CN1974738A

CN1974738A - Improved lubricant formulations containing extreme pressure agents

Info

Publication number: CN1974738A
Application number: CNA2006101718594A
Authority: CN
Inventors: J·L·米尔纳; A·卡德克霍达彦; D·K·德尔夫勒
Original assignee: Afton Chemical Corp
Current assignee: Afton Chemical Corp
Priority date: 2005-10-03
Filing date: 2006-09-30
Publication date: 2007-06-06
Also published as: EP1770155A1; KR20070037693A; JP2007100095A; US20070078066A1

Abstract

A method for improving the solubility of a sulfurized extreme pressure agent in a lubricant composition and improved lubricant compositions and uses therefor. The method includes pre-blending organic acid and amine components of a lubricant additive package for the lubricant composition to provide a premixture of organic acid and amine components. The premixture is combined with a sulfurized extreme pressure agent having a viscosity of less than about 5.5 centistokes at 100 DEG C to provide a lubricant additive package. By use of the foregoing process, a turbidity characteristic of the lubricant composition containing the additive package is lower than a turbidity characteristic of a lubricant composition that is made by combining the organic acid and amine components with the sulfurized extreme pressure agent in the absence of the premixture.

Description

The improved lubricant formulations that contains extreme pressure agent

Technical field

The present invention relates to lubricant formulations, relate in particular to lubricant formulations and make method with the lubricant that improves performance with enhanced stability.

Background technology

Thereby can in lubricant, allocate extreme pressure agent into and be used for specific purposes.The extreme pressure agent of existing many types.Useful especially extreme pressure agent is the extreme pressure agent of those sulfur-bearings.Yet sulfurized extreme pressure agent often is difficult to handle, and has the strong and stimulating smell, and costliness perhaps also needs the existence of compatible components when being used for lubricant formulations.

Therefore, still need to improve the lubricant formulations that contains the extreme pressure agent component.

Summary of the invention

Consider the aforementioned problem of mentioning, the invention provides a kind of deliquescent method that improves the sulfurized extreme pressure agent in the lubricant compositions and improved lubricant compositions and uses thereof.This method comprises that organic acid and the amine component to the slip additive combination (lubricant additive package) that is used for lubricant compositions carries out pre-mixing so that the premixture of organic acid and amine component to be provided.This premixture is combined with sulfurized extreme pressure agent so that the slip additive combination to be provided, and this sulfurized extreme pressure agent has the viscosity less than about 5.5 centistokes under 100 ℃.By using aforesaid method, this turbidity that contains the lubricant compositions of additive combination is lower than at the turbidity that does not carry out under the pre-mixing organic acid and amine component are mixed with sulfurized extreme pressure agent prepared lubricant compositions.

In another exemplary embodiment, provide a kind of method of making the muddy lubricant compositions of nothing of Containing Sulfur extreme pressure agent and a kind of basic nonpolar group oil ingredient.Sulfurized extreme pressure agent provides by sulfur monochloride/iso-butylene adducts and sodium sulfhydrate solution reaction, and its reaction conditions is to be enough to be provided at the sulfide isobutene that viscosity under 100 ℃ is not higher than 5.5 centistokes.The organic acid and the amine component of lubricant compositions are mixed in advance so that the additive combination premixture to be provided.Then this additive combination premixture is mixed with the sulfide isobutene of about 50～about 95 weight % and obtain compositions of additives.With obtaining not having muddy lubricant compositions behind this compositions of additives processing base oil.

Another exemplary of the present invention provides a kind of method of making sulfurized extreme pressure agent, and this extreme pressure agent has the characteristic that promotion contains the low turbidity lubricant formation of nonpolar substantially base oil.This method comprises: be enough to obtain under the condition of sulphur/olefin adducts sulfur monochloride and alkene to be reacted.Sulphur/olefin adducts and moisture sulphur source hybrid concurrency are given birth to reaction and are reached for some time, and this section period will be enough to obtain having the sulfurized extreme pressure agent in organic phase of the viscosity that is not higher than about 5.5 centistokes in the time of 100 ℃.After reaction is finished, that water is separated from one another with the organic phase that contains sulfurized extreme pressure agent.

An advantage of exemplary described herein is to make that to be difficult to the dissolved binder component easier to be dissolved and need not solvating agent or other expensive extreme pressure agents in the final lubricator component that forms.Therefore, solvating agent can be eliminated and/or use a spot of expensive components to replace the expensive components of using more amount.Especially, find it is after surprisingly, will have the sulfurized extreme pressure agent of relatively low viscosity and other multifunctional additive for lubricating oils and make up the solubility that has increased each component in the final lubricant compositions with the formative gear lubricant basically in conjunction with organic acid and amine component.

Embodiment

Term used herein " hydrocarbon substituent " or " hydrocarbyl group " use by their ordinary meaning, and this is well-known to those skilled in the art.Particularly, it is meant a carbon atom that directly is connected with the remainder of molecule and the group that mainly has the hydrocarbon feature.Alkyl is exemplified below:

(1) hydrocarbon substituent, promptly, aliphatics (for example alkyl or alkenyl), alicyclic (for example cycloalkyl, cycloalkenyl group) substituting group, aromatic substituents with aromatic series, aliphatics, alicyclic replacement, also has the cyclic substituent (for example, two substituting groups form an alicyclic group together) of finishing ring by the other parts of molecule;

(2) hydrocarbon substituent of Qu Daiing promptly, contains the substituting group of the non-hydrocarbyl group (for example halogen (especially chlorine and fluorine), hydroxyl, alkoxyl group, sulfydryl, alkyl thiol, nitro, nitroso-group and sulphur oxygen base) that does not change main hydrocarbon substituent;

(3) assorted substituting group, promptly following poly-Dai Ji, this substituting group has the hydrocarbon characteristic of dominance, and the atom beyond carbon atoms on ring or the chain, and described ring or chain are made of carbon atom.Heteroatoms comprises sulphur, oxygen, nitrogen, and comprises the substituting group as pyridyl, furyl, thienyl and imidazolyl and so on.Usually, in hydrocarbyl group, per ten carbon atoms have no more than two non-hydrocarbon substituent, a general no more than non-hydrocarbon substituent; In hydrocarbyl group, there is not non-hydrocarbon substituent typically.

Unless special explanation, term used herein " weight percent " is meant the per-cent of described composition with respect to whole composition weights.

Prepare final gear oil according to described exemplary embodiment here and may have different initial viscosities, according to the definition of ASTM D2983 in motor-driven gear of SAEJ306 and lubricant viscosity grade, this initial viscosity is 150 by viscosity, and the maximum temperature during 000cP is represented.Therefore, gear oil preparation described here contains a large amount of base oils usually, for example, base oil from about 75 weight % to about 98 weight %, with a spot of functional additive or multifunctional additive for lubricating oils, for example, the multifunctional additive for lubricating oils from about 2 weight % to about 25 weight %.

Base oil

The gear oil of composition described herein can be based on natural oil or synthetic oil or their blend, as long as lubricant has the appropriate viscosity that can be used for the gear oil purposes.Therefore, these base oils generally have from SAE50 to SAE 250 range of viscosities, and are more typically from SAE 70W to SAE 140.Suitable motor-driven gear oil also comprises multi-grade oil, for example 75W-140,80W-90,85W-140,85W-90 etc.

Be suitable for providing the base stock of base oil can use multiple different working method to be prepared, include but not limited to distillation, solvent treatment, hydrogen processing, oligomerization, esterification and re-refine.December in 1996 stipulated that all base stocks were divided into five basic classes in the 14 edition API 1509 " engine oil permission and the Verification Systems (Engine Oil Licensing and Certification) ":

Group I contains less than the saturates of 90wt% and/or greater than the sulphur of 0.03wt%, and has more than or equal to 80 and less than 120 viscosity index;

Group II contains more than or equal to the saturates of 90wt% and is less than or equal to the sulphur of 0.03wt%, and has more than or equal to 80 and less than 120 viscosity index;

Group III contains more than or equal to the saturates of 90wt% and is less than or equal to the sulphur of 0.03wt%, and has the viscosity index more than or equal to 120;

Group IV is polyalphaolefin (PAO); With

Group V comprises that all are not included in other base stock among group I, II, III or the IV.

Be used to define the ASTM D2007 that above-mentioned group testing method relates to saturated oil; The ASTM D2270 that relates to viscosity index; With one of the ASTM D 2622,4294,4927 that relates to sulphur and 3120.

Group IV base stock, just, polyalphaolefin (PAO) comprises the hydrooligomer of alpha-olefin, the most important method of oligomerization is free radical method, Ziegler catalyst method and positively charged ion, Friedel-Crafts catalyst method.

Polyalphaolefin generally has from 2 to 100cSt viscosity under 100 ℃, and it is desirable in the time of 100 ℃ is 4 to 8cSt.They can be for example to have the branching of 2 to 16 carbon atoms or the oligopolymer of linear alpha-olefin, and concrete example is polypropylene, polyisobutene, poly-1-butylene, poly--the 1-hexene, poly--the 1-octene, poly--1-decene.Comprise homopolymer, multipolymer and mixture.

Base oil can comprise the mixture of single base stock (base stock) or base stock.In the described here exemplary, base oil contains at least a base stock of nonpolar feature basically that has.For example, base oil can be base stock and a large amount of group II, the group III of small number of groups I or the mixture of organizing the base stock of IV.

Some additive components are dissolved in inert diluent or solvent with activeconstituents, and for example the form of the solution in thinning oil or the mineral oil provides.Unless opposite statement regulation is arranged, and the quantity of every kind of additive component and concentration are to explain according to active additive, that is, with these initial components may be relevant solvent or in the amount of thinner is not included in.

As previously mentioned, gear lubricant contains one or more additives usually.Additive is selected from dispersion agent, resist, extreme-pressure additive, antiwear additive, rust-preventive agent, antioxidant, deodorizing composition, deaerating agent, demulsifying compound, dyestuff, friction modifier, sealed expander and fluorescent colorant.Although unessential, this additive combination can be a kind of gear additive combination of preparation fully, such as, a kind of combination that can satisfy API GL-5 and/or API MT-1 and/or MIL-PRF-2105E and/or AGMA9005-D94 requirement.The type of component and amount depend on the expection end-use of product in the additive combination.

Dispersion agent

Operable dispersion agent comprises at least a oil soluble ashless dispersant, and this dispersion agent has a basic nitrogen and/or at least one hydroxyl in molecule.Suitable dispersion agent comprises alkenyl succinimide, alkenyl succinate, alkenyl succinate-acid amides, Mannich base, hydrocarbyl polyamine or polymkeric substance polyamines.

Wherein succsinic acid is that the alkenyl succinimide that group (succinic group) has contained the hydrocarbyl substituent of at least 30 carbon atoms is described in, for example in the U.S. Patent No. 3172892,3202678,3216936,3219666,3254025,3272746 and 4234435.Alkenyl succinimide can form by conventional method, for example by alkenyl succinic anhydrides, acid, acid esters, acyl chlorides or lower alkyl esters and the polyamines that contains at least one primary amino group are heated together.Mixture by heating alkene and maleic anhydride for example arrives about 180-220 ℃, can easily prepare alkenyl succinic anhydrides.Alkene can be rudimentary monoolefine, for example ethene, propylene, 1-butylene, polymkeric substance of iso-butylene etc. and composition thereof or multipolymer.The alkenyl source can be from polyisobutene, and the gel permeation chromatography that this polyisobutene has (GPC) number-average molecular weight arrives between about 2500 the scope about 500 usually up to 10,000 or higher, typically is in about 800 in about 1500 scope.

" succinimide " used herein be intended to comprise one or more polyamine reactant and the succsinic acid that replaces of hydrocarbon or acid anhydrides (or similarly succinic acylating agent) between the complete reaction product of reaction; and be intended to comprise such compound; wherein this product can also have acid amides, amidine and/or sat linkage except having the imide bond that is produced by primary amino and anhydride moiety reaction.

Aforesaid various types of ashless dispersant can pass through in the method phosphorylation described in U.S. Patent No. 3184411,3342735,3403102,3502607,3511780,3513093,4615826,4648980,4857214 and 5198133.

Dispersion agent also can be selected from the boronation dispersion agent.The method of the ashless dispersant of the various kinds that boronation is above-mentioned has description in U.S. Patent No. 3087936,3254025,3281428,3282955,2284409,2284410,3338832,3344069,3533945,3658836,3703536,3718663,4455243 and 4652387.

The method of phosphorylation and boronation ashless dispersant, for example above-mentioned method, on the books in U.S. Patent No. 4857214 and 5198133.

When ashless dispersant exists, its amount is based on becoming oil, and " in activeconstituents " (for example, the weight that does not comprise relevant with it usually impurity, thinner and solvent) arrive between about 7.5 weight percents about 0.5 usually, generally between about 0.5 to 5.0wt%, desirable between about 0.5 to about 3.0wt%, better arrives between about 3.0wt% about 2.0.。

Resist

Operable copper resist can comprise thiazole, triazole and thiadiazoles.Example comprises benzotriazole, tolyl-triazole, octyl group triazole, decyl triazole, dodecyl triazole, 2-mercaptobenzothiazole, 2,5-dimercapto-1,3,4-thiadiazoles, 2-sulfydryl-5-sulfo-alkyl-1,3,4-thiadiazoles, 2-sulfydryl-5-dithio alkyl-1,3,4-thiadiazoles, 2,5-two-(sulfo-alkyl (hydrocarbylthio))-1,3,4-thiadiazoles and 2,5-two-(dithio alkyl)-1,3, the 4-thiadiazoles.Suitable compound is 1,3,4-thiadiazoles, particularly 2-dithio alkyl-5-sulfydryl-1,3,4-thiadiazoles and 2,5-two (dithio alkyl)-1,3,4-thiadiazoles and their mixture, many can the acquisition by commodity wherein.

Other suitable copper resist comprises ether amine; The polyethoxye compound is amine ethoxylate for example, thanatol and ethoxy alcohol; Tetrahydroglyoxaline etc.Referring to, U.S. Patent No. 3663561 and 4097387 for example.General concentration in enriched material is up to about 3wt%.Suitable copper resist comprises ashless dialkyl group thiadiazoles.This ashless dialkyl group thiadiazoles can be from Richmond, and the Afton chemical company of Virginia obtains.

The general formula of operable dialkyl group thiadiazoles is:

R wherein ¹It is hydrocarbyl substituent with 6 to 18 carbon atoms; R ²It is hydrocarbyl substituent with 6 to 18 carbon atoms; And can with R ¹Identical or different.Usually, R ¹And R ²Have about 9-12 carbon atom, and general R ¹And R ²Each has 9 carbon atoms.

The dialkyl group thiadiazoles of formula (I) and the mixture of monoalkyl thiadiazoles also can be used for the scope of exemplary embodiment.Work as substituent R ¹Or R ²In one when being H, this monoalkyl thiadiazoles has just appearred.

Extreme pressure agent

Gear oil preparation disclosed by the invention can contain at least a sulfur-bearing extreme pressure (EP) agent.This sulfur-containing extreme-pressure additive can contain the sulphur of at least 25 weight %.The amount that joins the described EP agent in the gear oil generally is enough to provide at least 10 in final gear oil preparation, and the sulphur of 000ppm it is desirable to provide about 10,000 to about 30, the sulphur of 000ppm, and better provides about 12,000 to about 25, the sulphur of 000ppm.

The sulfur-containing extreme-pressure additive of numerous species or extreme pressure compound can be used for exemplary described here.The suitable groups compound that is used for this purposes comprises sulfurized animal or plant fat or oily, sulfurized animal or plant fatty acid ester, the all or part of esterification ester of trivalent or pentavalent phosphoric acid, olefine sulfide (referring to, for example U.S. Patent No. 2995569,3673090,3703504,3703505,3796661,3873454,4119549,4119550,4147640,4191659,4240958,4344854,4472306 and 4711736), dialkyl gather sulphur (referring to, for example U.S. Patent No. 2237625,2237627,2527948,2695316,3022351,3308166,3392201,4564709; With English Patent 1162334), the dialkyl of functional replacement gather sulphur (referring to, for example U.S. Patent No. 4218332) and poly-sulphur olefin product (referring to for example, U.S. Patent No. 4795576).

Another type of this preparation is the polysulphide that is made of one or more compounds, and the general formula of described compound is shown below: R ⁶-S _x-R ⁷, R wherein ⁶And R ⁷Be alkyl, wherein each all contains 3 to 18 carbon atoms, and x can be 2 to 8, and general scope is 2 to 5, and particularly 3.Alkyl can adopt various types, for example alkyl, cycloalkyl, alkenyl, aryl or aralkyl.Also can use the tertiary alkyl polysulphide, 2-tertiary butyl trisulphide for example, and can use the mixture that comprises 2-tertiary butyl trisulphide (for example, main or all by three, four and the mixture formed of pentasulfide).Other available dialkyl polysulphide comprises diamyl polysulphide, dinonyl polysulphide, dilauryl polysulphide and dibenzyl polysulphide.

By making alkene, can make a kind of specially suitable extreme pressure agent as iso-butylene and reaction of Salmon-Saxl.Its product, for example sulfide isobutene (SIB) particularly vulcanizes polyisobutene, contains the sulphur from about 10 weight % to about 55 weight % usually, it is desirable to the sulphur from about 30 weight % to about 50 weight %.Other alkene or unsaturated hydrocarbons of many kinds, for example, isobutene dimer or trimer can be used to form the olefine sulfide extreme pressure agent.The multiple method that is used for preparing olefine sulfide is disclosed in the prior art.Referring to, people's such as people's such as people's such as people's such as the U.S. Patent No. 3471404 of Myers, Papay U.S. Patent No. 4204969, Zaweski U.S. Patent No. 4954274, DeGonia U.S. Patent No. 4966720, Horodysky U.S. Patent No. 3703504 for example.

The method for preparing olefine sulfide comprises disclosed method in the above-mentioned patent, generally includes a plurality of steps.The first step is usually directed to be commonly referred to as the formation of the material of " adducts ", wherein alkene and halogenation sulphur, for example sulfur monochloride reaction.The reaction of this adducts and sulphur source provides olefine sulfide then.The quality of olefine sulfide is measured by multiple physical property usually, comprises for example viscosity, sulphur content, halogen amount and copper corrosion test weight loss (CCT).

U.S. Patent No. 4966720 relates to the olefine sulfide and their two-step reaction of preparation of extreme pressure (EP) additive that can be used as in the lubricant.In the first step, the temperature of reaction between alkene and the sulfur monochloride remains on 0 ℃ to 22 ℃, thereby makes the lower molecular weight adducts.In second step of reaction, sulfur monochloride/aliphatic monoolefine adducts in about 50 ℃ of reactions under the temperature condition that refluxes, forms olefine sulfide in the alkaline aqueous alcoholic solution of Containing Sulfur sodium.The conventional method for preparing olefine sulfide produces the product that dissolves readily in group I base oil.Yet when not having compatilizer, olefine sulfide very little is dissolved in the base oil of group II and group III.

Therefore,, the reaction times being minimized, and eliminate the adding of solid-state sulphur between the reaction period, can obtain the easier olefine sulfide that is dissolved in group II and group III base oil by improve adding the speed of adducts in the moisture sodium sulfide solution.Thus obtained olefine sulfide has the viscosity that is not higher than about 5.5 centistokes under 100 ℃, and sulphur content and is dissolved in group II and the group III base oil between about 40% to about 50% easily by weight.Especially, sulfur monochloride/aliphatic monoolefine adducts pass of joining interpolation speed in the sodium sulfide solution and viscosity ties up to following table and illustrates:

Table 1

The sample sequence number	Adducts interpolation speed (minute)	Viscosity under 100 ℃
The sample sequence number	Adducts interpolation speed (minute)	Viscosity under 100 ℃	1	25	4.7
2	45	5.21	1	25	4.7
2	45	5.21	3	60	6.23
4	75	6.56	3	60	6.23
4	75	6.56	5	90	6.91
6	120	7.33	5	90	6.91
6	120	7.33	7	135	9.27
8	240	16.25	7	135	9.27

According to above-mentioned form, adding speed less than about 60 minutes adducts can provide the sulfurized extreme pressure agent with desired viscosity.Being used for the illustrative methods that is dissolved in the sulfurized extreme pressure agent of group II and group III base oil easy to manufacture can prove by ensuing non-restrictive example.

Embodiment 1

The preparation of adducts

Liquid sulfur monochloride (700g) added to be equipped with agitator, thermometer, remain in the suitable reaction flask of 5 ℃ condenser and lower surface gas bubbler., gaseous state iso-butylene with the form of bubble blasted sulfur monochloride liquid level in reaction flask under, stir simultaneously and raise the temperature to 20 ℃, in entire reaction course, make reaction mixture remain on this temperature thereafter.The iso-butylene of 530g is altogether joined in the sulfur monochloride liquid.By highly basic washing, the HCl that iso-butylene and sulfur monochloride reaction are produced removes from waste gas.The adducts of Xing Chenging is transparent succinol thus, and it can be used for forming sulfide isobutene in second reactions steps.This adducts has about 1.183 ± 0.05 proportion under 15.6 ℃.

Dissolve in group II﹠amp; The preparation of the sulfide isobutene of group III base oil

In reaction flask, pack into n-propyl alcohol, the 50wt% aqueous sodium hydroxide solution of 135g and the 36wt% Sodium sulfhydrate aqueous solution of 410g of antifoams B, 325g of water, 1/2 dropper of 175g.Speed with 700rpm stirs and is heated to about 60 ℃ in nitrogen atmosphere to mixture, joined the above-mentioned adducts of 500g under the liquid level of mixture this moment in 30 minutes, and the temperature of reaction that raises gradually simultaneously temperature of charge before adducts adds the step end reaches about 90 ℃.Add after step finishes at adducts, under barometric point,, alcohol stripping from reaction mixture is come out by reacting by heating thing to 100 ℃.Behind pure stripping step, the pressure of reaction flask is reduced to 23 inches of mercury, make simultaneously reaction flask be cooled to about 70 ℃ to finish pure and mild most water removing from reactant.Water (300g) is joined in the product of generation, stirred product and water 10 minutes, then left standstill 15 minutes.The moisture salt deposit of bottom is separated by this layer of decant from flask, then at 100 ℃, 28 " organic layer was carried out coupling vacuum stripping 45 minutes under the mercury column.Filter by the organic layer of bed of diatomaceous earth after, obtain limpid butter stripping.The product of making by above-mentioned process is analyzed, its under 100 ℃, have usually 4.0 to 5.5cSt. viscosity, approximately 44-47 weight % sulphur content, less than the chlorinity of 1wt% and the copper corrosion test weight loss (CCT) of the about 30-80 milligram of every 100ml sample.

Antiwear agents

In order to reach purpose of the present invention, the composition that contains p and s in its chemical structure simultaneously is considered to phosphorated antiwear agents and/or extreme pressure agent, rather than the antiwear agents of sulfur-bearing and/or extreme pressure agent.Operable suitable phosphorous antiwear agents comprises the oil soluble amine salt of phosphoric acid ester, as U.S. Patent No. 5354484 and 5763372 the instruction those; Reaction product with dicyclopentadiene and thiophosphoric acid.

Can be by phosphoric acid ester and ammoniacal liquor or alkaline nitrogen compound, for example the reaction of amine prepares the amine salt of phosphoric acid ester.These salt can form respectively, phosphate ester salt can be added in the lubricant compositions then.

The phosphoric acid ester that can be used for preparing amine salt has following general formula:

R wherein ¹Be hydrogen or alkyl, R ²Be alkyl, two X groups are O or S.

Be used to prepare phosphoric acid ester oxy-compound be characterized as general formula R OH, wherein R is an alkyl.Can contain the mixture that general formula is the oxy-compound of ROH with the oxy-compound of phosphorus compound reaction, wherein alkyl R contains about 1 to 30 carbon atom.Highly desirable is that the amine salt of the phosphoric acid ester of the replacement that makes at last dissolves in the described lubricant compositions.Usually, the R group contains at least 2 carbon atoms, is generally 3 to 30 carbon atoms.

The R group can be aliphatics or aromatic series, for example alkyl, aryl, alkaryl, aralkyl and alicyclic hydrocarbon group.General formula is that the example of the useful oxy-compound of ROH comprises, for example, ethanol, sec.-propyl, propyl carbinol, amylalcohol, hexanol, 2-ethyl-hexanol, nonyl alcohol, dodecanol, stearyl alcohol, amyl phenol, octyl phenol, nonylphenol, methyl-cyclohexanol, alkylation naphthols etc.

Suitable alcohol roh is a fatty alcohol, more particularly is the aliphatic primary alcohol that contains about at least 4 carbon atoms.Therefore, the example of useful monobasic alcohol roh comprises amylalcohol, 1-octanol, 1-decanol, 1-dodecanol, 1-tetradecanol, 1-cetyl alcohol, 1-Stearyl alcohol, oleyl alcohol, inferior oleyl alcohol, linolenyl alcohol, phytol, myricyl alcohol, lauryl alcohol, tetradecyl alcohol, hexadecanol, stearic pure and mild behenyl alcohol.In business-like alcohol (comprising mixture) is also included within.

Amine salt of the present invention can react by above-mentioned phosphoric acid ester and at least a aminocompound and prepare, and this aminocompound can be primary amino compound or secondary amino compound.The amine that generates amine salt with the phosphoric acid ester reaction is uncle's alkylamine, and this uncle's alkylamine has following general formula:

R′NH ₂

Wherein R ' is the alkyl that contains the highest about 150 carbon atoms, is more typically to contain about 4 aliphatic alkyls to about 30 carbon atoms.

In an exemplary, the alkylamine that can be used for preparing amine salt is the alkyl primary amine, and it contains about 4 to about 30 carbon atoms in alkyl, is typically and contains about 8 to about 20 carbon atoms in alkyl.This alkyl can be saturated or unsaturated.The example of representational saturated primary amine is the aliphatics primary aliphatic amine.Typical aliphatic amide comprises alkylamine, for example normal hexyl Amine, n-octyl amine, n-Decylamine, positive amino dodecane, positive tetradecy lamine, positive pentadecyl amine, positive cetylamine, positive stearylamine (stearylamine) etc.Unsaturated primary amine comprises dodecylene amine, tetradecene amine, cetene amine, oleyl amine and inferior oleyl amine.

In another exemplary, amine salt is to be derived by the uncle's Armeen that has about at least 4 carbon atoms in the alkyl.Be to derive less than the alkylamine of about 30 carbon atoms mostly by having sum in the alkyl group.

Usually, uncle's Armeen is the monoamine shown in the following formula

Wherein R contains 1 alkyl to about 30 carbon atoms.This amine can carry out example with following material: TERTIARY BUTYL AMINE, uncle's hexyl primary amine, 1-methyl isophthalic acid-amino-hexanaphthene, uncle's octyl group primary amine, uncle's decyl primary amine, uncle's dodecyl primary amine, uncle's tetradecyl primary amine, uncle's hexadecyl primary amine, uncle's octadecyl primary amine, uncle's tetracosyl primary amine, uncle's octacosyl primary amine.Also can use the mixture of these amine.

The oil soluble amine salt can mix above-mentioned phosphoric acid ester and above-mentioned amine and prepare by in room temperature or be higher than under the room temperature.Usually, at room temperature mix approximately maximum one hour just enough.Be at least whenever the about 1 equivalent amine (in nitrogen) of amount phosphoric acid with the amount of the salifiable amine of phosphoric acid ester reaction shape, equivalence ratio is generally about 1.

The preparation method of this amine salt is well-known, can know from document.For example, referring to U.S. Patent No. 2063629,2224695,2447288,2616905,3984448,4431552,5354484, the open No.WO87/07638 of PCT international application.

Alternatively, when the gear oil itself of formative gear oil concentrate or preparation, when acid phosphoric acid ester and above-mentioned amine mixed, amine salt can original position form.For example, the uncle's alkylamine as rust-preventive agent can be added in the gear additive enriched material that contains acid phosphoric acid ester and forms phosphate amine salt.As following more detailed description, when the amine that will be used for enriched material or lubricant formulations and acidic cpd mix, and then with sulfurized extreme pressure agent with after multifunctional additive for lubricating oils or lubricant formulations mix, sulfurized extreme pressure agent enhanced solvability will display.

Rust-preventive agent

Lubricant formulations described herein contains rust-preventive agent usually.Rust-preventive agent can be to have to prevent that the ferrous metal surface from the single compound of corrosive performance or the mixture of multiple compound taking place.This material comprises the oil soluble monocarboxylic acid, as 2 ethyl hexanoic acid, lauric acid, tetradecanoic acid, palmitinic acid, oleic acid, linolic acid, linolenic acid, docosoic, cerinic acid or the like, with oil-soluble and comprise dimer and the poly carboxylic acid of tripolymer acid, for example make by ready denier oil acid, oleic acid, linolic acid etc.

Other suitable rust-preventive agent comprise the alkenyl succinic that contains 10 or more a plurality of carbon atoms in the alkenyl, for example, and tetrapropylene base succsinic acid, tetradecene base succsinic acid, cetene base succsinic acid etc.; The α of long-chain, molecular weight ranges from 600 to 3000, Ω-dicarboxylic acid; And other similar substances.

Rust-preventive agent recited above can be purchased by various different commercial source, for example, and dimer and tripolymer acid that Connecticut State Cromton Corporation of Middlebury sells.

Another useful acid rust-preventive agent is alkenyl succinic and the alcohol compound that 8 to 24 carbon atoms are arranged in the alkenyl, as the half ester of polyoxyethylene glycol.Useful especially rust-preventive agent comprises primary amine and secondary amine compound, is the amine moiety of described phosphate ester salt herein, and other the above-mentioned rust-preventive agent and the mixture of described amine.When the amine salt of phosphoric acid ester is used as the phosphorated extreme pressure compound, can in the gear oil preparation, adds other and contain amine rust-preventive agent.No matter primary amine and secondary amine compound are classified as the part of rust-preventive agent, anti-wear system or both combinations, they are the nitrogen of supply gear oil formulation 40-125ppm (in w/w) all.

Antioxidant

The antioxidant that can be used in the gear oil preparation contains phenolic compound and amine.It is generally just enough that its amount in enriched material reaches the highest about 5wt%.Gear lubricant can comprise one or more antioxidants, for example, one or more phenol antioxidant, hindered phenol antioxidant, other olefine sulfide, aromatic amine antioxidant, aromatic secondary amine antioxidant, sulfurized phenolic antioxidants, oil-soluble copper compounds and their mixture.

Suitable exemplary compounds comprises 2,6-DI-tert-butylphenol compounds, tert-butylation phenol, 2,6-di-tert-butyl-4-methy phenol, 4,4 '-methylene-bis (2, the 6-DI-tert-butylphenol compounds), 2, the methylene bridged polyalkylbenzene phenol of liquid mixture, blended, 4 of 2 '-methylene radical two (4-methyl-6-tert butyl phenol), 4 '-thiobis (2-methyl-6-tert butyl phenol), N, N '-two-secondary-butyl-p-phenylenediamine, 4-sec.-propyl aminobenzidine, alkylated biphenyls amine and phenyl-a-naphthylamine.

In amine antioxidants, the oil soluble aromatic secondary amine; Monobasic aromatic amines etc. all are suitable for.The monobasic aromatic amine comprises p-diaminodiphenyl, contains the alkyl biphenyl amine of 1～2 alkyl substituent, wherein each alkyl substituent has about 16 carbon atoms at most, phenyl-a-naphthylamine, the phenyl-a-naphthylamine that alkyl or aralkyl replace, it contains 1 or 2 alkyl or aralkyl, respectively has about 16 carbon atoms at most.

In phenol antioxidant, suitable compounds comprises: ortho-alkylated phenolic compound, for example, the 2-tert.-butyl phenol, 2,6 di t butyl phenol, 4-methyl-2,6 DI-tert-butylphenol compounds, 2,4,6-tri-butyl-phenol, and various analogue or homologue or their mixture; One or more as in the U.S. Patent No. 6096695 record the partial vulcanization phenolic compound and U.S. Patent No. 3211652 in the record methylene bridged alkylphenol.

Antioxidant can at random account for about 0.00%～about 5.00 weight % in final full preparation lubricant compositions, account for about 0.01～about 1.00 weight % usually.

Defoamer

Spendable defoamer comprises: have silicone oil, glyceryl monostearate, the polyoxyethylene glycol cetylate of proper viscosity, trialkyl-single thiophosphate ester, benzoyl acetone, wintergreen oil, XU 61518.10, glyceryl dioleate and the polyacrylic ester of sulforicinoleic acid.The general working concentration defoamer of the highest about 1wt% in multifunctional additive for lubricating oils.

Demulsifying compound

The typical additive that can be used as demulsifying compound in gear oil comprises: benzene sulfonamide acid esters, polyethylene oxide, poly(propylene oxide), oil-soluble acid fat etc.The general working concentration examples of such additives of the highest about 3wt% in multifunctional additive for lubricating oils.

Friction modifiers

Can contain one or more friction modifiers so that for example limited sliding capability and enhanced ormal traction (positraction performance) to be provided.Friction modifiers generally comprises such as aliphatic amide or ethoxy fatty amine, aliphatic fatty acid acid amides, oxyethyl group fatty ether amine, aliphatic carboxylic acid, glyceryl ester, aliphatic carboxylic acid esteramides and fatty tetrahydroglyoxaline, the such compound of fat tertiary amine, and wherein aliphatic group generally contains more than about eight carbon atoms to give compound with oil soluble.In addition, by one or more aliphatic succsinic acids or acid anhydrides and ammonia or the resulting aliphatic substituted succinimide of other primary amine reactions are suitable for too.

Sealed expander

The sealed expander that also can contain 0～20 weight % in the lubricant compositions.Suitable sealed expander comprises be obstructed polyol ester and oil soluble diester.Described diester comprises adipic acid ester, azelate and C ₈-C ₁₃The sebate of alkanol (or their mixture), and C ₄-C ₁₃The phthalic ester of alkanol (or their mixture).The mixture of two or more dissimilar esters (for example, hexanodioic acid dialkyl and dialkyl azelate etc.) also is suitable for.Such examples of material comprises: the n-octyl of hexanodioic acid, nonane diacid, sebacic acid, 2-ethylhexyl, isodecyl ester and tridecyl diester; Normal-butyl, isobutyl-, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, undecyl, dodecyl and tridecyl diester with phthalic acid.Concrete example comprises two-2-ethylhexyl adipic acid ester, diisooctyl adipic acid ester, (2-ethylhexyl) (isodecyl) adipic acid ester, two-2-ethylhexyl sebate and diiso decyl adipic acid ester.

Though binder component temporarily is described according to function, same component may provide one of other functions, and described function can not be understood that to force the function that limits.

Diluent oil

Multifunctional additive for lubricating oils described herein can comprise suitable diluent, is generally the oily thinner with appropriate viscosity.Such thinner can be by obtaining in the natural or synthetic resource.In mineral (hydrocarbon matter) oil, paraffinic base, cycloalkyl, asphaltic base and mixing base oil are arranged.Typical synthetic base oil comprises polyolefin oil (being meant hydrogenation-alpha-olefin low polymers especially), alkylation aromatic compound, polyalkylene oxide, aromatic oxide and carboxylicesters (particularly diester oil).Natural and synthetic oil also can mix use.Thinner can be the light hydrocarbon base oil of selecting from natural and synthetic base oil.Diluent oil has the viscosity of 13-35 centistoke under 40 ℃ in general.

For some application, pour point depressor can be joined in the gear oil preparation.If present, generally can contain the pour point depressor of the highest 5wt.% in the gear oil preparation compositions.

Composition of the present invention can be handled (top treated) for possessing multi-functional performance (promptly on automobile and industrial use) by the top.

Above-mentioned multi-stage gear oil is suitable for the automobile gear purposes and uses, for example final stage transmission of underloading or heavy-duty vehicle, power divider or axle, and the manual transmission in truck or the heavy equipment, and industrial gear is used.

What illustrate below is the gear oil additive combination that makes by ordinary method and method disclosed by the invention.This gear oil additive combination comprises each component of amount shown below.

Table 1

The gear oil additive component

Component	Wt.％
Component	Wt.％	Tolyl-triazole	0.0-0.3
Primary amine	2.0-7.0	Tolyl-triazole	0.0-0.3
Primary amine	2.0-7.0	Acid phosphate	5.0-15.0
The polyacrylic ester defoamer	1.0-5.0	Acid phosphate	5.0-15.0
The polyacrylic ester defoamer	1.0-5.0	The mineral oil thinner	5.0-10.0
Carboxylic acid rust-preventive agent	0.0-2.0	The mineral oil thinner	5.0-10.0
Carboxylic acid rust-preventive agent	0.0-2.0	The thiadiazoles resist	2.0-5.0
Sulfide isobutene	50.0-95.0	The thiadiazoles resist	2.0-5.0

Embodiment 2

In the present embodiment, the amount of the order of mixing aforementioned component and each component is shown in the table 2.Present embodiment is represented is the ordinary method that is used for making the multifunctional additive for lubricating oils of lubricant formulations.

Table 2

The interpolation order	Component	Wt.％
The interpolation order	Component	Wt.％	1	Sulfide isobutene	0.0-20.0
2	Primary amine	2.0-7.0	1	Sulfide isobutene	0.0-20.0
2	Primary amine	2.0-7.0	3	Tolyl-triazole	0.0-0.3
4	The mineral oil thinner	5.0-10.0	3	Tolyl-triazole	0.0-0.3
4	The mineral oil thinner	5.0-10.0	5	The thiadiazoles resist	2.0-5.0
6	Sulfide isobutene	0.0-95.0	5	The thiadiazoles resist	2.0-5.0
6	Sulfide isobutene	0.0-95.0	7	Acid phosphate	5.0-15.0
8	The polyacrylic ester defoamer	1.0-5.0	7	Acid phosphate	5.0-15.0
8	The polyacrylic ester defoamer	1.0-5.0	9	Carboxylic acid rust-preventive agent	0.0-2.0

Embodiment 3

In the following embodiments, the amount of the interpolation of said components order and each component is shown in the table 3.What present embodiment was represented is exemplary of the present invention, but is not for the present invention is made restriction.

Table 3

The interpolation order	Component	Wt.％
The interpolation order	Component	Wt.％	1	Tolyl-triazole	0.0-0.3
2	Primary amine	2.0-7.0	1	Tolyl-triazole	0.0-0.3
2	Primary amine	2.0-7.0	3	The thiadiazoles resist	2.0-5.0
4	Acid phosphate	5.0-15.0	3	The thiadiazoles resist	2.0-5.0
4	Acid phosphate	5.0-15.0	5	The polyacrylic ester defoamer	1.0-5.0
6	The mineral oil thinner	5.0-10.0	5	The polyacrylic ester defoamer	1.0-5.0
6	The mineral oil thinner	5.0-10.0	7	Carboxylic acid rust-preventive agent	0.0-2.0
8	Sulfide isobutene	50.0-95.0	7	Carboxylic acid rust-preventive agent	0.0-2.0

In table 2, in the preparation additive combination, sulfide isobutene adds in the first step with in the 6th step.In table 3, sulfide isobutene (SIB) adds in the final step of the mixing step of additive combination.Every kind of additive combination of preparation in table 2, the table 3 is mixed so that the lubricant compositions of the additive combination that contains the 4wt% that has an appointment to be provided with polyalphaolefin base gear oil and group II base oil.Polyalphaolefin base gear oil has 0.3 basic NTU (base NTU), and group II base oil has 2 basic NTU.During the turbidity of the every kind of lubricant compositions that is made by additive combination is listed in the table below.

Table 4

Sample number into spectrum	Base oil	Table 2 method (NTU)		Table 3 method (NTU)
	Base oil	Table 2 method (NTU)		Table 3 method (NTU)			Standard SIB	Low viscosity SIB	Standard SIB	Low viscosity SIB
	1	PAO	＞2000	-	-		Standard SIB	Low viscosity SIB	Standard SIB	Low viscosity SIB	-
2	1	PAO	＞2000	-	-	PAO	-	＞700	-	-	-
2	3	PAO	-	-	-	PAO	-	＞700	-	-	＜5
4	3	PAO	-	-	-	PAO	-	-	123	-	＜5
4	5	Group II	205	-	-	PAO	-	-	123	-	-
6	5	Group II	205	-	-	Group II	-	2	-	-	-
6	7	Group II	-	-	2	Group II	-	2	-	-	-
8	7	Group II	-	-	2	Group II	-	-	-	2	-

As above shown in the table, contain turbidity according to the lubricant formulations of the preparation of the additive combination of the method for table 3 preparation and unexpected and significant decline (sample 3,4 with sample 1 relatively) occurred, wherein at the final step interpolation sulfide isobutene of preparation additive combination technology.When lubricant and the preparation of at least a nonpolar substantially base oil, in any step before sulfurized extreme pressure agent being joined in additive combination or the lubricant, be mixed for the acidity of additive combination or lubricant and alkalescence or amine component and can obtain similar result.It is just inessential like this, whether the final step in the process of preparation additive or lubricant adds sulfide isobutene.

And, with sample 2 and 3 and sample 1 show that relatively and with sample 6,8 and sample 5 by using the SIB of low viscosity (solvable), the turbidity that can make PAO or organize the II base oil has significant decline after relatively.The result shows, shown in the contrast of sample 7 and sample 8, when adopting method shown in the table 3, uses the specific effect that SIB played not as at more nonpolar base oil in the layoutprocedure of group II base oil, and is remarkable as the effect of using among the PAO.Therefore, be used in combination low viscosity SIB and/or add the turbidity that SIB is particularly useful for the reduction preparation in above-mentioned blended acidity, alkalescence or amine component, described preparation comprises the nonpolar substantially base oil such as but not limited to group II, group III, group IV base oil and so on.

In sum, the present invention relates to following technical scheme:

1, a kind of raising contains the deliquescent method of the sulfurized extreme pressure agent in the lubricant compositions of basic nonpolar group oil ingredient, this method comprises: pre-mixing is used for the organic acid of slip additive combination of lubricant compositions and amine component so that the premixture of organic acid and amine component to be provided, this premixture is mixed so that the slip additive combination to be provided with having under 100 ℃ less than the sulfurized extreme pressure agent of the viscosity of about 5.5 centistokes, the turbidity that contains the lubricant compositions of this additive combination whereby is lower than at the turbidity that does not carry out under the pre-mixing organic acid and amine component are mixed with sulfurized extreme pressure agent prepared lubricant compositions again.

2, as scheme 1 described method, wherein sulfurized extreme pressure agent Containing Sulfur alkene.

3, as scheme 2 described methods, wherein olefine sulfide Containing Sulfur iso-butylene.

4,, further comprise the slip additive combination is mixed with basic nonpolar group oil ingredient as scheme 1 described method.

5, as scheme 4 described methods, wherein basic nonpolar group oil ingredient contains the polyolefine base oil.

6, as scheme 1 described method, wherein basic nonpolar group oil ingredient contains the polyolefine base oil.

7, as scheme 1 described method, wherein basic nonpolar group oil ingredient contains the base oil that is selected from group II base oil, group III base oil and group IV base oil.

8, the gear lubricant that makes according to the method for scheme 1.

9, a kind of vehicle, its moving-member contain the gear lubricant that is used for lubricated moving-member just like scheme 8.

10, a kind of preparation contains the method for the lubricant of extreme pressure agent, its improvement comprises: be mixed at least a organic acid of lubricant additive combination and amine component so that mixture to be provided, subsequently, again this mixture is mixed so that lubricant to be provided with sulfurized extreme pressure agent and base oil, wherein sulfurized extreme pressure agent makes by the method that the extreme pressure agent with certain limit viscosity is provided, and this range of viscosities can improve the solvability of extreme pressure agent in lubricant.

11, as scheme 10 described methods, wherein sulfurized extreme pressure agent Containing Sulfur alkene.

12, as scheme 11 described methods, wherein olefine sulfide Containing Sulfur iso-butylene.

13, as scheme 12 described methods, wherein sulfide isobutene has the viscosity that is not more than about 5.5 centistokes under 100 ℃.

14, as scheme 10 described methods, wherein base oil contains basic nonpolar group oil ingredient.

15, as scheme 14 described methods, wherein basic nonpolar group oil ingredient contains the polyolefine base oil.

16, a kind of gear lubricant that makes by the method for scheme 10.

17, a kind of vehicle, its moving-member contain the gear lubricant that is used for lubricated moving-member just like scheme 16.

18, a kind of method for preparing the muddy lubricant compositions of nothing of Containing Sulfur extreme pressure agent and basic nonpolar group oil ingredient, this method comprises:

Sulfur monochloride/iso-butylene the adducts and the Sodium sulfhydrate aqueous solution are reacted, and its reaction conditions is to be enough to be provided at have the sulfide isobutene that is not higher than about 5.5 centistoke viscosity under 100 ℃;

The organic acid and the amine component of lubricant compositions are pre-mixed so that the additive combination premixture to be provided;

Then this additive combination premixture is mixed to obtain compositions of additives with the sulfide isobutene of about 50～about 95 weight %; And

Adopt this compositions of additives to handle base oil so that no muddy lubricant compositions to be provided.

19, as scheme 18 described methods, wherein basic nonpolar group oil ingredient contains the polyolefine base oil.

20, a kind of gear lubricant, the compositions of additives that contains the mineral oil component and make by the method for scheme 18.

21, a kind of vehicle, its moving-member contain the gear lubricant that is used for lubricated moving-member just like scheme 20.

22, a kind of method for preparing sulfurized extreme pressure agent, this extreme pressure agent have the characteristic that promotion contains the low turbidity lubricant formation of nonpolar substantially base oil, and this method comprises:

Be enough to obtain under the condition of sulphur/olefin adducts sulfur monochloride and alkene to be reacted;

Make sulphur/olefin adducts mix with moisture sulphur source and react for some time, this section period is enough to obtain being in the organic phase and have the sulfurized extreme pressure agent that is not higher than about 5.5 centistoke viscosity under 100 ℃;

Water is separated from one another with the organic phase that contains sulfurized extreme pressure agent.

23, as scheme 22 described methods, wherein sulfurized extreme pressure agent Containing Sulfur iso-butylene.

24, as scheme 23 described methods, wherein the range of viscosities of sulfide isobutene under 100 ℃ is about 4.0～about 5.5 centistokes.

25, as scheme 23 described methods, wherein the sulfide isobutene sulphur content is about 40～about 50 weight %.

26, as scheme 22 described methods, wherein make sulphur/olefin adducts mix with moisture sulphur source and time of reacting be about 10～less than about 60 minutes.

Some United States Patent (USP)s have been quoted as a reference in a large number in many places of the full piece of writing of this specification sheets.During all these files that are cited are incorporated herein fully, as record fully here.

Above-mentioned embodiment can allow to do a lot of conversion in practice.Therefore, these embodiments are not limited only to above-mentioned disclosed specific embodiment.More appropriate is that previous embodiments should be meant that in the spirit and scope of appended claim it comprises the equivalent that is suitable on the legal sense.

The patent applicant not desire with all on literal not consistent with claim through improve or the embodiment of conversion all open to the public, but they all are considered to the part of its equivalent instruction at this.

Claims

2, the gear lubricant that makes according to the method for claim 1.

3, a kind of vehicle, its moving-member contain the gear lubricant that is used for lubricated moving-member as claimed in claim 2.

4, a kind of preparation contains the method for the lubricant of extreme pressure agent, its improvement comprises: be mixed at least a organic acid of lubricant additive combination and amine component so that mixture to be provided, subsequently, again this mixture is mixed so that lubricant to be provided with sulfurized extreme pressure agent and base oil, wherein sulfurized extreme pressure agent makes by the method that the extreme pressure agent with certain limit viscosity is provided, and this range of viscosities can improve the solvability of extreme pressure agent in lubricant.

5, a kind of gear lubricant that makes by the method for claim 4.

6, a kind of vehicle, its moving-member contain the gear lubricant that is used for lubricated moving-member as claimed in claim 5.

7, a kind of method for preparing the muddy lubricant compositions of nothing of Containing Sulfur extreme pressure agent and basic nonpolar group oil ingredient, this method comprises:

8, a kind of gear lubricant, the compositions of additives that contains the mineral oil component and make by the method for claim 7.

9, a kind of vehicle, its moving-member contain the gear lubricant that is used for lubricated moving-member as claimed in claim 8.

10, a kind of method for preparing sulfurized extreme pressure agent, this extreme pressure agent have the characteristic that promotion contains the low turbidity lubricant formation of nonpolar substantially base oil, and this method comprises: