix between the ratio of primary/secondary zinc antiwear agents definite relation is arranged improving fuel-saving effect, and these mixtures are given a certain amount of energy-saving effect of additive of unit weight just, and this is that this area was not recognized in the past.What have equivalence is, desirable character of other of lubricating oil and effect, and suitability for example, spatter property and dispersiveness, not therefore and impaired.

Component A

Component A is the salt of one or more following organic acid alkalescence calcium and magnesium, organic sulfonic acid (being mahogany acid or synthetic an alkarylsulphonic acid generally speaking), petroleum naphthenic acid, taste basic Phenylsulfonic acid, alkylphenol, alkylidene group diphenol, oil soluble lipid acid, Whitfield's ointment etc., the acid described in for example following United States Patent (USP), 2501731,2616904,2616905,2616906,2616911,2616924,2616925,2617049,2777874,3027325,3256186,3282835,3384585,3373108,3365396,3342733,3320162,3312618,3318809 and 3562159.For clearly, the content of above-mentioned patent disclosure has been narrated the useful mixture in the present invention at this and in this specification sheets thereby replenish.In sulfonated petro-leum, the most useful product is to remove the acid method preparation of becoming silted up and staying thing and purifying again with all suitable cuts of sulfonation.Synthetic an alkarylsulphonic acid is usually from alkylated benzenes preparation, for example the Friede-Crafts reaction product of benzene and polymkeric substance (as tetrapropylene).The acid that is suitable for the also alkyl derivative of available following compound prepares through sulfonation, diphenylene oxide base thianthrene for example, phenol diformazan thiophene (phcnolthioxine), diphenylene sulphur, the thiophene piperazine, diphenyloxide, phenylbenzene sulphur, diphenylamine, hexanaphthene, naphthane etc.

Make washing composition through high-alkali calcium magnesium sulfonate commonly used.Usually it is by the mixture heating up that will contain oil-soluble sulfonic acid salt or an alkarylsulphonic acid and excess base earth metal compound, form the method preparation of dispersive carbonate complex then by excessive alkaline-earth metal and carbon dioxide reaction, said excessive being meant surpasses the needed amount of all sulfonic acid that neutralization fully exists, and desirable high alkalinity is provided like this.Sulfonic acid generally is the method preparation with the aromatic hydrocarbons of sulfonated alkyl replacement, but aromatic hydrocarbons petroleum distillates and/or extract that alkyl replaces also can prepare from alkylated aromatic hydrocarbons, for example, alkylation benzene,toluene,xylene, naphthalene, biphenyl and halo derivatives thereof are as chlorobenzene, toluene(mono)chloride, chloronaphthalene.Alkylated reaction can be under the condition that catalyzer exists, with having 3 to carry out to the alkylating reagent more than 30 carbon atoms.For example, halogenated paraffin, the alkene that the paraffin dehydrogenation obtains, from ethene, the polyolefine that propylene etc. obtain etc. all is suitable for.Hydrocarbon aryl sulfonated bodies contains 9 to 70 or more a plurality of carbon atom usually, and it is more desirable that the aryl that replaces with each alkyl contains 16-50 carbon atom.

Be used for and an alkarylsulphonic acid comprises oxide compound with the alkaline earth metal compound that generates sulfonate oxyhydroxide, alkoxide, carbonate, carboxylate salt, sulfide, sulfhydrate, nitrate, borate and contain magnesium, the ether of calcium and barium.For example, calcium oxide, calcium hydroxide, magnesium acetate and magnesium borate.As above-mentioned, the consumption of alkaline earth metal compound is in will surpassing fully and the amount of an alkarylsulphonic acid.Usually consumption be fully in the required stoichiometric 100-220% of sulfonic acid, more desirable is at least 125%.

Known multiple other the method for preparing the alkaline-earth metal alkylaryl sulfonate, as the method in United States Patent (USP) 3150088 and 3150089, high alkalinity wherein is to be used in hydrocarbon diluting solvent W/O to separate the method for alcoxyl-carbonate and alkoxy aromatic yl sulfonate title complex and obtain.

Desirable sulfonic acid magnesium additive to be the total alkali number be an alkarylsulphonic acid magnesium of about 300-400 is about 25～32wt% by the content of the gross weight sulfonic acid magnesium that is distributed to the additive in the lubricating oil.Desirable calcium sulphonate additive is an alkarylsulphonic acid calcium of the about 300-400 of total alkali number, and by the total amount that is distributed to the additive in the lubricating oil, its consumption is about 25-32wt%.

Concrete grammar example as the used title complex of preparation, can be with oil-soluble sulfonic acid, two Witco 1298 Soft Acids of synthetic for example, in 50-150 ℃ with excessive lime (as every angelic acid 10 equivalent lime), reaction promotor such as methyl alcohol, heptyl phenol or its mixture, and certain solvent (as mineral oil) mixes mutually, then with these process stream carbonatings, up to forming equal phase materials.According to the process in the United States Patent (USP) 3312618, just can obtain sulfonic acid, the title complex of carboxylic acid or its mixing acid.Another example is the preparation sulfonic acid magnesium, can use common magnesium salts for this reason, excessive magnesium oxide, water, and alcohol, for example methyl alcohol.

The carboxylic acid that is used for preparing sulfoacid carboxylic acid title complex and carboxylate ligand compound (used the sulfoacid carboxylic acid mixture or only used carboxylic acid in a certain step of technological process as the title complex that obtains from above-mentioned technology) is an oil-soluble acid, comprises the one-level lipid acid that has at least 12 24 fatty carbon atoms are arranged at most.The example of this class acid comprises, palmitinic acid, stearic acid, tetradecanoic acid, oleic acid, linolic acid, tridecanoic acid, docosanoic acid etc.Certainly also the ring carboxylic acid be can use, aromatic acid and band lipid acid comprised.Aromatic acid is meant and contains benzene ring structure (as phenyl ring or naphthalene nucleus) and oil-soluble group or have the acid that adds up to 15-18 carbon atom at least, preferably contains 15-200 carbon atom.The example of aromatic acid has, stearyl phenylformic acid, phenyl stearic acid, phenylformic acid or naphthoic acid (its cerul has 18 carbon atoms at least) that single wax or many wax replace, hexadecane yl benzoic acid etc.Cycloaliphatic acids should have 12 at least, and about 30 carbon atoms that arrive are generally arranged more, and example has petroleum naphthenic acid, hexadecane basic ring cyclohexane carboxylic-acid, dilauryl naphthane carboxylic acid, dioctyl Cyclopentane carboxylic acid etc.On the carboxyl of above-mentioned acid, the thiocarboxylic acid that one or two Sauerstoffatom is replaced by sulphur is very to wish.In the mixture of sulfonic acid and carboxylic acid, sulfonic acid is at least 1 to the ratio of carboxylic acid: 1(is by chemical equivalent), generally be lower than 5: 1, be preferably in 1: 1～between 2: 1.

The meaning of term " basic salt " and " high alkali salt " is to calculate by stoichiometry, and the amount of metal in the salt is bigger than the amount of sulfonate radical.

In this specification sheets and claims, term " title complex " is meant alkaline metal salt, and wherein the amount of metal of Cun Zaiing is greater than the amount of metal of normal-salt or neutral salt." the alkali number " of title complex refers to measure with volumetry, the milligram number of the KOH suitable with 1 gram title complex.Usually the method for preparing basic salt comprises that as oxide compound, oxyhydroxide, carbonate, supercarbonate or sulfide heat (being higher than 5 ℃ at least) together with the oil solution and the metal neutralizing agent of acid with the normal-salt of metal, filters then.The help excess metal participation reaction of using at neutralization procedure " promotor " is known, and being that this based composition of preparation is preferential uses.The example of promotor has aldehydes matter such as phenol, naphthols, alkylphenol, the polycondensation product of thiophenol sulphurized alkyl phenols and formaldehyde and aldehydes matter; Alcohols such as methyl alcohol, 2-propyl alcohol, octanol, cellosolve, Trivalin SF, ethylene glycol, stearic alkanol and hexalin; Amine such as aniline, inferior phenylenediamine, thiodiphenylamine, phenol beta-naphthylamine and lauryl amine.

Usually the alkaline compositions that makes is as stated above used carbon dioxide treatment again, is lower than 50(by ASTM up to the alkali number, and D2896 measures).

Usually discovery, the method for following carbonating with alkaline substance and each interpolation back of the portion of pursuing interpolation calcium or magnesium is very favourable to the formation basic prod.Can obtain the product of containing metal ratio very high (10 or higher) with this method.Term " metal ratio " refers to the normal ratio of equivalent p-sulfonic acid root negatively charged ion of alkaline-earth metal in the sulfonate title complex herein.For example, the metal ratio of normal sulfonate is 1, and in the calcium sulphonate title complex, if when containing 2 times of calcium in the normal sulfonate, the ratio of metal is 2.Be suitable as the mixture of component A, metal ratio is at least 1.1.For example can be 1.1-30, desirable metal ratio is about 2-20.

Often find that alkaline sulfonate and anthranilic acid are heated to 140-200 ℃, and to make its reaction be very favourable.The consumption of anthranilic acid generally is lower than 1 weight fraction/10 weight fraction sulfonate, desirable 1 weight fraction/40～200 weight fraction.The existence of anthranilic acid can improve the anti-oxidant and erosion resistance of sulfonate.

This area neutral and alkali alkaline earth metal sulfonate is known, and discloses its preparation method in many pieces of patents, as United States Patent (USP) 3027325,3312618 and 3350308.These patents described sulfonate of other patent that neutralizes all can use in the present invention.

The basic salt that preferably prepares calcium and magnesium respectively mixes then according to quantity.In general, the condition fusion that exists at the used thinner of preparation or solvent these respectively the preparing washing inhibitor will be very easily.

Represent that with Ca the consumption of calcic washing composition inhibitor combination should be about 0.03% to 0.5%(weight of lubricating oil composition), with about 0.04% to 0.4%(weight) be good, and with about 0.05 to 0.2%(weight) better.Represent that with magnesium the consumption that contains magnesium washing composition inhibitor should be about 0.01% to 0.25%(weight of lubricating oil composition), with about 0.01% to 0.2%(weight) be good, and with about 0.02% to 0.11%(weight) better.Being preferably overbasic calcic washing composition inhibitor and the overbasic consumption that contains magnesium washing composition inhibitor and being every part contains magnesium washing composition inhibitor and uses about 0.3 to 6 part of calcic washing composition inhibitor, to use about 0.4 to 3 part is good, use about 0.8 to 1,2 part of the best (representing) with respective metal.

Component A also can contain other alkaline earth and/or basic metal washing composition inhibitor, as alkalescence or neutral sodium sulfonate, potassium sulfonate and sulfonic acid lithium and salicylate thereof and alkalescence or neutral barium sulfonate, phenylic acid barium and barium salicylate.The example that is used as the mixture of component A has the mixture of overbasic calcium sulphonate, overbasic sulfonic acid magnesium and overbasic sodium sulfonate washing composition inhibitor.

Component B:

This component is the metal-salt of (1) di-primary hydrocarbyl dithiophosphoric acid and the mixture of the metal-salt of (2) di-secondary hydrocarbyl dithiophosphoric acid.The acids that can produce the B-1 metal-salt can be illustrated by the acid of formula I

（Ⅰ）

R in the formula ¹And R ²Identical or different, can be the similar substantially alkyl of alkyl, cycloalkyl, aralkyl, alkaryl or structure.The acids that can form the B-2 metal-salt can be illustrated by the acid of formula II:

R in the formula ³, R ⁴, R ⁵, and R ⁶Identical or different, can be the similar substantially alkyl of alkyl, cycloalkyl, alkaryl or structure.

" alkyl that structure is similar substantially " is meant that group contains substituting groups such as ether, ester, nitro or halogen and the hydrocarbon characteristic of this group of not remarkably influenced.

Therefore can think that the acids of formula I contains di-primary hydrocarbyl substituent, wherein the carbon of each and oxygen bonding be primary carbon, promptly-CH ₂-O.Equally, can think that the acid of formula II contains the di-secondary hydrocarbyl substituent, wherein the carbon of each and oxygen bonding is secondary carbon, promptly

CH-O.

Suitable R ¹To R ⁶The object lesson of group comprises sec.-propyl, isobutyl-, normal-butyl, sec-butyl, n-hexyl, heptyl, the 2-ethylhexyl, diisobutyl, iso-octyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, butyl phenyl, adjacent, right-the diamyl phenyl, octyl phenyl, the phenyl that polyisobutene (molecular weight 350) replaces, the phenyl that tetrapropylene replaces, β-octyl group butyl naphthyl, cyclopentyl, cyclohexyl, phenyl, chloro-phenyl-, the orthodichlorobenzene base, bromophenyl, naphthylmethylidyne, the 2-methylcyclohexyl, benzyl, the benzyl chloride base, the chlorine amyl group, dichlorophenyl, nitrophenyl, dichloro decyl and xenyl.With with the alkyl of about 3 to 30 carbon atoms be advisable with the aryl of about 6 to 30 carbon atoms.Especially Shi Yi R ¹To R ⁶Group is the alkyl of 3 to 18 carbon.

By making the reaction of thiophosphoric anhydride and alcohol or phenol be easy to obtain phosphorodithioic acid.Reaction is included under about 20 to 200 ℃ 4 mol of alcohol or phenol is mixed mutually with one mole of thiophosphoric anhydride.React generation and discharge hydrogen sulfide.

Effectively metal-salt comprises the salt that contains I main group metal, II main group metal, aluminium, lead, tin, molybdenum, magnesium, cobalt and nickel in the present invention.The metal of recommending is a zinc.Can comprise Lithium Oxide 98min with the example of the metallic compound of this acid-respons, lithium hydroxide, Quilonum Retard, lithium valerate, sodium oxide, sodium hydroxide, yellow soda ash, sodium formiate, Sodium Propionate, sodium phenolate, potassium oxide, potassium hydroxide, salt of wormwood, potassium formiate, silver suboxide, silver carbonate, magnesium oxide, magnesium hydroxide, magnesiumcarbonate, magnesium acetate, propionic acid magnesium, the phenol magnesium salts, calcium oxide, calcium hydroxide, lime carbonate, calcium formiate, calcium propionate, valeric acid calcium, zinc oxide, zinc hydroxide, zinc carbonate, zinc propionate, strontium oxide, strontium hydroxide, Cadmium oxide, cadmium hydroxide, cadmium carbonate, cadmium acetate, barium oxide, hydrated barta, the barium hydrate, barium carbonate, barium acetate, valeric acid barium, aluminum oxide, propionic acid aluminium, plumbous oxide, lead hydroxide, lead carbonate, stannic oxide, butyric acid tin, cobalt oxide, cobaltous hydroxide, cobaltous carbonate, the valeric acid cobalt, nickel oxide, nickel hydroxide and nickelous carbonate.

In some cases, mix some composition such as little metal acetate or acetate and metal reaction agent and also produce the product that is improved with helping this reaction.For example, use up to about 5% the zinc acetate and the shared formation that helps zinc dithiophosphate of zinc oxide of requirement.

The method for making of phosphorodithioic acid metal-salt is well-known technically, does to introduce in a large amount of granted patent, comprises United States Patent (USP) 3293181; 3397145; 3396109 and 3442804, the organic disulfide of using among described relevant preparation the present invention draws at this for the disclosure of the method for phosphate metal salt and is reference.

Preferably prepare B-1 and B-2 metal-salt respectively, be mixed and made into the wear-resistant component B of blended then.In other words, primary acid para-acid I and II can form blended B-1 and B-2 metal-salt then and there, form the component B with required metal-salt B-1 and metal-salt B-2 equivalence ratio.

The consumption of component B in lubricating oil composition should effectively provide about 0.05% to 0.15%(weight) phosphorus compound, with about 0.07% to 0.12%(weight) for good, especially with about 0.08% to 0.11%(weight) be good.The relative consumption of used metal-salt B-1 and B-2 is quite crucial to the present invention.Metal-salt B-1(is the metal-salt of the di-primary hydrocarbyl dithiophosphoric acid of formula I) consumption be the di-secondary hydrocarbyl dithiophosphoric acid metal-salt of every approximately shares of metal B-2(formula II) with about 0.4 to 9 weight part, with 0.5 to 3 weight part is good, is the best with 0.7 to 1.8 weight part.

Component C:

Be used for dispersion agent ashless, nitrogenous or ester of the present invention and comprise and be selected from the list that (1) oil soluble salt, acid amides, imide, oxazoline and long chain hydrocarbon replace and ester class or its mixture of dicarboxylic acid or acid anhydrides, (2) band is the Manny phase condensation product that forms of the phenol that replaced by about 1 mole of long chain hydrocarbon of the long chain aliphatic hydrocarbon of coupled polyamine and (3) and about 1 to 2.5 mole formaldehyde and about 0.5 to 2 mole polyalkylene polyamine condensation directly; Wherein the long chain hydrocarbon groups described in (1), (2) and (3) is C ₂To C ₁₀(as C ₂To C ₅) the polymkeric substance of monoolefine, the number-average molecular weight of this polymkeric substance is about 300 to about 5000.

C(1): list or omega-dicarboxylic acids material that the long chain hydrocarbon groups used in dispersion agent replaces, i.e. acid, acid anhydrides or ester comprise the long chain hydrocarbon of replacement, generally are polyolefine, general every mole of polyolefine on average replaces have an appointment 0.8 mole of α or β-unsaturated C at least ₄To C ₁₀Di-carboxylic acid, acid anhydrides or its ester, about 1.0 to 1.8 to be good, as 1.1 to 1.6 moles.The example of this monobasic and di-carboxylic acid, acid anhydrides and ester thereof has fumaric acid, methylene-succinic acid, toxilic acid, maleic anhydride, chloromaleic acid, dimethyl fumarate, chloro maleic anhydride, vinylformic acid, methacrylic acid, Ba Dousuan and styracin etc.

The olefin polymer of the formation dispersion agent that be used for and the unsaturated dicarboxylic acid of recommending reacts is to contain big molar weight C ₂To C ₁₀(as C ₂To C ₅) the polymkeric substance of monoolefine.This alkene comprises ethene, propylene, butylene, iso-butylene, amylene, octene-1 and vinylbenzene etc.Polymkeric substance can be multipolymer such as the ethene and the propylene of homopolymer such as polyisobutene and two or more these class alkene; Butylene and iso-butylene; The multipolymer of propylene and iso-butylene etc.Other multipolymer comprises that the polymer monomers of wherein less molar weight [as 1 to 10%(mole)] is C ₄To C ₁₈The non-conjugated diene hydrocarbon, as the multipolymer of iso-butylene and divinyl, or ethene, propylene and 1, the multipolymer of 4-hexadiene etc.

In some occasion, olefin polymer can be saturated fully, the ethylene-propylene copolymer that for example uses hydrogen to produce by the Z-N synthesis method as conditioning agent control molecular weight.

The number-average molecular weight that is used for the olefin polymer of dispersion agent generally should be about 700 to about 5000, more generally is about 900 to about 3000.Particularly the number-average molecular weight of the olefin polymer of Shi Yonging is about 900 to about 2500, the about double-key end group of each polymkeric substance chain belt.Particularly the extremely effectively raw material of dispersant additives that is suitable for is a polyisobutene.Can measure the number-average molecular weight of this base polymer by several currently known methodss.A kind of conventional determining method is to adopt gel permeation chromatography (GPC), this method also provides molecular weight distribution data, see W.W.Yau, " the Modern Size Exclusion Liquid Chromatography " of J.J.Kirkland and D.D.Bly, John Wiley and Sons, New York, 1979.

Olefin polymer and C ₄To C ₁₀The reaction method of unsaturated two no carboxylic acids, acid anhydrides or ester is known technically.For example, can such as in United States Patent (USP) 3361673 and 3401118 introduction, simply heat olefin polymer and di-carboxylic acid material, heat " alkene " reaction is taken place.Or can first halogenated olefin polymer, for example, chlorination or bromination, by passing to about 0.5 to 10 hour of chlorine or bromine (being advisable) to polyolefine with 1 to 7 hour at 60 ℃ to 250 ℃ (as 120 ℃ to 160 ℃), based on the polymer weight meter, reach about 1% to 8%(weight) chlorine or bromine (being advisable) with about 3% to 7%.Make halogenated polymer and capacity unsaturated acid or anhydride reaction 0.5 to 10 hour (as 3 to 8 hours) then under 100 to 250 ℃ (generally being about 180 ℃ to 235 ℃), every mole of halogenated polymer of the product of Huo Deing will contain the unsaturated acid of required mole number like this.At United States Patent (USP) 3087436; 3172892; 3272746 and other this type of document in this class methods of touching upon.

On the other hand, when mixing and heating olefin polymer and unsaturated acid material, feed chlorine to this heatable substance.At United States Patent (USP) 3215707; 3211587; 3912746; 4110349; 4234435 and English Patent 1440219 in these class methods are introduced to some extent.

After using halogen, 65% to the 95%(weight of generally will having an appointment) polyolefine is (as polyisobutene and two no carboxylic acid substance reactions.And when not using halogen or catalyzer to carry out thermal response, 50% to the 75%(weight of then generally only having an appointment) polyisobutene reaction.Chlorination helps to increase reactive behavior.For simplicity, the unit that above-mentioned di-carboxylic acid produces and the ratio of polyolefinic functionality (as being 0.8 to 2.0 etc.) are based on the polyolefine total, promptly are used to the reaction and the unreacted polyolefinic total amount that manufacture a product.

The material that can produce di-carboxylic acid also can be further and reactions such as amine, alcohol (comprising polyvalent alcohol), amino alcohol, generates other useful dispersant additives.If therefore desire to make acid former further to react, as neutralize, then generally be that 50% acid unit down to whole larger proportions reacts at least.

Comprise as the amine compound of the nucleophilic reaction agent of hydrocarbyl substituted dicarboxylic carboxylic acid material neutralization reaction and to be with about 2 to 60(to be advisable in the molecule with 2 to 40, as 3 to 20) carbon atom and be with about 1 to 12 (to be advisable with 3 to 12, preferably 3 to 9) monoamine and polyamine (better), the preferably polyalkylene polyamine of nitrogen-atoms.These amine can be alkylamines or comprise other group such as the alkylamine of carboxyl, alkoxyl group, amide group, itrile group, mew quinoline base etc., and what particularly be suitable for is carboxyl amine with 1 to 6 carboxyl, is advisable to be with 1 to 3 carboxyl.The amine of recommending is the saturated amine of aliphatics, comprises the amine that general formula is following:

R, R ', R " and R " ' respectively are selected from hydrogen, C in the formula ₁To C ₂₅Straight or branched alkyl, C ₁To C ₁₂Alkoxy C ₂To C ₆Alkylidene group, C ₂To C ₁₂Carboxyamino alkylidene group and C ₁To C ₁₂Alkylamino C ₂To C ₆Alkylidene group, wherein R " ' also can comprise the following formula group:

（Ⅴ）

In the formula definition of R ' as above, S and S ' can be identical or different, are 2 to 6, are advisable with 2 to 4; T and t ' can be identical or different, are 0 to 10, are advisable with 2 to 7, be preferably about 3 to 7, but the summation of t and t ' are not more than 15.In order to ensure effecting reaction, preferably select R, R ', R ", R ' ", S, S ', t and t ' can make formula III and formula IV compound generally be with a primary amine or secondary amine group at least, be advisable to be with two primary amine or secondary amine group at least.This can by select in described R, R ', R ", R " ' group at least one as hydrogen or make t in the formula IV as R " ' be hydrogen or be at least 1 during when V group band secondary amino group and reach.The most desirable amine is the amine shown in the formula IV in the above general formula, contains at least two primary amine groups in this amine, and contains at least one primary amine group, is advisable with at least three.

The non-limitative example of suitable amine compound comprises: 1, the 2-diaminoethanes, 1, the 3-diaminopropanes, 1, the 4-diaminobutane, 1, the 6-diamino hexane, polyvinylamine such as diethylenetriamine, Triethylenetetramine (TETA), tetren, polypropylene amine is as 1, the 2-propylene diamine, two (1, the 2-propylidene) triamine, two (1, the 3-propylidene) triamine, N, N-dimethyl-1, the 3-diaminopropanes, N, N-two (2-amino-ethyl) quadrol, N, N-two (2-propyloic)-1, the 3-propylene diamine, 3-dodecyloxy propylamine, N-dodecyl-1, the 3-propanediamine, three carboxymethylamino methane (THAM), diisopropanolamine (DIPA), diethanolamine, trolamine, one, two and three fat amine, amino morpholine such as N-(3-aminopropyl) mixture of morpholine and above-mentioned amine.

Other amine compound that is suitable for comprises alicyclic diamine as 1,4-two (amino methyl) hexanaphthene and heterocyclic nitrogen compounds such as tetrahydroglyoxaline and general formula following (V N-aminoalkyl piperazine a):

P in the formula ₁And P ₂Identical or different, be 1 to 4 integer, n ₁, n ₂And n ₃Identical or different, be 1 to 3 integer.The non-limitative example of this class amine comprises 2-pentadecyl tetrahydroglyoxaline, N-(2-amino-ethyl) piperazine etc.

Use the mixture effect of commercially available amine compound better.For example, a kind of method for preparing alkylene amines comprises alkylene dihalide (as ethylene dichloride or propylene dichloride) and ammonia react, produce the complex mixture of alkylene amines, wherein alkylidene group all is connected with geminative nitrogen, forms compounds such as diethylenetriamine, Triethylenetetramine (TETA), tetren and isomery piperazine.The commercial goods is called " PolyamineH ", " Polyamine 400 " and poly-ethylene amines average per molecules such as " Dow Polyamine E-100 " 5 to 7 nitrogen-atoms of having an appointment, and its cost is lower.

Effectively amine also comprises the polyoxy alkylidene polyamines, this class amine following as general formula.

（Ⅵ）

Formula is that m is about 3 to 70, is advisable with 10 to 35; With

（Ⅶ）

" n " is about 1 to 40 in the formula, but all n ' sums are about 3 to 70, is advisable with about 6 to 35, and R is the multivalence saturated hydrocarbyl of maximum 10 carbon atoms, and wherein the replacement radix on the R base is by a value representation, and its numerical value is 3 to 6.Alkylidene group in formula VI or the formula VII can be the straight or branched that contains about 2 to 7 carbon atoms (being advisable with about 2 to 4).

The molecular-weight average of the polyoxy alkylidene polyamines of formula VI or formula VII (being advisable with polyoxy alkylidene diamines and polyoxy alkylidene triamine) is about 200 to about 4000, is advisable with about 400 to about 2000.The polyoxy alkylidene polyamines of recommending comprises polyoxyethylene diamines and polyoxy trimethylene diamine and polyoxy propylidene triamine (average molecular weight range is about 200 to 2000).For example, the polyoxy alkylidene polyamines can trade(brand)name " Jeffamine D-230, D-400, D-1000, D-2000, T-403 " etc. have been bought from Jefferson chemical company.

Contain 5% to 95%(weight by heating) the di-carboxylic acid material oil solution to about 100 to 250 ℃ (being advisable) 1 to 10 hour with 125 to 175 ℃ (as 2 to 6 hours, the water requirement until removing, then amine is easy to and selected di-carboxylic acid material such as the reaction of alkenyl succinyl oxide.Suitable heating helps forming the mixture of imide or imide and acid amides, rather than acid amides and salt.The di-carboxylic acid material can be with reagent and one-tenth's key type noticeable change to the reaction ratio of amine and other nucleophilic reaction agent equivalents described herein.Generally use the group (as grafted maleic anhydride) of 0.1 to 1.0 mole di-carboxylic acid whenever amount nucleophilic reaction agent (as amine), and with about 0.2 to 0.6(as 0.4 to 0.6) be advisable.For example, preferably use about 0.8 mole of five yuan of amine (two primary amine groups of per minute subband, and be 5 equivalent nitrogen) be converted into acid amides and imido mixture, this product is to make by the maleic anhydride reaction that makes 1 mole of alkene and capacity, every mole of alkene addition have 1.6 moles of succinic anhydride group both the consumption of the five yuan of ammonia amine that should be every nitrogen equivalent be enough to for about 0.4 mole of succinic anhydride group (being 1.6/(0.8 * 5) mole).

Nitrogenous dispersion agent also can further carry out the boration processing by the general argumentation in United States Patent (USP) 3087936 and 3254025 (it is reference that this paper draws).By using the boron compound treatment of selected acyl group nitrogen dispersion agent that is selected from boron oxide, halogenation boron, boric acid and boric acid ester; be easy to realize this processing; the boron of the consumption of boron compound for about 0.1 atomic ratio being provided for mole acylations nitrogen composition is so that the nitrogen of every atomic ratio acylations nitrogen composition provides the boron of about 20 atomic ratios.By this boration acyl group nitrogen compound total amount, the dispersion agent of the present composition generally contains about 0.05 to 2.0%(weight) boron of (as 0.05 to 0.7%).[show as dehydration boric acid polymkeric substance in product, mainly be (HBO to boron ₂) ₃] being considered to link to each other with imide with the dispersion agent imide becomes amine salt, as the metaborate of this imide.

By add about 0.05% to 4% to the acylations nitrogen compound; as 1% to 3%(weight) boron compound of (based on this acyl group nitrogen compound weight meter) (is good with boric acid especially; often add with the slurries form) and in about 135 ℃ to 190 ℃ (as 140 to 170 ℃) stirring heating 1 to 5 hour; again under this temperature with purging with nitrogen gas, be easy to carry out this processing.Perhaps also can carry out boron by dehydration simultaneously in the hot mixt that boric acid is added to di-carboxylic acid material and amine handles.

Three carboxymethylamino methane (THAM) can generate acid amides, imide or ester class additive (as described in English Patent 984409) or generate oxazoline compound and boration oxazoline compound (as described in United States Patent (USP) 4102798,4116876 and 4113639) with above-mentioned acid substance.

The ester that carboxylic compound such as the di-carboxylic acid material that ashless dispersant is also replaced by above-mentioned long chain hydrocarbon and a carboxyl and many carboxyls alcohol or aromatic substance such as phenol and naphthols generate.Many carboxyl alcohol are best oxy-compound, are advisable to about 10 carboxyls to contain 2, and for example ethylene glycol, Diethylene Glycol, triethylene glycol, TEG, dipropylene glycol and other aklylene glycol, wherein alkylidene group contains 2 to about 8 carbon atoms.Other many carboxyls alcohol that is suitable for comprises glycerol, glycerol monoleate, glycerol monostearate, glycerol monomethyl ether, tetramethylolmethane, dipentaerythritol and composition thereof.

The ester dispersion agent also can be generated by unsaturated alcohols such as vinyl carbinol, styryl carbinol, propargyl alcohol, the pure and mild oleyl alcohol of 1-hexamethylene-3-.Other alcohols that can produce ester of the present invention also comprises ether-alcohols and amino-alcohols, for example comprises the alcohols that oxyalkylene, oxygen arylidene, amino alkylidenyl and amino arylidene with one or more oxyalkylenes, amino alkylidenyl or amino arylidene, oxygen arylidene replace.The example has glycol monoethyl ether, ethyl carbitol, N, N, and N ', N '-tetracarboxylic three methanediamines and at most with the ether-alcohols of about 150 oxyalkylenes, wherein alkylidene group contains 1 to about 8 carbon atoms.

The ester dispersion agent can be succsinic acid diester or acid ester, be the succsinic acid of partial esterification; And many carboxylics of partial esterification alcohol or phenol, promptly have the ester of free alcohol or phenol carboxyl.The mixture of the ester class of more than enumerating is also thought and is belonged to scope of the present invention.

Can prepare the ester dispersion agent as enumerating method in the United States Patent (USP) 3381022 by one or more methods.Be similar to nitrogenous dispersion agent mentioned above, the ester dispersion agent also can be by boration.

Can replace carboxyl amine that the di-carboxylic acid substance reaction generates dispersion agent with above-mentioned long chain hydrocarbon and comprise 2-amino-1-butanols, 2-amino-2-methyl-1-propanol, right-(β-propyloic) aniline, 2-amino-1-propyl alcohol, 3-amino-1-propyl alcohol, 2-amino-2-methyl-1, ammediol, 2-amino-2-ethyl-1, ammediol, N-(β-carboxylic propyl group)-N '-(beta-aminoethyl) piperazine, three (carboxymethyl) aminomethane, 2-amino-1-butanols, thanomin, β-(β-hydroxy ethoxy) ethamine etc.Also can use the mixture of these amine or similar amine.Be suitable for comprising amine, alcohol and containing mixed amine and the compound of the reactive functional groups of carboxyl, i.e. amino-alcohol with the di-carboxylic acid of alkyl replacement or the above-mentioned nucleophilic reaction agent of anhydride reaction.

The no ash content dispersion agent of recommending is by replacing with succinic anhydride group and making with the polyisobutene of inferior propylamine of poly-ethyleneamines reaction (as tetren, penten), polyoxyethylene and polyoxy (as polyoxy trimethylene diamine, three carboxymethylamino methane and tetramethylolmethanes) and composition thereof reaction.A kind of disperser composition of special recommendation comprise that (1) succinic anhydride group replaces and with (2) carboxylic compound (as tetramethylolmethane), (3) polyoxy alkylidene polyamines (as the polyoxy trimethylene diamine) composition with the polyisobutene of (4) polyalkylene polyamine (as polyethyene diamine and tetren) reaction, every mole (1) described in its consumption such as the United States Patent (USP) 3804763 use respectively about 0.3 to about 2 moles (2) and (4) and about 0.3 to about 2 moles (3).The disperser composition of another recommendation comprises that the aliphatic primary amine of the many carboxyls alcohol of (1) polyisobutenyl succinic anhydride and (2) polyalkylene polyamine (as tetren) and (3) or many carboxyl substituted is (as the composition (as described in the United States Patent (USP) 3632511) of tetramethylolmethane or three carboxymethylamino methane.

C(2) also be suitable for as the nitrogenous dispersion agent of no ash content of the present invention, shown in United States Patent (USP) 3275554 and 3565804, the nitrogenous polyamines in this dispersion agent directly is connected with the long chain aliphatic hydrocarbon phase, and wherein the halogen on the halohydrocarbon is replaced by the many alkane of different alkylidene groups.

C(3): operable another kind of nitrogenous dispersion agent be contain as technically known mannich base or those dispersion agents of Manny phase condensation product.As at United States Patent (USP) 3442808,3649229 and the disclosed content of 3798165(this all draw be with reference to) described in, produce this class Manny phase condensation product and generally be and make list that about 1 mole of high-molecular-weight hydrocarbons replaces or polyhydroxy-benzene (is 1000 or higher as number-average molecular weight) and about 1 to 2.5 moles of formaldehyde or paraformaldehyde and about 0.5 to 2 mole of polyalkylene polyamine carry out condensation.This class Manny phase condensation product can contain the long-chain high-molecular-weight hydrocarbons or can react (as shown in the above-mentioned United States Patent (USP) 3442808) with the compound that contains this class hydrocarbon (as polyalkenyl succinic anhydrides) on phenolic group.

Component D

Be used for oxidation inhibitor of the present invention and comprise the carboxylic acid copper compound, this compounds can be used as the source of oil-soluble copper in the lubricating oil.This copper can be used as any suitable oil-soluble carboxylic acid copper's compound and is blended among the oil.Our said oil soluble be meant this carboxylate compounds at oil or contain in the whole series prescription of additive, be that part is oil-soluble at least under normal mixing condition.This copper compound can cuprous or cupric form exist.Although one mole of Red copper oxide or cupric oxide can be respectively and one or two mole of phosphorodithioic acid reaction, copper still can the dialkyl sulfo-or the form of phosphorodithioic acid copper exist, wherein replace zinc in above-claimed cpd and the reaction with copper.In addition, copper can synthesize or the form of natural carboxylic acid's mantoquita is added.The example comprises C _10-18Lipid acid such as stearic acid or palmitinic acid because the processing and the solubility characteristic of resulting copper carboxylate can improve, thereby are that naphthenic acid or the synthesis of carboxylic acid of 200-500 is good with unsaturated acid such as oleic acid or branched carboxylic acids such as molecular weight.Same be suitable for also have general formula be (the oily fusibleness dithiocarbamic acid copper of nCu of RR ' NCSS), n is 1 or 2 in the formula, R and R ' are identical or different C _1-18Alkyl is with C _2-12Alkyl is good, and they comprise the base such as alkyl, alkenyl, aryl, aralkyl, alkaryl and this class of alicyclic hydrocarbon radical.Especially be C with R and R ' _2-8Alkyl is good.Therefore, for instance, this class group can be ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, sec-butyl, amyl group, n-hexyl, isohexyl, n-heptyl, n-octyl, decyl, dodecyl, octadecyl, 2-ethylhexyl, phenyl, butylbenzene base, cyclohexyl, methylcyclopentyl, propenyl, butenyl etc.In order to possess oil soluble, (R and R's ') the total number of carbon atoms generally is about 5 or more.Also can adopt sulfonic acid copper, copper phenates and acetylacetone copper.

In final lubricating oil or fuel composition, the consumption of copper antioxidant (for example copper naphthenate, cupric oleate or its mixture) is generally about 40-500ppmw metal.

Be used for the cheap of copper antioxidant of the present invention, and can under lower concentration, bring into play effectiveness, therefore, adopt this antioxidant that the cost of product is not had materially affect.The result who is produced usually is better than and adopts the result that oxidation inhibitor produced in the past, and antioxidant in the past is cost height but also working concentration height not only.In any case, the consumption of copper compound all must not influence the performance of other component in the lubricating composition, when except B component, and when copper compound is unique antioxidant, the result that can obtain to be entirely satisfactory.Adopt copper antioxidant to reduce or eliminate demand fully auxiliary antioxidant.Like this, only under special exacting terms, just need to adopt traditional auxiliary antioxidant.Yet, required consumption when the consumption of required auxiliary antioxidant is less than no copper compound far away and exists.

When the copper antioxidant with any significant quantity adds in the lubricating oil composition, this significant quantity that desired is is enough to make that about 40-500(is arranged in the above-mentioned lubricating oil composition that contains copper antioxidant is good with 50-200, be more preferably 80-150) ppm copper, this copper content is that the weight with lubricating oil composition is that benchmark calculates.Certainly, the consumption span also depends on the other factors that can exert an influence to the quality of base stock lubricating oil preferably.

Lubricating oil composition

Lubricating oil composition, for example automatic transmission fluid, be applicable to the heavy-duty oil of petrol motor and diesel engine etc., can adopt additive preparation of the present invention.Can also prepare the universal crankcase oil that lubricating oil composition wherein not only had been applicable to petrol motor but also had been applicable to diesel engine.These lubricant formulas generally contain multiple different additive, and these additives give prescription required characteristic just.These diverse additives comprise viscosity index improver, antioxidant, inhibiter, other washing, ashless dispersant, pour point depressant, other wear preventive additive etc.

In the preparation process of lubricant formula, the common practice be import with 10-80%(heavy) [for example 20-80%(is heavy)] additive that active ingredient enriched material form exists, these concentrate and are present among hydrocarbon ils (for example mineral lubricating oils) or other suitable solvent.At the preparation finished lube, for example in the process of crankcase automotive engine oil, with respect to a whole set of prescription of every weight part additive, common available 3-100, for example rare these enriched materials of the lubricating oil of 5-40 weight part.Certainly, the purposes of these enriched materials is to make in the processing of various materials to be convenient to carry out and to be easy to be dissolved or dispersed among the finished product mixture.Therefore, for instance, in lubricating oil distillate, usually adopt heavy with 40-50%() enriched material form the component A-Ca/Mg hydrocarbyl sulfonic salt mixture or the Ca/Mg alkyl phenate that exist.

Component A of the present invention, B, C and D generally with contain the oil product that possesses lubricating oil viscosity, the lube oil base stocks that comprises natural and ucon oil and composition thereof mixes use.

Can adopt any traditional mode that component A, B, C and D are added among the lubricating oil.Therefore, these mixtures can directly add in the oil by dispersing or dissolving, and make that the concentration of washing composition inhibitor and wear preventive additive reaches required numerical value respectively in the oil.If these materials are added in the additional lubricating oil, carry out under then must or heating up in room temperature.In addition, these components and the oil-dissolving solvent and the base oil that suit can be mixed,, this enriched material be mixed with lube oil base stocks obtain end formulation so that form enriched material.

The lubricant base that is applicable to component A and B can play a role selectively by combine formation lubricating oil composition (i.e. prescription) with additional additive.

Natural oil product comprises that animal oil and vegetables oil (for example Viscotrol C, lard), liquid oils oil and paraffinic, cycloalkane and combination chain alkane-cycloalkane are to cross hydrofining, solvent treatment or acid-treated mineral lubricating oils.The oil product that possesses lubricant viscosity that is obtained by coal or shale also is the base oil that is suitable for.

Oxyalkylene base polymer and interpolymer and wherein hydroxyl constituted another kind of known ucon oil by the derivative that reactions such as esterification, etherificate obtain modification.The example that can Gong enumerate has the polyoxyalkylene polymers that makes by oxyethane and propylene oxide polymerization, the alkyl and the aryl ethers (for example the methyl of molecular-weight average 1000-poly-Isopropanediol ether, molecular weight are that phenyl ether, the molecular weight of the polyoxyethylene glycol of 500-1000 are the diethyl ether of the polypropylene glycol of 1000-1500) of these polyoxyalkylene polymers; And monobasic and multi-carboxylate, for example acetic ester, mixed C _3-8The C of fatty acid ester and tetraglycol ₁₃The oxygen acid diester.

Another kind of suitable ucon oil comprises di-carboxylic acid (for example phthalic acid, succsinic acid, alkyl succinic acid and alkenyl succinic, toxilic acid, nonane diacid, suberic acid, sebacic acid, fumaric acid, hexanodioic acid, linoleic acid dimer, propanedioic acid, alkyl propanedioic acid, thiazolinyl propadiene) and the formed ester of various alcohol (these alcohol are just like butanols, hexanol, dodecyl alcohol, 2-Ethylhexyl Alcohol, ethylene glycol, Diethylene Glycol monoether, propylene glycol).The specific examples of these esters comprises Polycizer W 260, sebacic acid two (2-ethylhexyl) ester, the 2-ethylhexyl diester of the just own ester of fumaric acid two, dioctyl sebacate, diisooctyl azelate, nonane diacid two isodecyls, dioctyl phthalate, phthalic acid didecyl ester, sebacic acid two (eicosyl) ester, linoleic acid dimer and the mixed ester of being gone by 1 mole of sebacic acid and two moles of tetraglycols and two moles of 2 ethyl hexanoic acid reactions.

Ester class as synthetic oil product comprises that also those are by C _5-12The ester that monocarboxylic acid and polyvalent alcohol and polyhydroxy ethers such as neopentyl glycol, TriMethylolPropane(TMP), tetramethylolmethane, Dipentaerythritol and tripentaerythritol constitute.

Silicone oil such as poly-alkyl one, poly-aryl one, poly-alkoxyl group one or poly-aryloxy siloxanes oil product and silicic acid ester oil has been formed another kind of suitable ucon oil; They comprise tetraethyl orthosilicate, silicic acid four isopropyl esters, silicic acid four (2-ethylhexyl) ester, silicic acid four (4-methyl-2-ethylhexyl) ester, silicic acid four (to tert-butyl-phenyl) ester, six (4-methyl-2-pentyloxy) sily oxide, poly-(methyl) siloxanes and gather (tolyl) silica and wash.Other ucon oil comprises phosphorous acid esters of liquid (for example diethyl ester of Tritolyl Phosphate, trioctyl phosphate, decylphosphonic acid) and polytetrahydrofuran.

Without refining, through refining and all can be used among the lubricating oil of the present invention through the oil product of re-refining.Not direct by oil product natural or that synthetic source obtains without the purified oil product through further purification processes for those.For instance, can be the shale oil that directly obtains, the petroleum oil that distillation directly obtains or the ester oil that just is not used that directly obtains without the purified oil product through further processing by esterification process by the destructive distillation operation.Treated oil is similar to unrefined oil, thereby different is treated oil is purified through a step or multistep its a kind of or multifrequency nature is improved.To those skilled in the art, many these class purification techniquess such as distillation, solvent extraction, acid or alkali extraction, filtration and diafiltration all are known.Smart again ester oil can by will with obtain the treated oil similar methods and be applied to the treated oil that had been used and obtain.This treated oil also can be considered rerefined oil or reprocessing lubricating oil, and usually adopts the technology that removes inactivation additive and oil breaking product that it is carried out additional processing.

Thereby New-type detergent inhibitor of the present invention/wear preventive additive mixture can use with viscosity index improver and form multistage General Motors engine oil.Viscosity modifier is given lubricating oil high-temp and cold operation performance and is made it still can keep the state of adhesion when heating up and present acceptable viscosity or flowability at low temperatures.Viscosity modifier generally also comprises the high-molecular-weight hydrocarbons base polymer of polyester.This class viscosity modifier can also make it have other characteristic or function by deriving, as dispersing characteristic.Adopt gel permeation chromatography or osmometry to measure as can be known, the number-average molecular weight of these oil soluble viscosity modified polymkeric substance is generally 10 ³-10 ⁶, with 10 ⁴-10 ⁶Be the best, for example 20000-250000.

The example of suitable hydrocarbon polymer comprises by two or more C _2-30(C for example _2-8) homopolymer and multipolymer that olefinic monomer constitutes, this class monomer comprises x-alkene and internal olefin, they can be straight or branched aliphatic series, aromatics, alkyl aromatic, alkene such as alicyclic.Above-mentioned polymkeric substance is ethene and C normally _3-30The polymerisate of alkene, especially the multipolymer with ethene and propylene is good.Can be for other polymkeric substance of selecting for use just like polyisobutene, C ₆With the homopolymer of senior x-alkene and hydrogenation polymkeric substance and multipolymer and the terpolymer and the hydroderivating thing thereof of multipolymer, atactic polypropylene(APP), vinylbenzene and (for example) isoprene and/or divinyl.For instance, by mastication, extrude, oxidation or thermal destruction can reduce the molecular weight of this polymkeric substance, and makes it oxidized and contain aerobic.The example of suitable hydrocarbon polymer comprises that also derived polymer such as ethylene-propylene and reactive monomer are as can (for example alkylene polyamine or oxyamine are as United States Patent(USP) Nos. 4,089,794 with alcohol or amine; 4,160,739; 4,137, shown in 185) the further back graft copolymerization body that maleic anhydride constituted of reaction, or ethene and propylene and nitrogen compound be (as U.S. Patent No. 4,068,056; 4,068,058; 4,146,489 and 4,149, shown in 984) multipolymer that forms of reaction or grafting.

Hydrocarbon polymer is that to contain 15-90%(heavy preferably) ethene, heavy with 30-80%() ethene be good and 10-85%(heavy), heavy with 20-70%() be good one or more C _3-28(with C _3-18For good, be more preferably C _3-8) ethylene copolymer of x-alkene.Measure as can be known by X-light and Differential Scanning Calorimeter, the degree of crystallinity of this multipolymer is heavy to be lower than 25%() for good, this point is unimportant.With the copolymer from ethylene and propylene is best.Be fit to instead of propylene formation multipolymer or make up other x-alkene that is used to form terpolymer, tetrapolymer etc. comprise 1-butylene, 1-amylene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene etc. with ethene and propylene; Side chain x-alkene such as 4-methyl-1-pentene, 4-methyl isophthalic acid-hexene, 5-Methyl-1-pentene, 4,4-dimethyl-1-amylene and 6-methyl isophthalic acid-heptene etc., and composition thereof.

Also can use by ethene, above-mentioned C _3-28Terpolymer, tetrapolymer that alpha-olefin and non-conjugated dienes or this class diene mixture constitute.The consumption of non-conjugated dienes is a benchmark in the total amount of ethene and x-alkene, generally is about the 0.5-20%(mole), with about 1-7%(mole) be good.

The polyester viscosity index improver is generally olefinic C _3-8The polymkeric substance of the ester of unsaturated monobasic and di-carboxylic acid such as methacrylic acid toxilic acid, maleic anhydride, fumaric acid etc.

The example of the unsaturated ester that can Gong select for use comprises the ester class of the aliphatic saturated monohydroxy alcohol that contains 1 carbon atom (is good with 12-20 carbon atom) at least such as decyl acrylate, dodecylacrylate, vinylformic acid stearyl, vinylformic acid eicosyl ester, vinylformic acid docosyl ester, decyl-octyl methacrylate, fumaric acid diamyl ester, methacrylic acid dodecyl ester, methacrylic acid cetyl ester, methacrylic acid stearyl or the like and composition thereof.

Other ester class comprises C _2-22Lipid acid or monocarboxylic acid (with saturated be good) ethene alcohol ester such as vinyl-acetic ester, vinyl laurate, palmitinic acid vinyl acetate, stearic acid vinyl ester, oleic acid vinyl acetate etc. and composition thereof.Also can use the multipolymer of ethene alcohol ester and insatiable hunger acid esters such as the multipolymer of vinyl-acetic ester and fumaric acid dialkyl.

After esterification, these esters can the other unsaturated monomer, for example with respect to the 0.2-5 mole C of every mole of unsaturated ester or every mole of unsaturated acid or anhydride _2-20Aliphatic series or atomatic olefins carry out copolymerization.For example pass through maleic anhydride and the formed multipolymer of vinylbenzene with the alkohol and amine esterification, see United States Patent (USP) 3,702,300.

This class ester polymer can with can participate in the unsaturated nitrogen containing monomer of polymeric and carry out grafting or copolymerization, thereby give the viscosity index improver dispersiveness.The example of suitable nitrogenous unsaturated monomer comprises the compound that contains 4-20 carbon atom such as amino substituted olefine-to (β-diethyllaminoethyl) vinylbenzene, be connected with the unsaturated substituent nitrogenous alkaline heterogeneous ring compound of the olefinic that can participate in polyreaction for example vinyl pyridine and vinyl alkyl pyridine such as 2-vinyl-5-ethylpyridine, 2-methyl-5-vinylpyrine, 2-vinyl-pyridine, 4-vinylpridine, the 3-vinyl pyridine, 3-methyl-5-vinyl pyridine, 4-methyl-2-vinyl pyridine, 4-ethyl-2-vinyl pyridine and 2-butyl-5-vinyl pyridine etc.

Same N-vinyl lactam, for example N-alkene N-ethyl pyrrole N-ketone or the N-vinyl piperidone in addition that is suitable for.

Be good wherein with vinyl pyrrolidone, its illustration is just like N-vinyl pyrrolidone, N-(1-methyl ethylene) pyrrolidone, N-vinyl-5-methyl-2-pyrrolidone, N-vinyl-3-, 3-dimethyl pyrrolidone, N-vinyl-5-ethyl pyrrolidone etc.

Inhibiter also is sanitas, can slow down the aging of the metal spare and accessory parts that contact with lubricating oil composition.The example of inhibiter reacts and the product that obtains just like phosphosulfurized hydrocarbon with by phosphosulfurized hydrocarbon and alkaline earth metal oxide or oxyhydroxide (be preferably in the presence of alkylated phenol or alkylphenol sulfuric acid, be preferably equally in the presence of carbonic acid gas).By under 66-320 ℃, making suitable hydrocarbon such as terpenes, C _2-6The heavy crude fraction of olefin polymer such as polyisobutene and 5-30%(are heavy) the sulfide reaction of phosphorus just can make phosphosulfurized hydrocarbon in 0.5-15 hour.Can adopt US Patent No 1,969,324 described methods this phosphosulfurized hydrocarbon that neutralizes.

Oxidation retarder can reduce the rotten possibility of use mineral oil in fluid, and the increase of the sludge of oxidation products such as metallic surface and sedimental generation of varnish shape and viscosity all can aggravate this denaturalization phenomenon.This oxidation retarder comprises and contains C preferably _5-12The alkaline earth salt of the alkyl phenolic ester of alkyl group side chain, nonylphenol sulfurated lime, uncle's octyl phenyl barium sulphide, dioctyl aniline, phenyl x-ALPHA-NAPHTHYL AMINE, phosphorus sulfuration or sulfuration hydrocarbon etc.

Friction modifiers can make lubricating oil composition such as automatic fluid transmission possess suitable rubbing characteristics.

As the suitable representational example of friction modifiers, US Patent No 3,933,695 disclosed be fatty acid ester and acid amides; US Patent No 4,176,047 disclosed be polyisobutenyl amber acid anhydrides-amino alcohol molybdenum match, US Patent No 4,105,571 disclosed be the glyceryl ester of dimer (fatty acid) yl; US Patent No 3,779,928 disclosed be alkyl phosphonate, US Patent No 3,778,375 disclosed be the reaction product of phosphonate and oleylamide; US Patent No 3,852,205 what disclose is S-carboxyl-alkylidene group hydrocarbyl succinic imide, S-carboxyl-hydroxyalkyl hydrocarbon succinic amide acid and composition thereof, US Patent No 3,879,306 disclosed N(hydroxyalkyls) thiazolinyl-succinamic acid or succinimide; U.S. Patent No. 3,932,290 disclosed be the reaction product of two (low alkyl group) phosphites and epoxide, US Patent No 4,028,258 disclosed be phosphorus sulfuration N-(hydroxyalkyl) alkylene oxide adduct of alkenyl succinimide.The content that above document discloses is only for reference at this.Best friction modifiers is the succinate of list and glyceryl dioleate and alkyl replacement amber acid or anhydride and thiobis alcohol, or its metal-salt, and as US Patent No 4,344,853 is described.

The temperature that pour point depressant can reduce fluid flow or topple over.These all are known depressants.The additive that typically can make fluid possess best low-temperature fluidity is C _8-18Dialkyl group fumarate/vinyl acetate copolymer, polymethacrylate and content of wax naphthalene.

Can bubble by adopting polysiloxane type foam preventer such as silicone oil and poly-24 basic oxygen alkane controls.

Be used for oil soluble organic compound of the present invention as rust-preventive agent and comprise nonionogenic tenside such as the many alcohol of polyoxyalkylene and ester and anion surfactant such as alkylsulphonic acid.This antirust compound is known and can be by traditional method preparation.Be used for the nonionogenic tenside of oleaginous composition of the present invention as rust-inhibiting additive, its surface active properties is entirely by its contained many weak stablize group such as ehter bond.By using excessive rudimentary alkylene oxide (as oxyethane and propylene oxide) to make the organic substrates generation alkoxylation that contains reactive hydrogen, produce until intramolecularly till the alkoxyl group of desired number, just can make the nonionic rust-preventive agent that contains ehter bond.

Used rust-preventive agent is good with many alcohol of polyoxyalkylene and derivative thereof.This class material is taken from multiple commercial source; The liquid triol that the polyoxyethylene glycol 112-2(that the many alcohol of the Pluronic of Wyandotte chemical company, Dow chemical company produce is obtained by oxyethane and propylene oxide), He Wukang (polyene glycol and derivative thereof) Tergitol(dodecylphenyl or the single phenyl polyglycol ether of producing by Union Carbide Corporation).These materials only account for as rust-preventive agent and are applicable to that the present invention improves the sub-fraction of the commodity of composition).

Except many alcohol self, also be suitable for by making many alcohol and the resulting ester of all kinds of carboxylic acid reaction.The acid that is used to prepare these esters be lauric acid, stearic acid, succsinic acid and wherein alkyl or alkenyl contain nearly that the alkyl or the basic alkene of 20 carbon atoms replace succsinic acid.

Prepared many alcohol is good with block polymer.Therefore, n is 1-6 in the hydroxyl substitution compound R-(OHn(formula, and R is the residue of list or polyhydroxy-alcohol, phenol, naphthols etc.) can form hydrophobic alkali with propylene oxide reaction.Then, this alkali and reacting ethylene oxide produce hydrophilic segment, and like this, existing hydrophobic part has hydrophilic segment again in a part.Can wait the relative size of regulating these parts by quantitative proportion and the reaction times adjusted between the reactant, this it will be apparent to those skilled in the art that.Therefore, this two-part ratio can adopt the technology preparation of this area to it is characterized in that existing hydrophobic part in the molecule has the how alcohol of hydrophilic segment again, although must make at different base oils and exist under the condition of other additive rust-preventive agent all can be applicable among any lubricating oil composition.

If need its oil soluble in given lubricating oil composition bigger, can increase its hydrophobic part and/or reduce its hydrophilic segment.If need the breakdown of emulsion ability of stronger emulsion oil-in-water, can assign to finish by adjusting its hydrophobic and/or hydrophilic portion.

R-(OH) _nThe illustration of compound comprises that the many alcohol of alkylidene group are as aklylene glycol, alkylidene group triol, alkylidene group tetrol etc., as ethylene glycol, propylene glycol, glycerine, tetramethylolmethane, sorbyl alcohol, mannitol etc.Also can use aromatic hydroxy compound such as alkylation single and polyhydroxy phenol and naphthols, for example heptyl phenol, 4-dodecylphenol etc.

Other suitable demulsifying compound comprises US Patent No 3,098,827 and 2,674,619 disclosed ester classes.

How pure and mild other similar how pure particularly suitable of liquid of the many alcohol of the Pluronic by name that Wyandotlec chemical company produces is made rust-preventive agent.These Pluronic are many, and alcohol is shown below:

HO-（CH ₂CH ₂O） _x（

） _y（CH ₂CH ₂O） _zH （Ⅷ）

X, Y and Z are the integer greater than 1 in the formula, and group-CHCHO-accounts for the 10-40%(weight of 1 total molecular weight like this), the molecular-weight average of this 1 is about 1000-500.At first make propylene oxide and propylene glycol condensation generate hydrophobic alkali (IX),

（Ⅸ）

Then with this condensation product of ethylene oxide treatment, hydrophilic segment is added to the two ends of molecule, so just can make above-mentioned those products.In order to produce optimum, the 10-40%(that the oxyethane chain link should account for molecule is heavy).The molecular weight of wherein many alcohol be about 2500-4500 and the ethylene oxide chain saving to account for the 10-15%(of molecule heavy) those product particularly suitables.Molecular weight is about 4000, wherein about 10% and is (CH ₂CH ₂O) many alcohol of chain link are good especially.Same alkoxylated fats amine, acid amides, the alcohol etc. in addition that are suitable for comprise and use C _9-16Alkyl-substituted phenols (as one and diheptyl, octyl group, nonyl, decyl, undecyl, dodecyl and tridecyl phenol) handle the derivative that this class alkoxylated fatty acid obtains, United States Patent (USP) 3,849,501 is described, this patent documentation is only for reference at this.

These compositions of the present invention cannot contain other additive those materials and other containing metal (for example barium and sodium) additive as previously mentioned.

This does not comprise the inhibiter that contains copper-lead to lubricating oil composition of the present invention.Typical this compounds is thiadiazole polysulphide and derivative and the polymkeric substance that contains 5-20 carbon atom.With such as US Patent No 2,719,125,2,719,126 and 3,087,932 and so on documents are described 1,3, and the derivative of 4-thiadiazoles is good, especially with the compound 2 of its commodity Amoco150 by name, and two (the uncle's octyl group dithio)-1,3 of 5-, the 4-thiadiazoles is good.Similar substance such as United States Patent (USP) 3,821,236,3904537,4,097,387,4,107,059,4,136,043,4,188,299 and 4,193 that other is suitable for equally, 882 is described.

Other suitable additive is sulfo-and the poly-sulfo-sulfinyl amine such as british patent specification 1560830 described thiadiazoles.Weight in lubricating composition is as the criterion, and the content of these compounds is that 0.01-10%(is heavy in this lubricating oil composition), heavy with 0.1-0.5%() be good.

Some this class additive can produce multiple effect, for example can be used as dispersion agent-oxidation retarder.As known content, this be need not to give unnecessary details.

When containing these traditional additives in the composition, be said composition to be blended among the base oil generally speaking with effective level that common attach feature can be provided.In the sufficient oil product of preparation, the effective level of (being used as active ingredient respectively) this class additive is as shown in behind the literary composition:

The present invention's lubricating oil composition preferably contains the 0.05-0.2(weight of having an appointment) component (A) (1) (representing) of % with Ca; About 0.02-0.11(weight) component (A) (2) (representing) of % with Mg; Be enough to provide about 0.08-0.11(weight) B component of % phosphorus; About 1.5-3(weight) %A.I. component C ashless dispersant; And about 80-150ppm component D antioxidant (ppm with Cu represents).

When using other additive, although do not require, but may wish to prepare multifunctional additive for lubricating oils, this enriched material contains the present invention's novel washing inhibitor/anti-wear agent enrichment of mixture solution or dispersion liquid (amount in enriched material was above narrated), also contain more than one described other additive (described concentrated insult is called a whole set of prescription of additive when constituting the interpolation mixture) simultaneously, thereby can in matrix oil, add several additives simultaneously to form lubricating oil composition.Utilize solvent and have to help multifunctional additive for lubricating oils dissolving in lubricating oil, but this is not main with the mixing of fusion heating.The general prescription of a whole set of prescription of enriched material or additive is obtaining desirable concentration when being the additive that contains appropriate amount with the matrix mix lubricant of a whole set of prescription of convenient additive and predetermined amount in final the composition.Therefore, the present invention's the washing inhibitor/anti-wear agent mixture and the additive of other hope add to together and form a whole set of prescription of the additive that contains active ingredient in a small amount of matrix oil or other intermiscibility solvent, collective's weight of additive generally is about 2.5-90%, about 15-75% is for well, and preferably 25～60%(is the proper ratio of matrix oil by residuum).

Generally the end formulation that may adopt is about 10(weight) a whole set of prescription of the additive of % (residuum is a matrix oil).

The described weight percent (unless otherwise indicated) that illustrates herein is based on active ingredient (A.I) content of additive entirely, and/or based on a whole set of gross weight of filling a prescription of additive, or the A.I weight of each additive adds the summation of total oil or thinner weight.

Further understand the present invention with reference to following examples, wherein, all " parts " are " weight part ", and (unless otherwise indicated), and this will be suitable for optimum implementation of the present invention.

Embodiment

Prepare one group of total composition lubricating oil, it is contained in the washing inhibitor of selection, zinc dialkyl dithiophosphate anti-wear agent, ashless dispersant, antioxidant and conservation of fuel additive.The data that obtain thus are summarized in table I (table is seen the literary composition back)

Annotate:

(1) (weight %Ca): high alkaline calcium sulfonate, 400TBN, 55(weight) %A.I.

(2) (weight %Mg): overbased magnesium sulphonates, 400TBN, 52(weight) %A.I.

(3) (weight % phosphorus): di-primary alkyl zinc dithiophosphate enriched material oil in rare mineral is 75 weight %A.I), the mixture of alkyl or this group has 4-5 carbon atom in this enriched material, and by PS and about 65(weight) % isopropylcarbinol and about 35(weight) the % amylalcohol mixture reaction and make.

(4) (weight % phosphorus): di-sec-alkyl zinc dithiophosphate enriched material is 71 weight %A.I in rare mineral oil), the 3-6 of the mixture of an alkyl or this group carbon atom in this enriched material, and make by the mixture reaction of PS and isopropylcarbinol (30%) and methyl tertbutyl Trivalin SF (70%).

(5) the rare mineral oil solution of volume % ashless dispersant I-50 weight %A.I. contains nitrogen content and is about the boronation polyisobutenyl amber imines that 1.47 weight % boron content are about 0.35 weight %, and this boronation polyisobutenyl succinimide by in each polyisobutene molecule (by number-average molecular weight be about 1300 polyisobutene derive obtain) be about the polyisobutenyl succinic anhydride of the ratio of 1.1 succinyl oxides part, the commercial grade mix polyethylene amination of 5-7 nitrogen is arranged and derive and obtain with each molecule.Ashless dispersant II=50(weight) the rare mineral oil solution of %A.I., contain nitrogen content and be about 0.976(weight) %, boron content be about 0.25(weight) the boronation polyisobutenyl succinimide of %, and this boronation polyisobutenyl succinimide be by by each polyisobutene molecule (by number-average molecular weight be about 2200 polyisobutene derive obtain) about 1.1 succinyl oxides, the commodity mix polyethylene amine amination of 5-7 nitrogen is arranged and derives with each molecule to obtain.

(6) rare mineral oil (38 weight %A.I.) of the single cupric oleate of volume %

(7) volume % oleic acid-glyceryl ester; The total monoglyceride of 50 weight %A.I.

The consumption of (8) five cars

* data point as shown in fig. 1

Fig. 1 illustrates the conservation of fuel data of accumulative total in the enforcement.Among Fig. 1, with graphics Ca and the Mg metal detergent of implementing 1-27 are shown and represent that with the relative proportion X-axis of uncle and the observed conservation of fuel data of secondary ZDDP Ca/Mg washs the relative percentage of inhibitor, and the y axle is represented the relative percentage of primary/secondary ZDDP, in the round-robin number (for example 1.98/1), divide the deserved average fuel of subrepresentation to save, and denominator represent to specify the embodiment sequence number of embodiment or zone (specifying in A, B, C, D and E).

By above test can find out the A district (embodiment 1 and 2,100%Mg, 100% uncle 2DDP) in the conservation of fuel data statistically than C district (embodiment 14-17,50/50, Ca/Mg, 50/50, primary/secondary ZDDP) the conservation of fuel data difference of Huo Deing, (99% confidence level).B district (embodiment 3-13,100%Mg, 100 secondary ZDDP) conservation of fuel is statistically than the present invention's C district poor (99% confidence level).

The conservation of fuel in C district is better than E district (embodiment 18-20 is characterized in that high Ca/Mg ratio and Gao Zhong/uncle ZDDP ratio) (99% confidence level) statistically.

The additional fuel of embodiment 22-27 is saved a data point and is shown in Fig. 1.

As in embodiment impression 1-27, prepared other one group of lubricating oil and carried out the conservation of fuel test.Those additional tests among the embodiment 28-37 are in the following table II.Do not contain the XU 61518.10 friction modifiers in these test recipes.

Claims (34)

1, a kind of lubricating oil composition, it comprises lubricant viscosity oil and following accessory constituent as main ingredient:

(A) mixture of (1) at least a calcium high alkalinity washing inhibiter and (2) at least a magnesium high alkalinity washing inhibiter;

(B) mixture of (1) at least a di-primary hydrocarbyl dithiophosphoric acid zinc and (2) at least a di-secondary hydrocarbyl dithiophosphoric acid zinc;

(C) at least a ashless dispersant;

(D) carboxylic acid copper compound of at least a antioxidant significant quantity;

Wherein, component (A) (1) is represented with Ca, is 0.03～0.5 (weight) % of lubricating oil composition; Component (A) (2) is represented with Mg, is 0.01-0.25 (weight) % of lubricating oil composition; The usage quantity of component (B) should be enough to provide 0.05-0.15 (weight) phosphorus of % in lubricating oil composition; Blended calcium and magnesium washing inhibitor is that the weight ratio according to component (A) (1) component (A) (2) is that 0.3: 1～6: 1 measuring is existing; Di-primary hydrocarbyl dithiophosphoric acid zinc of blended and di-primary hydrocarbyl dithiophosphoric acid zinc anti-wear agent are by component (B) (1): (B) weight ratio of (2) is that 0.4: 1～9: 1 amounts exist.

2, oily composition according to claim 1, wherein, above-mentioned ashless dispersant comprises the oil-soluble reaction products of reaction mixture, this reaction mixture comprises:

(a) by number-average molecular weight be the C of 700-5000 ₂～C ₁₀The olefin polymer of monoolefine and C ₄～C ₁₀What single unsaturated acid substance reaction formed can produce the C that alkyl replaces ₄～C ₁₀The material of single unsaturated dicarboxylic acid, each olefin polymer molecule on average has at least 0.8 to generate the dicarboxylic acid part in the acidic material of described energy, and this olefin polymer is the olefin polymer that is used to form in the described reaction mixture that can produce acid substance;

(b) the nucleophilic reaction body is selected from amine, ethanol, amino alcohol and composition thereof.

3, the composition according to claim 2, wherein, described nucleophilic reaction body (b) is an amine.

4, the composition according to claim 3, wherein, described amine is the polyethylene polyamines.

5, the composition according to claim 2, wherein, described nucleophilic reaction body (b) is an ethanol.

6, the composition according to claim 2, wherein, described nucleophilic reaction body (b) is an amino alcohol.

7, according to each described composition among the claim 2-6, wherein, the described acid substance (a) that can produce is that each described olefin polymer molecule has 1.0-2.0 to generate the dicarboxylic acid part.

8, the composition according to claim 7, wherein, described olefin polymer comprises that molecular weight is the C of 900-3000 ₂～C ₄The polymkeric substance of monoolefine, described single unsaturated acid material comprise α-or β-unsaturated C ₄And C ₁₀Dicarboxylic acid, acid anhydride or acid.

9, the composition according to claim 1, wherein, the usage quantity of copper carboxylate antioxidant, the weight of adding copper according to the form of described copper carboxylate is 40-500ppm

10, according to claim 1 or 9 described compositions, wherein, contained interpolation copper is 50-200ppm.

11, according to claim 1 or 9 described compositions, wherein, copper compound is selected from C ₁₀～C ₁₈The mantoquita of lipid acid and molecular weight are the mantoquita of the naphthenic acid of 200-500.

12, the composition according to claim 1, wherein, calcium washing inhibitor comprises sulfonate, phenates or the salicylate of high alkalinity calcium.

13, the lubricating oil composition according to claim 1, wherein, magnesium washing inhibitor comprises sulfonate, phenates or the salicylate of high alkalinity magnesium.

14, according to claim 1 or 12 described lubricating oil compositions, wherein, the content of calcium washing inhibitor in lubricating oil composition represents it is 0.04-0.4(weight with Ca) %.

15, the lubricating oil composition according to claim 14, wherein, the content of magnesium washing inhibitor in lubricating oil composition represents it is 0.01-0.2(weight with magnesium) %.

16, the lubricating oil composition according to claim 15, wherein, the content of calcium washing inhibitor and magnesium washing inhibitor represents it is the 0.4-3(weight part with metal separately in the lubricating oil composition) calcium washing inhibitor: the magnesium washing inhibitor 1(weight part).

17, the lubricating oil composition according to claim 1, wherein, di-primary hydrocarbyl dithiophosphoric acid zinc is to be derived by the zinc salt with following general formula acid to form:

Wherein, R ¹And R ²Identical or different, be alkyl, cycloalkyl, aralkyl, the alkyl of alkaryl or similar structures.

18, the lubricating oil composition according to claim 1, wherein, two sechy-drocarbyl thiophosphoric acid zinc are to be derived and got by the zinc salt with following general formula acid:

Wherein, R ³; R ⁴, R ⁵And R ⁶Identical or different, be alkyl, cycloalkyl, aralkyl, the alkyl of alkaryl or similar structures.

19, the lubricating oil composition according to claim 14, wherein, the content of phosphorodithioic acid salt mixture B in lubricating oil composition is represented with phosphorus, is 0.07-0.12(weight) %.

20, the lubricating oil composition according to claim 1, wherein, the content of phosphorodithioic acid salt mixture in lubricating oil composition is represented with phosphorus, is 0.08-0.11(weight) %.

21, the lubricating oil composition according to claim 19, wherein, di-primary alkyl thiophosphoric acid zinc and the content of two sechy-drocarbyl thiophosphoric acid zinc in lubricating oil composition are 0.5-3(weight) part di-primary alkyl thiophosphoric acid zinc: 1(weight) part two sechy-drocarbyl thiophosphoric acid zinc.

22, a kind of lubricating oil composition, after it comprises as the lubricant viscosity of main component oil and following submember:

(A) mixture of (1) at least a calcium high alkalinity washing inhibitor and (2) at least a magnesium high alkalinity washing inhibitor, wherein blended calcium and magnesium wash the content of inhibitor, by component A(1): weight ratio A(2) is 0.3: 1～6: 1, the content of component (A) (1) wherein, be expressed as 0.03～0.5(weight with Ca) %, and the content of component (A) (2) is expressed as 0.01～0.25(weight with Mg) %;

(B) mixture of (1) at least a di-primary hydrocarbyl dithiophosphoric acid zinc and (2) at least a di-secondary hydrocarbyl dithiophosphoric acid zinc is a 0.05-0.15(weight) %, the content of di-primary hydrocarbyl dithiophosphoric acid zinc of blended and di-secondary hydrocarbyl dithiophosphoric acid zinc wherein is by B(1): weight ratio B(2) is 0.4: 1～9: 1;

(C) 0.1～10(weight) at least a oil-soluble dispersant of %;

(D) at least a oil-soluble carboxylic acid copper is 40-500ppm so that the weight of copper that adds by described copper carboxylate form to be provided.

23, the oily composition according to claim 22, wherein said ashless dispersant comprises the oil-soluble reaction products of reaction mixture, this reaction mixture comprises:

(a) by number-average molecular weight be the C of 900-5000 ₂-C ₁₀The olefin polymer of monoolefine and C ₄-C ₁₀What single unsaturated acid substance reaction formed can produce the C that alkyl replaces ₄-C ₁₀The material of single unsaturated dicarboxylic acid describedly can generate that each olefin polymer molecule on average has at least 0.8 to generate the dicarboxylic acid part in the acid substance, and this olefin polymer is the olefin polymer that is used to form among the reaction mixture of described generation acid substance;

(b) the nucleophilic reaction body is selected from amine, ethanol, amino alcohol and composition thereof.

24, the composition according to claim 23, wherein nucleophilic reaction body (b) is an amine.

25, the composition according to claim 24, wherein said amine is the polyethylene polyamines.

26, the composition according to claim 23, wherein nucleophilic reactant (b) is an ethanol.

27, the composition according to claim 23, wherein nucleophilic reactant (b) is an amino alcohol.

28, according to each described composition among the claim 23-27, wherein, each described olefin polymer molecule has 1.0-2.0 to generate the dicarboxylic acid part in described sour resultant (a).

29, the composition according to claim 28, wherein said olefin polymer comprises that molecular weight is the C of 900-3000 ₂-C ₄The polymkeric substance of monoolefine, and described C ₄-C ₁₀Single unsaturated acid material comprises α-or β-unsaturated C ₄-C ₁₀Dicarboxylic acid, acid anhydride or ester.

30, the composition according to claim 22, wherein, the usage quantity of described copper carboxylate antioxidant is 40-500ppm by the weight of described copper carboxylate form Additive Cu.

31, the composition according to claim 30, it contains the described interpolation copper of 50-200ppm.

32, according to claim 22 or 30, the compound of wherein said copper is selected from C ₁₀-C ₁₈The mantoquita of lipid acid and molecular weight are the naphthenate of 200-500.

33, a kind of enriched material, it comprises 25-85(weight) the % matrix oil and:

(A) mixture of (1) at least a calcium high alkalinity washing inhibitor and (2) at least a magnesium high alkalinity washing inhibitor;

(B) mixture of (1) at least a di-primary hydrocarbyl dithiophosphoric acid zinc and (2) at least a di-secondary hydrocarbyl dithiophosphoric acid zinc;

(C) at least a ashless dispersant,

(D) carboxylic acid copper compound of at least a antioxidant significant quantity; Wherein component (A) (1) is expressed as 0.03～0.5(weight of lubricating oil composition with Ca) %, component (A) (2) is represented with Mg, 0.01～0.25(weight for lubricating oil composition) %, the usage quantity of component (B) should be enough to 0.05-0.15(weight is provided in lubricating oil composition) phosphorus of %; Blended calcium and magnesium washing inhibitor are by component A(1): weight ratio A(2) is existence in 0.3: 1～6: 1; Di-primary hydrocarbyl dithiophosphoric acid zinc of blended and di-secondary hydrocarbyl dithiophosphoric acid zinc anti-wear agent, by B component (1): weight ratio B(2) is to exist in 0.4: 1～9: 1.

34, the enriched material according to claim 33, the content of wherein said matrix oil in enriched material is 75(weight) %.