CN101343591A - Lubricating oils having improved friction stability - Google Patents

Lubricating oils having improved friction stability Download PDF

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Publication number
CN101343591A
CN101343591A CNA2008101319413A CN200810131941A CN101343591A CN 101343591 A CN101343591 A CN 101343591A CN A2008101319413 A CNA2008101319413 A CN A2008101319413A CN 200810131941 A CN200810131941 A CN 200810131941A CN 101343591 A CN101343591 A CN 101343591A
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oil
friction modifiers
friction
hydrocarbyl substituent
alkyl
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CN101343591B (en
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R·F·沃茨
J·R·小诺莱斯
K·R·戈尔达
K·L·科根
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Infineum International Ltd
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Infineum International Ltd
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
    • C10M169/04—Mixtures of base-materials and additives
    • C10M169/048—Mixtures of base-materials and additives the additives being a mixture of compounds of unknown or incompletely defined constitution, non-macromolecular and macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M149/00—Lubricating compositions characterised by the additive being a macromolecular compound containing nitrogen
    • C10M149/12—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M149/14—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds a condensation reaction being involved
    • C10M149/22—Polyamines
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    • C10M137/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus
    • C10M137/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus having no phosphorus-to-carbon bond
    • C10M137/04—Phosphate esters
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    • C10M141/00—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential
    • C10M141/10—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential at least one of them being an organic phosphorus-containing compound
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    • C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
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    • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
    • C10M2203/1006—Petroleum or coal fractions, e.g. tars, solvents, bitumen used as base material
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    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/02—Hydroxy compounds
    • C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/026—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings with tertiary alkyl groups
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    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2207/125—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids
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    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/08—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type
    • C10M2209/084—Acrylate; Methacrylate
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    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
    • C10M2215/064—Di- and triaryl amines
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    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/08—Amides
    • C—CHEMISTRY; METALLURGY
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    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/086—Imides
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/22—Heterocyclic nitrogen compounds
    • C10M2215/223—Five-membered rings containing nitrogen and carbon only
    • C10M2215/224—Imidazoles
    • C—CHEMISTRY; METALLURGY
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    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/28—Amides; Imides
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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    • C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2217/04—Macromolecular compounds from nitrogen-containing monomers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2217/046—Polyamines, i.e. macromoleculars obtained by condensation of more than eleven amine monomers
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    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
    • C10M2219/046—Overbasedsulfonic acid salts
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    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/06—Thio-acids; Thiocyanates; Derivatives thereof
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    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/10—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring
    • C10M2219/102—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring containing sulfur and carbon only in the ring
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    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/10—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring
    • C10M2219/104—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring containing sulfur and carbon with nitrogen or oxygen in the ring
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    • C10M2223/049—Phosphite
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    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
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    • C10N2030/08—Resistance to extreme temperature
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    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/04—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives
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    • C10N2040/04—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives
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    • C10N2040/04—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives
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    • C10N2060/00—Chemical after-treatment of the constituents of the lubricating composition

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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

Lubricating oil compositions having excellent friction stability comprise a base lubricating oil, an oil soluble source of phosphorus and a defined polyalkylene polyamine-based friction modifier that has been reacted with an acylating agent to convert at least one secondary amine group into an amide.

Description

The improved lubricating oil of friction stability
The present invention relates to compositions of additives, described composition can be lubricating oil splendid friction stability is provided, especially to picture automatic transmission fluid (hereinafter referred to as " ATF "), continuously variable transmission fluid (" CVTF "), with double-clutch automatic transmission liquid (" DCTF ") homenergic transmission fluid, more particularly, described composition can be liquid splendid nature of friction is provided when the high speed clutch coupling engages.
The present invention comprises on the other hand makes this kind lubricating oil have the method for friction stability, comprises the compositions of additives that uses in the lubricating oil, to improve friction stability and other aspects as described below.
The transmission mechanism that the present invention is suitable for is meant that those contain the transmission mechanism of the lubricated humid clutch that uses under high-energy dissipation condition.The device of these types comprises the clutch coupling that is used for ratio or speed change on the automatic driver; At automatic driver, vari-speed drive, or the wet starting clutch in the double clutch transmissions; Or be used in clutch coupling on torque orientation (torque vectoring) or the shaft space difference speed.The characteristics of these clutch couplinges are that very high velocity contrast is arranged between the two elements of clutch coupling, and (engagement) or on " locking " (lock up) very high waste of energy are arranged at " joint " of clutch coupling.
Therefore, another aspect of the present invention also relates to energy driver, described device contains by transmission ofenergy liquid of the present invention lubricated veneer or multi-plate clutch device, wherein clutch coupling uses under the high-energy condition, promptly about 500rpm (rpm) more than speed on engage, particularly on speed, engage greater than 500rpm.
Automaker's common objective all is to produce the automobile of more durable and more reliable performance in its working life.Weather resistance that improves and reliability are to produce to need few as far as possible automobile of repairing in working life on the one hand.Second aspect is automobile to be showed stablize in its whole " life-span " process.For automatic driver, transmission mechanism does not only have fault in the life-span of automobile, and obvious variation does not take place its gear shift character during this period yet.Because the gear shift character of automatic driver depends on the rubbing characteristics of ATF to a great extent, so As time goes on liquid need with the increase of mileage very stable frictional behaviour to be arranged.This performance of ATF is exactly a friction stability.Present many automakers turn to the automatic transmission fluid of " using throughout one's life "; This trend has further increased the needs to the ATF friction stability, because will no longer change liquid 15,000 to 50,000 miles service intervals in the time.
The method that is commonly used to measure ATF friction weather resistance is to use SAE#2 friction testing instrument.The high velocity engagement of this instrument by using clutch coupling to make its energy that absorbs specified quantitative come simulated clutch as brake.System capacity is equal to clutch coupling and finishes the energy that once conversion is absorbed in the automobilism of reality.This machine uses specific bonding speed, 3600rpm normally, and the inertia that calculates provides required energy to test clutch coupling and liquid.Clutch coupling lubricates with evaluated liquid, and each deceleration of system (i.e. brake) is defined as a circulation.Assess friction stability by a plurality of circulations of successive.OEM (OEM) to hammering at of friction stability impel be used for showing the good circulation sum of friction weather resistance from the hundreds of in the 1980's bring up to some standards at present 10,000 or even higher.Specific examples is referring to Ford MERCON
Figure A20081013194100071
V automatic transmission fluid service standard.
Estimate improved friction weather resistance two kinds of methods are arranged.First kind is to keep specific rubbing characteristics in the longer time cycle (promptly more circulations).Second kind is to allow each friction parameter that littler variation takes place in through the process of same loop number.Two kinds of methods illustrate that all the gear shift character of automobile can keep constant in long mileage.
ATF, the friction control in CVTF or the DCTF homenergic transmission fluid is the major function of friction modifiers in the liquid.Yet, be used in the degraded that suffered heat of liquid in the transmission mechanism and oxidative stress can cause additive, therefore can cause the change of liquid property.The oxidation of friction modifiers or cause thermal damage at first show as the rising of stiction in the liquid usually.The stiction rising can cause stiff gearshift, and when whole gearshift was finished, the people in the automobile had the sensation of jolting or tilting.It is the common form that transmission ofenergy liquid lost efficacy that stiction rises.Yet in some cases, the oxidation of friction modifiers can convert them to active higher form.In these situations, stiction was actually and can reduces in the maintenance period.Although the reduction of stiction is not the problem that owner is concerned about usually, it can reduce the hold facility (holding capacity) of clutch coupling in the transmission mechanism.The reduction of hold facility then can cause clutch coupling in high loading lower slip such as traction or quick acceleration, thereby this can make their that overheated ultimate failure takes place easily.Therefore best transmission ofenergy liquid has the stiction level that in use can keep stabilizer pole well.
Usually, there is dual mode can improve transmission ofenergy liquid friction stability.First kind of mode is by increasing the content of friction modifiers in the liquid.Though the reserves that improve friction modifiers in oil can be obtained the effect of the improvement friction stability of expection, but the increase of friction modified agent content has but brought the undesirable side effect of people, and the frictional coefficient (particularly static friction coefficient) that is about to liquid is reduced under the aspiration level.The second way is an oxidation-resistance of using the oxidation suppressant additive to improve liquid by collaborative, particularly reduces the generation that can compete the polarity oxidation products of friction surface with friction modifiers.Therefore, the oxidation that reduces liquid might improve secular friction control.
United States Patent (USP) the 5th, 750,476 and 5,840, disclosed antioxidant No. 662, the composition of oil soluble phosphorus compound and special low effect friction modifiers can provide outstanding friction weather resistance for ATF.In case the characteristics of these low effect friction modifiers are that the concentration of friction modifiers reaches capacity in the liquid, continue to increase its concentration and can not further reduce the friction level of measuring before.Therefore, can come treatment liq increasing the reserves of additive in the oil with the low effect friction modifiers of this class of high density, and liquid still show satisfied friction level.Believe that when the friction modified agent molecule of low effect is consumed by shearing or oxidation the friction modifiers that also always has enough high densitys on friction surface is to substitute the part that consumes.Be used for preventing that the oil soluble P contained compound of system wear from also being necessary.
Yet this type of solution requires to use a large amount of additives certainly.This class solution need more effectively utilize chemical resource and more economically.
Similarly, the extra demand to oxidation retarder causes complicated more prescription, development prospect and cost of use.
We have had been found that a class friction modifiers now; it is polyalkylene polyamine base friction modifiers; the acylations that partly goes up at least one secondary amino group by its polyamines obtains, and this friction modifiers has more high thermal stability and oxidative stability, and the ability of its control friction is not subjected to any loss.When having an above secondary amino group in the polyamines chain, secondary amino group carries out acylations can make it have good especially stability to the great majority in the friction modifiers (all preferred).
This type of friction modifiers demonstrates the improvement character that surpasses existing approach, and it is for solving in the oil, and particularly the problem of friction weather resistance provides more economical approach in the transmission ofenergy liquid.
On the one hand; the present invention relates to lubricating oil (particularly transmission ofenergy liquid) composition; comprise oil soluble P contained compound and the polyalkylene polyamine base friction modifiers that has at least one hydrocarbyl substituent; this hydrocarbyl substituent or each hydrocarbyl substituent contain 6 to 30 carbon atoms, and wherein at least one secondary amino group on the friction modifiers polyamines chain is changed into the corresponding amide base by acyl group.
More specifically, the present invention relates to lubricating oil (particularly transmission ofenergy liquid) composition, comprising:
(a) account for the lubricating oil of main amount; With
(b) friction stability improves the compositions of additives of significant quantity, comprising:
(i) contain acylation agent R 3COX (R wherein 3Be alkyl, X is a leavings group) be selected from compound (I), (II) and the friction modifiers of the reaction product of one or more compounds in the group (III), wherein (I), (II) He (III) structure is as follows:
Figure A20081013194100091
Wherein:
R is C 6To C 30Alkyl or alkenyl; R 1Be the polyalkylene polyamine group shown in structure (IV):
Figure A20081013194100092
N and m each integer of from 1 to 6 independently naturally respectively wherein; R 2Be the heteroatomic derivative that contains of alkyl or aryl or they, or be selected from following V, the structure shown in VI and the VII;
Figure A20081013194100101
(ii) oil soluble P contained compound.
In the embodiment of back, structure I, the secondary nitrogen-atoms of at least one on the structure I V among II and the III (preferably each) respectively by being transformed into acid amides with the acylting agent reaction, obtains corresponding structure (VIII), (IX) and (X):
Figure A20081013194100102
Figure A20081013194100111
R wherein, R 1, R 2, R 3Define as above with n, wherein p+q=m (wherein the m definition as above) and p 〉=1.It is q=0 and p=m that yet choosing is arranged most.
In above all structures, R 3Preferred C 1To C 20Hydrocarbyl substituent, more preferably wherein a kind of in the heteroatomic analogue contained in alkyl or aryl or they.Even R 3More preferably C 1To C 10Alkyl or aryl, R 3C most preferably 1To C 6Alkyl or aryl, particularly methyl, ethyl, propyl group or butyl.
Others of the present invention comprise itself, and polyalkylene polyamine base friction modifiers (b) is (i) as defined above; Contain the compositions of additives of friction modifiers and oil soluble P contained compound combination as defined above; For lubricating oil provides the method for friction stability, be included in and use the additive combination as defined above that friction stability is improved significant quantity in the lubricating oil; And the compositions of additives as defined above that uses significant quantity in lubricating oil is to improve its friction stability.
Other aspects of the present invention and embodiment specify by following description.
Embodiment
The method that the present invention relates to improve the lubricating oil friction stability and do not reduce the shortcoming of frictional coefficient.Described method is included in unites self-defining polyalkylene polyamine friction modifiers in use source and oil-soluble phosphorus source in the oil.This combination of additive can be lubricating oil (especially transmission fluid) splendid friction stability is provided.
Though expectability benefit of the present invention is applicable to the lubricating oil (for example crankcase machine oil etc.) of various use friction modifiers, but particularly preferred composition branch is a transmission ofenergy liquid, especially automatic transmission fluid (ATF), continuously variable transmission fluid (CVTF) and double-clutch automatic transmission liquid (DCTF).The example that comprises the transmission ofenergy liquid of other less preferred type within the scope of the present invention is a gear oil, hydraulic efficiency oil, used with tractor oil, all-purpose tractor oil and analogue.These transmission ofenergy liquid can be by the additive and the preparation of base oil structure of various additional properties.
Polyalkylene polyamine base friction modifiers of the present invention
The preferred friction modifiers of the present invention can be made by the succinimide that has at least one hydrocarbyl substituent, and wherein this hydrocarbyl substituent or each hydrocarbyl substituent contain 6 to 30 carbon atoms, and preferably thiazolinyl or saturated alkyl analogue fully; Perhaps can be made by the carboxylic acid amides with at least one thiazolinyl or alkyl chain, described thiazolinyl or alkyl chain contain 6 to 30 carbon atoms, and have one or more structures that formed by corresponding alkenyl or alkyl carboxylic acid and polyalkylene polyamine reaction.
Most preferred friction modifiers type at first is by alkyl or alkenyl succinyl oxide and one or more polyalkylene polyamines, and preferably with one or more polyethylene polyamines prepared in reaction, the alkyl or alkenyl substituting group on the described succinyl oxide is the isomery chain.In this type of preferable material, the isomery chain combines with the alpha-carbon atom of succinimide ring, makes two substitution in side chain bases go up alpha-carbon atom by tertiary carbon atom and ring and links to each other, the alkenyl substituted structure of reacting with the polyethylene polyamines shown in for example following structure:
Figure A20081013194100121
Wherein x and y are respectively integers independently, and they and be from 1 to 25, z is from 1 to 10 integer.
The preparation method of isomerization alkenyl succinic anhydride is known by people, and is described in as United States Patent (USP) the 3rd, 382, in No. 172.The common preparation method of these materials makes its pair key move on to interior location by alpha-olefin is heated under the condition that has an acidic catalyst to exist.The mixture of alkene (2-alkene, 3-alkene etc.) carries out thermal response with maleic anhydride subsequently.Usually use from C 6(1-hexene) is to C 30The alkene of (1-30 alkene).Suitable isomerization alkenyl succinic anhydride as structure (I) comprises isodecyl succinyl oxide (x+y=5 in the following formula), Permethyl 99A. base succinyl oxide (x+y=7), different tetradecyl succinyl oxide (x+y=9), isocetyl succinyl oxide (x+y=11), isooctadecane base succinyl oxide (x+y=13) and Isoeicosane base succinyl oxide (x+y=15).Preferred isocetyl succinyl oxide and isooctadecane base succinyl oxide, they all demonstrate good performance.
All contain a two key (thiazolinyl) on the alkyl chain of the material that obtains by described prepared.The succinyl oxide of alkenyl substituted can be easy to by being hydroconverted into its saturated alkyl analogue.
The succinyl oxide that isomerization thiazolinyl or isomerization alkyl replace can generate the friction modifiers as structure (I) shown type subsequently with suitable amine reaction, and this friction modifiers can pass through R subsequently 3The acylations of COX forms friction modifiers of the present invention (b) (i).
Surrogate as isomerization thiazolinyl or isomerization alkyl succinic anhydride, also can select for use the carboxylic acid that has at least one thiazolinyl or alkyl chain and suitable amine reaction to generate as the structure (II) and (III) friction modifiers of shown type, described thiazolinyl or alkyl chain contain 6 to 30 carbon atoms.This type of acid preferably contains 12 to 22 carbon atoms, particularly contains the alkyl or alkenyl acid of 16 to 20 carbon atoms.Friction modifiers of the present invention passes through R subsequently 3The acylations of COX forms.
Be suitable for preparation as structure (I), (II) with (III) shown in the amine of friction modifiers shown in structure (XI):
Figure A20081013194100131
Wherein n and m are respectively from 1 to 6 integers independently, R 2Definition as above.
And the amine shown in structure XI can make by the reaction of uncle's polyamines.In this type of amine useful especially a kind of be polyalkylene polyamine shown in general formula (XII), general formula (XII) is:
Figure A20081013194100141
Wherein a is from 1 to 5 integer, preferably from 2 to 4; Each n is from 1 to 6 a integer independently, preferably from 1 to 4.
The non-limiting example of suitable polyamine compounds comprises: diethylenetriamine, triethylene tetramine, tetraethylene pentamine and five ethene hexamines.The low-cost polyamine mixture that per molecule contains 5 to 7 nitrogen-atoms can be the Polyamine H of Dow Chemical Co., Polyamine 400 and Polyamine E-300.
This class polyamines can be by reacting generating structure I with the succinyl oxide of above-mentioned alkenyl substituted or their complete saturated alkyl analogue; Perhaps generate II or III with above-mentioned thiazolinyl or alkyl carboxylic acid reaction.Generate or III.
The preferred friction modifiers of the present invention is usually by heating above-mentioned isomerized alkenyl succinic anhydride (or its saturated alkyl analogue) and above-mentioned polyamines, and the water of removing generation prepares.Yet also can use other known preparation method.The ratio of primary amine group and succinic anhydride group normally 1 to 1.In the molecule two ends were situation with primary amine terminated diamines or polyamines, the amino at molecule two ends all wished to generate material shown in structure (XIII) with the succinyl oxide reaction that replaces:
Figure A20081013194100142
R wherein, a and n definition are as above.
Acylting agent of the present invention is meant those materials that secondary amine can be converted to acid amides.The general formula of this class material is R 3COX, wherein R 3Be alkyl, X is a leavings group, described leavings group also can with the R of acylting agent 3Group connects to form ring structure.
R 3Preferably from C 1To C 20Hydrocarbyl substituent, the wherein a kind of of heteroatomic analogue contained in preferred alkyl or aryl or they.R 3More preferably from C 1To C 10Alkyl or aryl, R 3Most preferably from C 1To C 6Alkyl or aryl.Most preferred alkyl can be methyl, ethyl, propyl group or butyl.
Especially, acylting agent preferably uses diacetyl oxide, propionic anhydride, butyryl oxide, trifluoroacetic anhydride, Acetyl Chloride 98Min., propionyl chloride, butyryl bromide, butyrolactone, caprolactone, methyl acetate, ethyl acetate, butylacetate, butyl propionate, and butyl butyrate.Most preferably use diacetyl oxide.
The preferred anti-friction composition of the present invention be alkenyl succinic anhydride at first with polyamines (XI) reaction, make with acetic anhydride more subsequently.The most preferred product of the present invention be the isomerization alkenyl succinic anhydride at first with polyamines (XII) reaction, make with acetic anhydride more subsequently.
The most preferred friction modifiers of the present invention (b) structure (i) is as follows:
Figure A20081013194100151
It can obtain by the reaction product of diethylenetriamine and essential isomerization octadecylene base succinyl oxide is carried out acylations.This material demonstrates splendid performance in the present invention.The friction modified agent addition agent and the described compound itself that contain described compound have all further embodied the present invention.
Although can use the friction modifiers of any significant quantity in the present invention, this friction modifiers is handled ratio (treat rate) and is about 0.1 to 10% of lubricating composition branch weight usually, and is preferred 0.5 to 7%, most preferably 1.0 to 5.0%.
Below provide the embodiment of the preparation of the friction modified agent material of the present invention typical case.The purpose of these embodiment is explanation, and the present invention is not subjected to the restriction of detail among the embodiment.
Preparation embodiment
Embodiment A (preparation of isomerization succinimide)
In one liter of round-bottomed flask that mechanical stirrer, nitrogen purging device, Dean-Stark separator and condenser have been installed, place the different octadecylene base succinyl oxide of 352gm (1.00 moles) (ODSA that DixieChemical Co. produces).Begin nitrogen purging slowly, start agitator and heat this material to 130 ℃.Subsequently, in the different octadecylene base succinyl oxide of heat agitated, slowly add 95gm (0.50 mole) commodity tetraethylene pentamine by dropping funnel immediately.Mixture is warming up to 150 ℃, and under this temperature, kept two hours.In heat-processed, collect 10mL water (be approximately theoretical yield 50%) by the Dean-Stark separator.The cooling flask is to obtain product.Output: 435gm.Nitrogen per-cent: 8.1.
Embodiment B (preparation of isomerization succinimide)
Except using following amount, use with embodiment A in identical step: different octadecylene base succinyl oxide, 700gm (2.0 moles) and diethylenetriamine 103gm (1.0 moles).Recycle-water 32mL.Output: 765gm.Nitrogen per-cent: 5.5.
Embodiment C (preparation of acylations isomerization succinimide of the present invention)
In one liter of round-bottomed flask that mechanical stirrer, nitrogen purging device, Dean-Stark separator and condenser have been installed, place the product of 765gm (1.0 moles) Embodiment B.Begin nitrogen purging slowly, start agitator and heat this material to 90 ℃.Drip 102gm (1.0 moles) diacetyl oxide by dropping funnel.Promptly be warming up to 140 ℃ after being added dropwise to complete, and kept 3 hours.Under the condition of 150 ℃ and 50mmHg, remove remaining acetate by distillation.Output: 805gm.Nitrogen per-cent: 5.2.
Embodiment D (preparation of acylations isomerization succinimide of the present invention)
Except using following amount, use with Embodiment C in identical step: the product of Embodiment B, 765gm (1.0 moles); With caprolactone 131gm (1.15 moles).With mixture heating up to 170 ℃ and kept 6 hours, add the 2ml stannous octoate subsequently.Octylate adds and to be warming up to 180 ℃ and kept 4 hours after finishing.Output: 895gm.Nitrogen per-cent: 4.7.
Embodiment E (preparation of acylations isomerization succinimide of the present invention)
In one liter of round-bottomed flask that mechanical stirrer, nitrogen purging device, Dean-Stark separator and condenser have been installed, place the product of 429gm (0.5 mole) embodiment A.Begin nitrogen purging slowly, start agitator and heat this material to 90 ℃.Drip 61gm (0.5 mole) diacetyl oxide by dropping funnel.Promptly be warming up to 140 ℃ after being added dropwise to complete, and kept 3 hours.Under the condition of 150 ℃ and 50mmHg, remove remaining acetate by distillation.Output: 485gm.Nitrogen per-cent: 7.1.
Embodiment F (preparation of the acylations product of Unimac 5680-TEPA)
In one liter of round-bottomed flask that mechanical stirrer, nitrogen purging device, Dean-Stark separator and condenser have been installed, place 402gm (1.37 moles) Unimac 5680.Begin nitrogen purging slowly, start agitator and heat this material to 100 ℃.In one hour, drip 130gm (0.69 mole) tetraethylene pentamine (TEPA) by dropping funnel.Add and promptly to be warming up to 160 ℃ after finishing, and kept 6 hours, during this period recycle-water 24gm (theoretical 98%).Raw material is cooled to 100 ℃, and drips 71gm (0.69 mole) diacetyl oxide by dropping funnel.Promptly be warming up to 140 ℃ after being added dropwise to complete, and kept 3 hours.Under the condition of 130 ℃ and 50mmHg, remove remaining acetate.Output: 560gm.Nitrogen per-cent: 8.8%.
The oil soluble P contained compound
On wide significance, can be used for oil soluble P contained compound of the present invention can in wide in range scope, select, and be not subject to chemical type.Unique restriction is that this material should be oil soluble, so that P contained compound disperses in lubricating oil system and is transported to its action site.The example of the phosphorus compound that is fit to is: phosphorous acid ester and thiophosphite (analogue of monoalkyl, two alkyl, trialkyl and its partial hydrolysis); Phosphoric acid ester and thiophosphatephosphorothioate; Amine through inorganic phosphorus (for example, phosphorous acid, phosphoric acid or their thip-analogues) processing; Dithio bisphosphate zinc; Phosphamide (amine phosphate).The example of particularly suitable phosphorus compound comprises: single normal-butyl hydrogen phosphorous acid ester (mono-n-butyl-hydrogen-acid-phosphite); Di-n-butyl hydrogen phosphorous acid ester (di-n-butyl-hydrogen phosphite); The triphenyl phosphorous acid ester; The triphenyl thiophosphite; Three normal-butyl phosphoric acid ester; Dimethyl octadecylene base phosphonic acid ester is through H 3PO 3And H 3BO 3900MW polyisobutenyl succinic anhydride (PIBSA) the polyamines dispersion agent (for example referring to United States Patent (USP) the 4th, 857, No. 214) of aftertreatment; Two (2-ethylhexyl) zinc dithiophosphate.
Preferred oil soluble phosphorus compound is the ester of phosphoric acid and phosphorous acid.These materials should comprise dialkyl group, trialkyl and triarylphosphite and phosphoric acid ester.Preferred oil soluble phosphorus compound is a blended alkylthio phosphorous acid ester, for example, lists in that United States Patent (USP) in this paper reference produced for the 5th, 314, No. 633.Most preferred phosphorus compound is the alkylthio phosphorous acid ester, and for example following embodiment G is described.
Phosphorus compound of the present invention can use in lubricating oil with any significant quantity.Yet the typical effective concentration of these compounds should be for providing about 5 concentration to about 5000ppm phosphorus in lubricating oil.Preferred concentration range is to contain about 10 to about 1000ppm phosphorus in processed oil, and most preferred concentration range is about 50 to about 500ppm.
Embodiment
Embodiment G
194 gram (1 mole) hydrogen dibutyl phosphites (dibutyl hydrogen phosphite) are placed and are equipped with reflux exchanger, in the flask with four necks,round bottom of agitator and nitrogen bubble device with preparation alkyl phosphite mixture.With this flask nitrogen wash, sealing also starts agitator.Vacuum (90kPa) under the condition, heating hydrogen dibutyl phosphite to 150 ℃, and in about a hour, add 190 gram (1 mole) hydroxyethyl n-octyl sulphur by dropping funnel.In the interpolation process, use the refrigerative trap to reclaim about 35mL butanols.Finish the interpolation of hydroxyethyl n-octyl sulphur, do not have extra butanols to distribute after, continue about one hour of heating.Reaction mixture, and its p and s analyzed.The TAN of end product is 115, and contains 8.4% phosphorus and 9.1% sulphur.
Other additive as known in the art also can join in the lubricating oil of the present invention, can contain these additives in the compositions of additives perhaps of the present invention.These additives comprise dispersion agent, anti-wear agent, inhibiter, washing agent, extreme-pressure additive and similar additive.They for example be disclosed in usually C.V.Smallheer and R.Kennedy Smith show " Lubricant Additives " (1967, pp.1-11) and in No. the 4th, 105,571, the United States Patent (USP).
The typical content of these additives is summarized as follows among the ATF:
Additive Weight % (wide region) Weight % (preferably)
The VI improving agent 1-12 1-4
Inhibiter 0.01-3 0.02-1
Dispersion agent 0.10-10 2-5
Defoamer 0.001-5 0.001-0.5
Washing agent 0.01-6 0.01-3
Anti-wear agent 0.001-5 0.2-3
Pour point depressant 0.01-2 0.01-1.5
Sealed expander 0.1-8 0.5-5
Lubricating oil Surplus Surplus
The dispersion agent that is fit to comprises hydrocarbyl succinic imide and the hydrocarbon succinic amide that long-chain (promptly more than 40 carbon atoms) replaces, long-chain (promptly more than 40 carbon atoms) alkyl replaces the mixed ester/acid amides of succsinic acid, this alkyl replaces the hydroxy ester of succsinic acid, and the phenol of long-chain (promptly more than 40 carbon atoms) alkyl replacement, the Mannich condensation product of formaldehyde and polyamines.Also can use the mixture of these dispersion agents.
Preferred dispersing agent is a long chain alkenyl succinimides.They comprise and extensively are disclosed in the succinimide that acyclic hydrocarbon group in the patent documentation and that various kinds of amine or sulfonamide derivatives form replaces.Also be suitable for composition of the present invention through the mineral acid (or its acid anhydrides) of phosphorus and the alkenyl succinimide of boronation agent treated because they and better by the consistency between the elastic sealed body of making as the material of fluoroelastomer and silicon-containing elastomer etc.What especially be fit to by polyisobutenyl succinic anhydride and alkylene polyamines (for example is, triethylene tetramine or tetraethylene pentamine) polyisobutenyl succinimide that forms, wherein, the polyisobutenyl substituting group is derived from the polyisobutene of number-average molecular weight in 500 to 5000 (preferred 800 to 2500) scope.Can use a lot of reagent well known to those skilled in the art to dispersion agent carry out aftertreatment (referring to, for example United States Patent (USP) the 3rd, 254, No. 025, the 3rd, 502, No. 677 and the 4th, 857, No. 214).
Compositions of additives of the present invention can make up to form enriched material with other required lubricating oil additive.Typical activity composition (a.i.) horizontal extent of this enriched material is 20 to 90%, is preferably 25 to 80%, most preferably the enriched material of 35 to 75 weight %.The surplus of this enriched material is common thinner by lubricating oil or solvent composition.
Be used for lubricating oil of the present invention derived from natural lubricating oil, ucon oil and its mixture.Usually, natural and ucon oil all has from about 1 to about 100mm in the time of 100 ℃ separately 2The kinematic viscosity of/s (cSt) scope, though typically used needs each lubricating oil in the time of 100 ℃, kinematic viscosity about 2 to 8mm 2In/s (cSt) scope.
Natural lubricating oil comprises the oil of animal oil, vegetables oil (for example, Viscotrol C and lard), oil, mineral oil and derive coal or shale.Preferred natural lubricating oil is mineral oil.
The mineral oil that is fit to comprises all common mineral oil basis oil.This comprises that chemical structure is the oils of cycloalkanes or alkane.These oil can be to use acid, and alkali and clay or other reagent (for example aluminum chloride) is by traditional method purified oil, or the extract oil that uses solvent (for example, phenol, sulfurous gas, furfural, dichloroethyl ether etc.) for example to produce by solvent extraction.Can carry out hydrotreatment or hydrofining to these oil, dewax by cooling or catalytic dewaxing process, or carry out hydrocracking.Mineral oil can originate from natural origin, or is made up of isomery wax material or other treating process residue.
Usually, mineral oil has from 2.0mm in the time of 100 ℃ 2/ s (cSt) is to 8.0mm 2The kinematic viscosity of/s (cSt) scope.Preferred mineral oils has from 2 to 6mm 2The kinematic viscosity of/s (cSt) scope, most preferred mineral oil has from 3 to 5mm in the time of 100 ℃ 2The kinematic viscosity of/s (cSt) scope.
Synthetic lubricating oil comprises hydrocarbon ils and halo hydrocarbon ils, for example oligomeric, polymeric and mutual poly-alkene are (for example, polybutene, polypropylene, propylene, isobutylene copolymers, chlorination polylactone (chlorinatedpolylactene), poly-(1-hexene), poly-(1-octene), poly-(1-decene) etc., and composition thereof); Alkylbenzene (for example, dodecylbenzene, tetradecyl benzene, dinonyl benzene, two (2-ethylhexyl) benzene etc.); Polyphenyl (for example, biphenyl, terphenyl, alkylation polyphenyl etc.); With alkylation phenyl ether, alkylation diphenyl sulfide, and their derivative, analogs and homologue, and analogue.Preferred oil is the oligopolymer of the oligopolymer of alpha-olefin, particularly 1-decene in this class synthetic oil.
Ucon oil also comprises alkylene oxide polymer, interpretation, multipolymer and derivative thereof, and its terminal hydroxyl is through over-churning, modifications such as etherificate.The example of this class synthetic oil has: the polyoxyalkylene polymers by oxyethane or propylene oxide polymerization preparation is arranged; The alkyl oxide of this class polyoxyalkylene polymers and aryl ethers (for example, molecular-weight average is methyl-poly-Isopropanediol ether of 1000, and molecular-weight average is 1000 to 1500 polypropylene glycol phenyl ether); With its monocarboxylate and polycarboxylate (for example, acetic ester, blended C 3-C 8The C of fatty acid ester and Tetraglycol 99 12The oxygen acid diester).
Another kind of suitable ucon oil comprises that dicarboxylic acid (for example, phthalic acid, succsinic acid, alkyl succinic acid and alkenyl succinic acid, toxilic acid, nonane diacid, suberic acid, sebacic acid, fumaric acid, hexanodioic acid, linoleic acid dimer, propanedioic acid, alkyl propanedioic acid, thiazolinyl propanedioic acid etc.) and the formed ester of multiple alcohol (for example, butanols, hexanol, dodecanol, 2-ethylhexyl alcohol, ethylene glycol, Diethylene Glycol monoether, propylene glycol etc.).The specific examples of these esters comprises two (2-ethylhexyl) ester of Polycizer W 260, two (2-ethylhexyl) sebate, di-n-hexyl fumarate, dioctyl sebacate, diisooctyl azelate, two different decayl esters of azelaic acid, dioctyl phthalate (DOP), didecyl phthalate, two (eicosyl) sebate, linoleic acid dimer, with by one mole of sebacic acid and two moles of TEGs and two moles of complex ester and its analogues that the 2 ethyl hexanoic acids reaction forms.Preferred kind is C in this class synthetic oil 4-C 12The adipic acid ester of alcohol.
The ester class that is used for ucon oil also comprises by C 5-C 12Those of monocarboxylic acid and polyvalent alcohol and polyol ethers (for example neopentyl glycol, TriMethylolPropane(TMP), tetramethylolmethane, TriMethylolPropane(TMP) tetramethylolmethane, Dipentaerythritol, tripentaerythritol and analogue) preparation.
Silicon-based oil (for example, poly-alkyl-, poly-aryl-, poly-alkoxyl group-or poly-aryloxy-silicone oil and silicic acid ester oil) constitute another kind of useful ucon oil.These oil comprise tetraethyl orthosilicate, silicic acid four isopropyl esters, four (2-ethylhexyl) silicon ester, four (4-methyl-2-ethylhexyl) silicon ester, four (to tert-butyl-phenyl) silicon ester, six (4-methyl-2-pentyloxy)-sily oxide, polymethyl siloxane and poly-(aminomethyl phenyl) siloxanes and analogue thereof.Other ucon oil comprises liquid ester (for example, Tritolyl Phosphate, trioctyl phosphate and decylphosphonic acid diethyl ester), polytetrahydrofuran, poly-(alpha-olefin) of phosphorated acid, and analogue.
Lubricating oil can be derived from purified oil, oil of re-refining and their mixture.Unrefined oil is meant that those directly do not pass through the oil that is further purified or handles from natural or synthetic source (for example, coal, shale or tar sand, pitch).The example of unrefined oil comprises the shale oil that is directly obtained by destructive distillation, by the petroleum oil that directly obtains of distillation, or the ester oil that directly obtains by esterification technique, every kind of unrefined oil promptly uses without further processing subsequently.Treated oil is similar to unrefined oil, just they through a step or more the purification process of multistep improve one or more character.Purification technique is known in the art, comprises distillation, hydrotreatment, dewaxing, solvent extraction, acid or alkaline extraction, filtration and diafiltration.Rerefined oils is by producing with the similar art breading used oil of technology that obtains treated oil.These rerefined oils also refer to the oil of regenerating or reprocessing, and they usually will be through removing the additional processing of useless additive and oil decomposition product.
Another kind of suitable lubricating oil is meant the prepared base oil of isomery of the oligomeric or wax that those pass through gas material.These base oils can be found in a lot of methods, but they are commonly called solution-air (GTL) or fischer-tropsch base oil.
When lubricating oil is the mixture (being partial synthesis) of natural lubricating oil and ucon oil, the one-tenth component selections of partial synthesis oil can be quite extensive, yet useful especially combination contains mineral oil and gathers (alpha-olefin) (PAO), particularly the oligopolymer of 1-decene.
Following examples are used for illustrating claim of the present invention.It should be understood, however, that the present invention is not subject to the detail that proposes among the embodiment.Except as otherwise noted, all umbers and per-cent are all calculated by weight.
Embodiment
Select the Ford MERCON of change
Figure A20081013194100221
Friction testing (MERCON
Figure A20081013194100222
AutomaticTransmission Fluid Specification for Service, on September 1st, 1992, the 3.8th joint) the friction weather resistance of liquid of the present invention is described.The Ford test is given prominence to the friction weather resistance by using the high test of small volumes of liquids and every circulation energy.Repeatedly with this high-energy by dissipate in this small volume test liquid appraisal procedure of effort of the ability that is liquid-retentive constant friction characteristic of 10,000 circulations.The following change of this Ford test process:
Test mode:
Friction materials: Borg Warner 6100 (unslotted)
Probe temperature: 115 ℃
Total test loop: 10,000
Cpm: 3
Each round-robin total energy: 20,400J
Use piston pressure: 275kPa
Stiction is measured:
Speed: 4.37rpm
Application pressure: 275kPa
Stiction: rotate test after 2 seconds
Because the main task of friction modifiers of the present invention is to reduce stiction and keep the level of liquid in work-ing life, comes static friction coefficient (Mu-s or the μ of comparison product of the present invention and non-acylations sample by above-mentioned SAE#2 friction testing s) stability.
Use identical lubricating base oils, dispersion agent, antioxidant and viscosity modifier mix three kinds of test liquids.The test mixing thing contains most preferred oil soluble phosphorus source (the foregoing description G), presses United States Patent (USP) the 5th, 314, No. 633 description preparation.By following mode, in each liquid, add 3.0 quality % friction modifiers:
Fluid A contains the product of Embodiment B
Fluid B contains the product of Embodiment C
Fluid C contains the product of embodiment D
The composition of test liquid and the summary of test result are shown in the following table 1.
As seen from Table 1, the stiction of the common friction modifiers (liquid A) of Embodiment B in 500 to 10,000 loop cycles reduces to be changed to 0.013.In containing the liquid of product of the present invention, the product of Embodiment C and D shows less stiction to be changed: reduce 0.002 for liquid B, C reduces 0.003 for liquid.
Therefore, obviously the friction modifiers based on alkylene amine is carried out acylations and handle the improvement that causes its friction stability in test process.
Table 1
Test formulations and test result
Mixture
Composition 123
Boronation PIBSA/PAM dispersion agent 3.60 3.60 3.60
Non-boronation PIBSA/PAM dispersion agent 1.50 1.50 1.50
Alkylated diphenylamine antioxidant 0.75 0.75 0.75
Hindered phenol antioxidant 0.25 0.25 0.25
Alkyl thiol thiadiazoles 0.09 0.09 0.09
The product 0.40 0.40 0.40 of embodiment G
The product 0.30 0.30 0.30 of embodiment A
The product 3.30 of Embodiment B
The product of Embodiment C-3.30-
The product of embodiment D--3.30
Alkylthio ester 0.10 0.10 0.10
Longer chain fatty acid 0.10 0.10 0.10
Long-chain fat acid amides 0.10 0.10 0.10
Calcium sulphonate, 300TBN 0.20 0.20 0.20
Tetramethylene sulfone base sealed expander 1.5 1.5 1.50
Polymethacrylate viscosity modifiers 3.00 3.00 3.00
III class base oil 84.81 84.81 84.81
Amount to 100.00 100.00 100.00
Stiction changes
500 to 10,000 loop cycles interior 0.013 0.002 0.003
Above specification sheets has been described principle of the present invention, preferred embodiment and operator scheme.Yet the invention that is protected of expectation herein should not limited by particular forms disclosed, because these should be understood that it is explanation that the present invention is made and unrestricted.Those skilled in the art can improve under the prerequisite that does not break away from spirit of the present invention and change.

Claims (7)

1. lubricating oil composition; it comprises lubricating base oils; at least a oil soluble P contained compound; with the polyalkylene polyamine base friction modifiers that has at least one hydrocarbyl substituent; wherein said hydrocarbyl substituent or each hydrocarbyl substituent contain 6 to 30 carbon atoms, and at least one secondary amino group on the friction modifiers polyamines chain is changed into the corresponding amide base by acyl group.
2. composition, it comprises:
(a) account for the lubricating base oils of main amount; With
(b) friction stability improves the additive combination of significant quantity, comprises:
(i) at least a friction modifiers, described friction modifiers contains acylation agent R 3COX be selected from compound (I), (II) and the reaction product of one or more compounds in the group (III), wherein R 3Be alkyl, X is a leavings group, wherein (I), and (II) He (III) structure is as follows:
Figure A2008101319410002C1
Wherein R is C 6To C 30Alkyl or alkenyl; R 1Be the polyalkylene polyamine group shown in structure (IV):
Figure A2008101319410002C2
N and m each integer of from 1 to 6 independently naturally respectively wherein; R 2Be the heteroatomic derivative that contains of alkyl or aryl or they, or be selected from following V, the structure shown in VI and the VII;
Figure A2008101319410003C1
(ii) at least a oil soluble P contained compound.
3. composition as claimed in claim 2, wherein friction modifiers (b) (i) comprises as structure (VIII), the reaction product shown in (IX) and (X) one or more:
Figure A2008101319410004C1
R wherein, R 2, R 3, n and m such as claim 2 definition, p+q=m, and p 〉=1.
4. composition as claimed in claim 1, wherein composition is a transmission ofenergy liquid.
5. compositions of additives; it contains friction modifiers and the oil soluble P contained compound that has a hydrocarbyl substituent at least; wherein said hydrocarbyl substituent or each hydrocarbyl substituent contain 6 to 30 carbon atoms, and at least one secondary amino group on the friction modifiers polyamines chain is changed into the corresponding amide base by acyl group.
6. composition as claimed in claim 5, wherein phosphorus compound is the ester of phosphoric acid and phosphorous acid.
7. method that friction stability is provided for lubricating oil; comprise and in lubricating oil, add the friction modifiers that has a hydrocarbyl substituent at least; wherein said hydrocarbyl substituent or each hydrocarbyl substituent contain 6 to 30 carbon atoms, and at least one secondary amino group on the friction modifiers polyamines chain is changed into the corresponding amide base by acyl group.
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