CN1021344C - Improved lubricant compositions for low-temp internal combustion engine - Google Patents

Improved lubricant compositions for low-temp internal combustion engine Download PDF

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Publication number
CN1021344C
CN1021344C CN88107967A CN88107967A CN1021344C CN 1021344 C CN1021344 C CN 1021344C CN 88107967 A CN88107967 A CN 88107967A CN 88107967 A CN88107967 A CN 88107967A CN 1021344 C CN1021344 C CN 1021344C
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Prior art keywords
acid
alkyl
zinc
lubricating oil
inhibitor
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CN88107967A
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CN1034753A (en
Inventor
埃米尔·约瑟夫·麦内
克里斯托弗·帕特里克·赫拉·吉奥
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ExxonMobil Chemical Patents Inc
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Exxon Chemical Patents Inc
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    • C10M163/00—Lubricating compositions characterised by the additive being a mixture of a compound of unknown or incompletely defined constitution and a non-macromolecular compound, each of these compounds being essential
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    • C10M137/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus having no phosphorus-to-carbon bond
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    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2070/00—Specific manufacturing methods for lubricant compositions
    • C10N2070/02—Concentrating of additives

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  • Chemical & Material Sciences (AREA)
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  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Lubricants (AREA)

Abstract

In accordance with the present invention, there are provided lubricating oil compositions which comprise an oil of lubricating viscosity as the major component and as the minor component (A) a mixture of (1) at least one calcium overrbased sulfonate or phenate detergent inhibitor, and (2) at least one magnesium overbased sulfonate or phenate detergent inhibitor, and (B) a mixture of (1) at least one zinc di-(primary hydrocarbyl) dithiophosphate and (2) at least one zinc di-(secondary hydrocarbyl) dithiophosphate, wherein the mixed calcium and magnesium detergent inhibitors and the mixed zinc di(primary hydrocarbyl) dithiophosphate and the zinc di(secondary hydrocarbyl) dithiophosphate antiwear agents are present in controlled ratios.

Description

Improved lubricant compositions for low-temp internal combustion engine
The present invention relates to obviously to improve the lubricating oil composition of low temperature cylinder body wearing and tearing.Specifically, the present invention relates to except that containing dispersant additives, 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 be an industrial big task obtaining tangible improvement and prolong engine life simultaneously aspect low temperature cylinder body and the ring wearing and tearing.At low temperatures in Cao Zuo the engine, as for do not operate with thermosistor and under the situation that does not have conventional antifreeze/coolant (as ethylene glycol) with the petrol engine of water-cooled, the wear problem particularly important of cylinder body.The lubricating oil that the high temperature that makes is used down, general incomplete satisfactory for the cold petrol engine of glycol/water.
United States Patent (USP) 29 11 367 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) 35 62 159 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) 37 14 042 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) 39 33 659 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) 43 08 154 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) 44 17 990 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) 43 08 154 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 carboxyl acid acid anhydride, phosphoric acid, phosphoric acid ester, the reaction of the acidic cpd of thiophosphatephosphorothioate or its mixture.
United States Patent (USP) 4614692 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) 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 400 TBN sulfonic acid magnesiums (magnesium that contains 9.2wt%) that also contain 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) 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.14, pp.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 abrasion 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.
The invention provides and impel the lubricating oil composition that suppresses cylinder body and ring erosion corrosion, it comprises as the oil of the lubricant viscosity of principal constituent with as the improved following mixture of ancillary component:
(A) mixture of at least a high-alkali sulfonic acid calcium salt or phenates washing inhibitor (1) and the high-alkali sulfonate of at least a magnesium or phenates washing inhibitor (2);
(B) mixture of at least a di-primary hydrocarbyl dithiophosphoric acid zinc (1) and at least a di-secondary hydrocarbyl dithiophosphoric acid zinc (2);
Wherein, component (A) comprises the lubricating oil composition of about 0.7～0.9wt%, and component (B) comprises the lubricating oil composition of about 0.7-1.2wt%; And (A) (1) in the blended calcium magnesium washing inhibitor: (A) weight ratio of (2) is about 0.3: 1～1.3: 1, mixture (B) antiwear agents (B) (1): (B) weight ratio of (2) is between about 0.7: 1～3.1: 1.
Basis of the present invention is to be surprised to find that, washing inhibitor with blending calcium/magnesium in the crankcase lubricating oil composition and mix between the ratio of primary/secondary zinc antiwear agents in the effect of the ring wearing and tearing that reduce cylinder body has definite relation, and these mixtures are given the additive reduction cylinder body to a certain degree of unit weight and are encircled abrasive effect 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, alkyl benzene sulphonate (ABS), 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 (phenolthioxine), 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 fontanel thereof are for derivative, 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, the fontanel fossil waxes, 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, prepares this based composition and preferably uses.The example of promotor has aldehydes matter such as phenol, naphthols, alkylphenol, thiophenol, the polycondensation product of 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 about 1.1.For example can be about 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.
Be preferably overbasic calcic washing composition inhibitor and the overbasic consumption that contains magnesium washing composition inhibitor and be every part and contain magnesium washing composition inhibitor and use about 0.3 to 1.3 part of calcic washing composition inhibitor, use about 0.8 to 1.2 part to be good (representing) with respective metal.
Component A(is A(1) and (2) sum) consumption in full composition lubricating oil is generally about 0.7-0.9wt%.
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
Figure 881079677_IMG7
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:
Figure 881079677_IMG8
R in the formula 3, R 4, R 5And 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 fontanel element 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＞and 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.
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 0.7 to 3.1 weight part, with 0.8 to 1.55 weight part is good, is the best with 0.7 to 1.8 weight part.B component (being B(1) and B(2) sum) consumption in full composition lubricating oil is generally about 0.7-1.2wt%, is preferably 0.8-1.1wt%.
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.
Lubricating oil composition
Lubricating oil composition for example is 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 these enriched materials of the lubricating oil dilution 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 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 are added among the lubricating oil.Therefore, these mixtures can directly be added 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.These enriched materials generally contain (in activeconstituents (A.I.)) about 9-18wt% component A washing suppressant additive, generally contain about 10-25wt% B component antiwear additive, and be generally about 30-90wt%, be preferably the bottoming oil of about 40-60wt%, in enriched material weight.
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 petroleum and paraffinic, cycloalkane and combination chain alkane-cycloalkane are through 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 molecular-weight average is that methyl-poly-Isopropanediol ether of 1000, phenyl ether, the molecular weight that molecular weight is 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 the 2-ethylhexyl diester of Polycizer W 260, sebacic acid two (2-ethylhexyl) ester, the just own ester of fumaric acid two, dioctyl sebacate, diisooctyl azelate, two different decayl esters of azelaic acid, dioctyl phthalate, phthalic acid didecyl ester, sebacic acid two (eicosyl) ester, linoleic acid dimer and by 1 mole of sebacic acid and two moles of tetraglycols and two moles of mixed esters that the 2 ethyl hexanoic acids reaction is generated.
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 silicon ester oil product 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 poly-(tolyl) siloxanes.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 6For good, 20000-250000 for example.
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 alpha-olefin 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 high alpha-olefin 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. 4068,056; 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 alpha-olefin.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 alpha-olefin 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 alpha-olefin 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 3-28The terpolymer that alpha-olefin and non-conjugated dienes or this class diene mixture constitute, tetrapolymer etc.The consumption of non-conjugated dienes is a benchmark in the total amount of ethene and alpha-olefin, 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 and vinylformic 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, lauryl methacrylate, 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 with 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-vinyl pyrrolidone 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.
Be used for ashless dispersant 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 acid anhydrides or its mixture of dicarboxylic acid or acid anhydrides that 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 700 to about 5000.
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 0.8-2.0 mole α or β-unsaturated C at least 4To C 10Di-carboxylic acid, acid anhydrides or its ester, about 1.0 to 1.6 to be good, as 1.1 to 1.3 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 800 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 dicarboxylic acid, 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 fontanel 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 fontanel fluidized 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 fontanel fluidized 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; 3231587; 3912764; 4110349; 4234435 and English Patent 1440219 in these class methods are introduced to some extent.
After using the fontanel element, 65% to the 95%(weight of generally will having an appointment) polyolefine (as polyisobutene) is put reaction with the di-carboxylic acid thing.And when not using fontanel element 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 hydroxyl, alkoxyl group, amide group, itrile group, imidazolinyl etc.Particularly be suitable for be with 1 to 6 hydroxyl oxyamine, be advisable to be with 1 to 3 hydroxyl.The amine of recommending is the saturated amine of aliphatics, comprises the amine that general formula is following:
Figure 881079677_IMG9
R, R ', R " and R ' " are selected from hydrogen, C respectively in the formula 1To C 25Straight or branched alkyl, C 1To C 12Alkoxy C 2To C 6Alkylidene group, C 2To C 12Hydroxyl amino alkylidene group and C 1To C 12Alkylamino C 2To C 6Alkylidene group, wherein R " ' also can comprise the following formula group:
Figure 881079677_IMG10
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 " or 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-hydroxyethyl)-1, the 3-propylene diamine, 3-dodecyloxy propylamine, N-dodecyl-1, the 3-propanediamine, Tutofusin tris (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):
Figure 881079677_IMG11
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 alkylidene group two fontanelle compounds (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 " Polyamine H ", " 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.
M is about 3 to 70 in the formula, is advisable with 10 to 35; With
Figure 881079677_IMG13
" 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 has 1.6 moles of succinic anhydride group, and promptly the consumption of the five yuan of ammonia amine that should be every nitrogen equivalent is enough to supply with 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, fontanel 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.
Tutofusin tris (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 oxy-compound such as the di-carboxylic acid material that ashless dispersant is also replaced by above-mentioned long chain hydrocarbon and monohydroxy and polyhydroxy-alcohol or aromatic substance such as phenol and naphthols generate.Polyhydroxy-alcohol is best oxy-compound, is advisable to about 10 hydroxyls 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 polyhydroxy-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 '-tetrahydroxy 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 the polyhydric alcohol of partial esterification or phenol, promptly have the ester of free alcohol or phenolic hydroxyl group.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 oxyamine 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-(beta-hydroxyethyl) 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-hydroxypropyl)-N '-(beta-aminoethyl) piperazine, three (methylol) 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 hydroxyl, 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, Tutofusin tris and tetramethylolmethane) and composition thereof reaction.A kind of disperser composition of special recommendation comprise that (1) succinic anhydride group replaces and with (2) oxy-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 the composition (as described in the United States Patent (USP) 3632511) of the aliphatic primary amine (as tetramethylolmethane or Tutofusin tris) of (1) polyisobutenyl succinic anhydride and (2) polyalkylene polyamine (as tetren) and (3) polyhydroxy-alcohol or poly-hydroxy replacement.
Be used for antioxidant packages oil scraper dissolubility copper compound of the present invention.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 lipid acid such as stearic acid or palmitinic acid, because the processing and the solubility characteristic of resulting copper carboxylate can improve, thereby is 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.The same general formula in addition that is suitable for is the oil soluble dithiocarbamic acid copper of (RRNCSS) nCu, n is 1 or 2 in the formula, R and R are identical or different C alkyl, are good with the C alkyl, and they comprise the group such as alkyl, alkenyl, aryl, aralkyl, alkaryl and this class of alicyclic hydrocarbon radical.Especially be that the C alkyl is good with R and R.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.
Effectively the example of copper compound is the Cu[Cu(I of alkenyl succinic acid) and/or the Cu(II)] salt or acid anhydrides.Salt itself is alkalescence, and is neutral or acid.One of (a) top material with at least one free carboxy acid (or acid anhydrides) root of mentioning when speaking of ashless dispersant and (b) active metallic compound can be reacted and make.Suitable acid (or acid anhydrides) active metallic compound comprises copper or cuprous oxyhydroxide, oxide compound, acetate, borate and carbonate or verdigris etc.
The Cu salt (calling Cu-PIBSA in the following text) that metal-salt example of the present invention is a polyisobutenyl succinic anhydride and the Cu salt of polyisobutenyl succsinic acid.Used preferable alloy is its bivalent form such as Cu + 2Preferred substrate is the polyalkenyl succsinic acid, and wherein the number-average molecular weight of thiazolinyl (Mn) is greater than about 700.Require thiazolinyl to have about 900-1400, be preferably about 950 up to 2500 Mn.Polyisobutylene succinic acid (PIBSA) most preferably in the compound that above-mentioned dispersion agent is partly listed.Requirement is dissolved in these materials in solvent such as the mineral oil, and heating in the presence of the metallic substance aqueous solution (or slurry).Heating temperature is about 200 ℃ of 70-, but 110-140 ℃ just fully suitable.According to the situation of the salt of new production, needn't make to be reflected to keep long-time more than 140 ℃ as more than 5 hours, if not, can decompose.
In final lubricating oil or fuel composition, the consumption of copper antioxidant (for example Cu-PIBSA, cupric oleate or its mixture) is generally about 50-500ppmw 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 ZDDP, 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 50-500(is arranged in the above-mentioned lubricating oil composition that contains copper antioxidant is good with 10-200, be more preferably 10-180 and be preferably 20-130(such as 90-120)) 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.
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 150-600 °F, making suitable hydrocarbon such as terpenes, C 2～C 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～C 12The alkaline earth salt of the alkylphenol thioesters of alkyl group side chain, nonylphenol sulfurated lime, uncle's octyl phenyl barium sulphide, dioctyl aniline, phenyl 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 3,933,659 disclosed be fatty acid ester and acid amides; US Patent No 4,176,074 disclosed be the molybdenum match of polyisobutenyl succinic anhydride-amino alcohol, 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-alkylidene group hydrocarbon succinic amide acid and composition thereof, US Patent No 3,879,306 disclosed be the N(hydroxyalkyl) thiazolinyl-succinamic acid or succinimide; US 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～C 18Dialkyl group fumarate/vinyl acetate copolymer, polymethacrylate and content of wax naphthalene.
Can bubble by adopting the control of polysiloxane type foam preventer such as silicone oil and polydimethylsiloxane.
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 alkenyl of 20 carbon atoms replaces succsinic acid.
Prepared many alcohol is good with block polymer.Therefore, hydroxyl substitution compound R-(OH) n is 1-6 in the n 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) illustration of n 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 Wyandotte chemical company produces is made rust-preventive agent.These Pluronic are many, and alcohol is shown below:
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),
Figure 881079677_IMG15
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 be about 4000, wherein about 10% for many alcohol of (CHCHO) chain link good especially.Same be suitable for also have alkoxylated fats amine, acid amides, alcohol etc., comprise with the C alkyl-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, as United States Patent (USP) 3,849,501 is described, and this patent documentation is only for reference at this.
These compositions of the present invention can also contain other additive those materials and other containing metal (for example barium and sodium) additive as previously mentioned.
Lubricating oil composition of the present invention also comprises the inhibiter that contains copper-lead.Typical this compounds is thiadiazole polysulphide and derivative and the polymkeric substance that contains 5-20 carbon.With such as United States Patent (USP) № 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) 3,821,236,3,904,537,4,097,387,4,107,059,4,136,043,4,188,299 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 lubricated right composition is as the criterion, and the amount of opening 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, (being used as active ingredient respectively) effective level of this class additive is as follows:
Form (weight) %A.I. (weight) %A.I.
(optimum range) (rough range)
Total component
A(1) 1A(2) washing composition *0.7-0.9 0.7-0.9
B component anti-wear agent 0.8-1.1 0.7-1.2
Viscosity modifier 0.01-4 0.01-12
Inhibiter 0.01-1.5 0.01-5
Oxidation retarder 0.01-1.5 0.01-5
Dispersion agent 0.1-8 0.1-5
Pour point reducer 0.01-1.5 0.01-5
Antifoams 0.001-0.15 0.001-3
Friction modifiers 0.01-1.5 0.01-5
Mineral base oil surplus surplus
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 additive (residuum is a matrix oil) of %.
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 the gross weight of a whole set of 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 contains 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 the following table I.
Figure 881079677_IMG16
Annotate:
(1) high alkaline calcium sulfonate, 400TBN contains 15.5wt% Ca, 55(weight) %A.I.
(2) overbased magnesium sulphonates, 400TBN contains 9.2wt% Mg, 52(weight) %A.I.
(3) 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) di-sec-alkyl zinc dithiophosphate enriched material is 71 weight %A.I in rare mineral oil), the mixture of alkyl or this group has 3-6 carbon atom in this enriched material, and is made by the mixture reaction of PS and isopropylcarbinol (30%) and methyl tertbutyl Trivalin SF (70%).
(5) respectively with wt%Ca and Mg in the lubricating oil of Ca washing inhibitor and the preparation of Mg washing inhibitor.
(6) total P of wt% and Zn in the lubricating oil of ZDDP-1 ° of usefulness and ZDDP-2 ° of preparation
(7) 0=is best; 10=is the poorest
(8) 10=is best; 0=is the poorest
(9) 10=is best; 0=is the poorest
The gained test-results it is believed that it is uncommon among the embodiment 3.
* adds composition (using with constant volume) in each prescription in the oil of each preparation: (a) ashless dispersant (dilution mineral oil solution, boracic acidifying polyisobutenyl succinimide wherein, be to derive out, and the polyisobutenyl molecule is to be that 2200 polyisobutene derives out by number-average molecular weight by the have an appointment polyisobutenyl succinic anhydride of 1.1 succinyl oxide residues of each polyisobutene molecule; (b) nonyl phenol sulfide antioxidant; (c) cupric oleate antioxidant (120ppm wt% Cu); (d) (except that embodiment and) glyceryl monooleate fuel saving additive, (e) multifunctional viscosity modifier is (in the amination ethylene-propylene copolymer; (f) 150N basestock.
Table one data have reduced the Cam wearing and tearing compared with the control according to modification of lubricating oils prescription of the present invention, do not reduce Camnose merits again simultaneously, and can reach excellent Rocker pad demrits.
Example 7: comparative example B
Prepare an assembly side again and as lubricating oil with the water-cooled Fuel Petroleum test car of no thermostatted power operation.The gained data II that is listed in the table below.
Find that unexpectedly cylinder body wearing and tearing that occur during with example 7 oily and Lifter wear and tear and be lower than comparative example B, though longer in the oil dripping interval of example 7 and test period also be like this.
The table II
Composition * comparative example
（wt.%） B 7
Ca washs inhibitor 0 0.74
Mg washs inhibitor 1.29 0.69
ZDDP-1°（3） 1.19 0.76
ZDDP-2°（4） 0 0.76
The field test conditions:
SAE（5） 40 10W40
API（6） SE/CC SF/CC
The oil dripping interval, km 5,000 10, and 000
Test distance, km 50,000 80, and 000
Instruction carriage (7) (7)
Test-results:
The cylinder body wearing and tearing, mm (8) 0.026 (9) 0.011
The Lifter wearing and tearing, mm(9) 0.17 0.15
Annotate.
(1) high alkaline calcium sulfonate, 400TBN contains 15.5wt% Ca, 55(weight) % A.I.
(2) overbased magnesium sulphonates, 400TBN contains 9.2wt% Mg, 52(weight) % A.I.
(3) 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) di-sec-alkyl zinc dithiophosphate enriched material is 71 weight %A.I in rare mineral oil), the mixture of alkyl or this group has 3-6 carbon atom in this enriched material, and is made by the mixture reaction of PS and isopropylcarbinol (30%) and methyl tertbutyl Trivalin SF (70%).
（5）Society of Automotive Engineers。
（6）American Petroleum Lnstitute。
(7) General Motors Caprice, V-6, does not have thermostatted in the engine cold water system by 4.1 liters.
(8) the 3-car is average
(9) the 2-car is average
* newly add component in every kind of oil except feel secure oil and also comprise ashless dispersant (polyisobutenyl succinimide); With copper oxidation inhibitor (120wppm Cu).The oil of enforcement 7 is formulated as multi-grade oil and also contains multi-functional viscosity modifier and oleic acid glyceride fuel saving additive.
Above-mentioned is principle of the present invention, preferred embodiment and mode.But claimed the present invention is not limited in concrete open form, because open form is an illustrative, does not provide constraints.Those skilled in the art can make various improvement and further perfect under design situation of the present invention.

Claims (21)

1, the invention provides and impel the lubricating oil composition that suppresses cylinder body and ring erosion corrosion, it comprises as the oil of the lubricant viscosity of principal constituent with as the improved following mixture of ancillary component:
(A) mixture of at least a high-alkali sulfonic acid calcium salt or phenates washing inhibitor (1) and the high-alkali sulfonate of at least a magnesium or phenates washing inhibitor (2);
(B) mixture of at least a di-primary hydrocarbyl dithiophosphoric acid zinc (1) and at least a di-secondary hydrocarbyl dithiophosphoric acid zinc (2);
Wherein, component (A) comprises the lubricating oil composition of about 0.7～0.9wt%, and component (B) comprises the lubricating oil composition of about 0.7-1.2wt%; And (A) (1) in the blended calcium magnesium washing inhibitor: (A) weight ratio of (2) is about 0.3: 1～1.3: 1, mixture (B) antiwear agents (B) (1): (B) weight ratio of (2) is between about 0.7: 1～3.1: 1.
2, the composition of claim 1, wherein Ca washing inhibitor comprises high-alkali calcium sulphonate.
3, the composition of claim 1, wherein Mg washing inhibitor comprises high-alkali sulfonic acid magnesium.
4, the composition of claim 1, wherein Ca washing inhibitor and the consumption of Mg washing inhibitor in lubricating oil composition wash inhibitor for about 0.8-1.1 weight part Ca washing inhibitor/weight part Mg.
5, 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:
Figure 881079677_IMG1
Wherein, R 1And R 2Identical or different, be alkyl, cycloalkyl, aralkyl, the alkyl of alkaryl or similar structures.
6, 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:
Figure 881079677_IMG2
Wherein, R 3, R 4, R 5, and R 6Identical or different, be alkyl, cycloalkyl, aralkyl, the alkyl of alkaryl or similar structures.
7, the lubricating oil composition according to claim 1, wherein, di-primary alkyl thiophosphoric acid zinc and the content of two sechy-drocarbyl thiophosphoric acid zinc in lubricating oil composition are 0.8-1.55(weight) part di-primary alkyl thiophosphoric acid zinc: 1(weight) part two sechy-drocarbyl thiophosphoric acid zinc.
8, a kind of method that forms lubricating oil composition, it comprises:
(a) preparation
(1) at least a calcium overbased sulfonate or phenates washing composition and
(2) mixture (A) of at least a magnesium overbased sulfonate or phenates washing inhibitor, wherein blended calcium and magnesium wash the content of inhibitor, by component A(1): weight ratio A(2) is about 0.3: 1～1.3: 1;
(b) preparation
(1) at least a di-primary hydrocarbyl dithiophosphoric acid zinc and
(2) mixture (B) of at least a di-secondary hydrocarbyl dithiophosphoric acid zinc, 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 0.7: 1～3.1: 1;
(c) mixture A and B are mixed the lubricating oil composition that contains about 0.7-0.9wt% mixture A and about 0.7-1.2wt% mixture B with formation with the lubricating oil of main amount.
9, the method for claim 8, wherein Ca washing inhibitor comprises high-alkali calcium sulphonate.
10, the method for claim 8, wherein Mg washing inhibitor comprises high-alkali sulfonic acid magnesium.
11, the method for claim 8, wherein Ca washing inhibitor and the consumption of Mg washing inhibitor in lubricating oil composition wash inhibitor for about 0.8-1.1 weight part Ca washing inhibitor/weight part Mg.
12, method according to Claim 8, wherein, di-primary hydrocarbyl dithiophosphoric acid zinc is to be derived by the zinc salt with following general formula acid to form:
Figure 881079677_IMG3
Wherein, R 1And R 2Identical or different, be alkyl, cycloalkyl, aralkyl, the alkyl of alkaryl or similar structures.
13, method according to Claim 8, wherein, two sechy-drocarbyl thiophosphoric acid zinc are to be derived and got by the zinc salt with following general formula acid:
Figure 881079677_IMG4
Wherein, R 3, R 4, R 5And R 6Identical or different, be alkyl, cycloalkyl, aralkyl, the alkyl of alkaryl or similar structures.
14, method according to Claim 8, wherein, di-primary alkyl thiophosphoric acid zinc and the content of two sechy-drocarbyl thiophosphoric acid zinc in lubricating oil composition are 0.8-1.55(weight) part di-primary alkyl thiophosphoric acid zinc: 1(weight) part two sechy-drocarbyl thiophosphoric acid zinc.
15, a kind of lubricant oil concentrate is comprising about 30-90wt% lubricant viscosity oil; About 9-18wt%(A) mixture of (1) at least a high alkalinity sulfonic acid Ca salt or phenates washing inhibitor and (2) at least a high alkalinity sulfonic acid Mg salt or phenates washing inhibitor; And about 10-25wt%(B) mixture of (1) at least a two primary hydroxyl zinc dithiophosphates and (2) at least a di-secondary hydrocarbyl dithiophosphoric acid zinc, wherein the calcium of mixture and magnesium washing inhibitor is according to component (A) (1): the weight ratio of component (A) (2) is about 0.3: 1～1.3: 1 measuring now; The di-primary hydrocarbyl dithiophosphoric acid zinc of blended anti-wear agent is by component (B) (1): (B) weight ratio of (2) is that about 0.7: 1～3.1: 1 amounts exist.
16, the enriched material of claim 15, wherein Ca washing inhibitor comprises high-alkali calcium sulphonate.
17, the enriched material of claim 15, wherein Mg washing inhibitor comprises high-alkali sulfonic acid magnesium.
18, the enriched material of claim 15, wherein Ca washing inhibitor and the consumption of Mg washing inhibitor in lubricating oil composition wash inhibitor for about 0.8-1.1 weight part Ca washing inhibitor/weight part Mg.
19, according to the enriched material of claim 15, wherein, di-primary hydrocarbyl dithiophosphoric acid zinc is to be derived by the zinc salt with following general formula acid to form:
Figure 881079677_IMG5
Wherein, R 1And R 2Identical or different, be alkyl, cycloalkyl, aralkyl, the alkyl of alkaryl or similar structures.
20, according to the enriched material of claim 15, 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.
21, according to the enriched material of claim 15, wherein, di-primary alkyl thiophosphoric acid zinc and the content of two sechy-drocarbyl thiophosphoric acid zinc in lubricating oil composition are 0.8-1.55(weight) part di-primary alkyl thiophosphoric acid zinc: 1(weight) part two sechy-drocarbyl thiophosphoric acid zinc.
CN88107967A 1987-11-20 1988-11-19 Improved lubricant compositions for low-temp internal combustion engine Expired - Fee Related CN1021344C (en)

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CA1337293C (en) 1995-10-10
AU2569288A (en) 1989-05-25
KR960013615B1 (en) 1996-10-09
CN1034753A (en) 1989-08-16
JPH01201399A (en) 1989-08-14
BR8806068A (en) 1989-08-08
EP0317348A1 (en) 1989-05-24
KR890008308A (en) 1989-07-10
AU617712B2 (en) 1991-12-05

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