CN1206331C - Gear oil composition capable of raising performance of main drive system - Google Patents

Gear oil composition capable of raising performance of main drive system Download PDF

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Publication number
CN1206331C
CN1206331C CNB011331569A CN01133156A CN1206331C CN 1206331 C CN1206331 C CN 1206331C CN B011331569 A CNB011331569 A CN B011331569A CN 01133156 A CN01133156 A CN 01133156A CN 1206331 C CN1206331 C CN 1206331C
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China
Prior art keywords
lubricating oil
oil composition
gear
composition
composite additive
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Expired - Lifetime
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CNB011331569A
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CN1344784A (en
Inventor
V·巴拉苏布拉马尼亚姆
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Afton Chemical Intangibles LLC
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Ethyl Corp
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    • 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
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    • C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
    • C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
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    • C10N2040/046—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives for traction drives

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

Abstract

A lubricant composition comprises a mineral oil as the base and a viscosity index improver mixture of (B) a vinyl aromatic-diene copolymer, an olefin copolymer or a mixture thereof and (C) at least one poly-alpha-olefin having a kinematic viscosity of at least 40 cSt at 100 deg.C, and exhibits excellent low and high temperature rheological properties and is particularly suitable for use in the automotive and industrial gear applications. This lubricant composition exhibits improved performances such as increased axle efficiency and a lowered axle oil sump temperature compared to other lubricant compositions having a mineral oil base without containing the above viscosity index improver mixture.

Description

Improve the gear oil composition of main transmission performance
Technical field
The present invention relates to the new gear oil compositions, these compositions contain the particular combinations of viscosity index improver, have excellent low temperature high temperature rheology energy, high shaft efficiency and low shafting oil groove temperature.
Background technology
The major function of gear grease is reliability and the wearing quality that height was provided for it in the usage period of gear apparatus.Gear grease also helps to save motor vehicle fuel by improving shaft efficiency.Referring to, for example, people's such as O ' Connor article " relation that laboratory shaft efficiency and motor vehicle fuel consume " (The Relationship Between Laboratory AxleEfficiency and Vehicle Fuel Comsumption) (" Society of automotive engineers " be paper 811206 (SAE)).
In people's such as O ' Connor paper " the ucon oil component is to the response (AxleEfficiency Response to Synthetic Lubricant Components) of shaft efficiency " (SAE paper 821181), the author points out, to part and whole studies show that based on the preparation of synthetics, compare with the gear oil based on oil of routine, they have demonstrated improvement.Use all is that the preparation on synthetics basis can obtain maximum interests.The paper of O ' Connor and failing is pointed out the advantage that the present invention is had based on the gear oil preparation of oil.
United States Patent (USP) 4,370,247 disclose a kind of semi-synthetic gear and axle oil composition, and it comprises: (a) the conventional gear of 5-50m%/axle level mineral oil; (b) a kind of polyoxyalkylene glycol of 5-30m%; (c) at least a dicarboxylic acid two C of 25-60m% 8-C 12Alkyl ester.Be somebody's turn to do ' 247 patents and fail to instruct or moderately provide the suggestion of the present invention based on the gear oil preparation of oil.
European patent 790294 A2 disclose lubricating composition, and it comprises, at least a Mw of the about 30wt% of about 5wt%-is lower than 10000 polymkeric substance and a kind of Mw of the about 12wt% of about 2wt%-is higher than 15000 polymkeric substance.Reference that should ' 294 patents does not instruct being used in combination of high viscosity poly-alpha olefins and olefin copolymer or the use by this combination to improve shaft efficiency and reduced axle temperature.
Summary of the invention
The present invention relates to a kind of gear oil composition, it comprises:
(A) a kind of mineral oil;
(B) be selected from least a in vinyl-arene-diene copolymer, olefin copolymer and composition thereof;
(C) at least a its kinematic viscosity under 100 ℃ is the poly-alpha olefins of 40cSt at least; With
(D) a kind of gear composite additive.
With respect to the gear oil preparation that contains other viscosity index improver based on mineral oil, gear oil preparation of the present invention shows excellent low temperature and high temperature rheology energy, higher shaft efficiency and lower shafting oil groove temperature.
The present invention relates to a kind of gear oil composition, it comprises:
(A) based on the gear oil composition gross weight meter that is as the criterion, a kind of mineral oil of about 40-70wt%;
(B) based on the gear oil composition gross weight meter that is as the criterion, about 2-20wt% is selected from least a in vinyl-arene-diene copolymer, olefin copolymer and composition thereof;
(C) based on the gear oil composition gross weight meter that is as the criterion, at least a poly-alpha olefins of about 2-20wt%, its kinematic viscosity under 100 ℃ is 40cSt at least; With
(D) based on the gear oil composition gross weight meter that is as the criterion, a kind of composite additive of about 3-20wt%;
Wherein, the viscosity index of the gear oil composition of final preparation is greater than 140.
Mineral oil of the present invention (A) can be mineral oil arbitrarily.In a preferred embodiment, this mineral oil is the mineral oil through hydrotreatment, hydrocracking and/or isomerization dewaxing, and its viscosity index is preferably more than 90 greater than 80; Contain greater than the stable hydrocarbon of 90vol% with less than the sulphur of 0.03wt%.
American Petroleum Institute (API) is classified as follows oil base stock: I group, the sulphur of＞0.03wt% and/or＜stable hydrocarbon of 90vol%, viscosity index is between 80-120; II group, the sulphur of≤0.03wt% and 〉=stable hydrocarbon of 90vol%, viscosity index is between 80-120; III group, the sulphur of≤0.03wt% and 〉=stable hydrocarbon of 90vol%, viscosity index＞120.The base oil of II group and III group is particularly useful for the present invention, and normally reduces aromatic hydrocarbons, sulphur and nitrogen component by the raw material of routine with a kind of step of hydrogenation of harshness, prepares the finished product base oil through dewaxing, hydrofining, extraction and/or distillation afterwards.The oil base stock of II group and III group with organize the oil base stock difference with the solvent-refined I of routine and be that its sulphur, nitrogen and aromaticity content are very low.Therefore, these base oils on forming with very different with conventional solvent-refined base oil.The blend of I group, II group and/or III group base oil also can be used for component of the present invention (A).
Not restriction of chemical constitution as for used various oil base stock.Such as, the ratio of aromatic hydrocarbons, paraffinic hydrocarbon and naphthenic hydrocarbon can have basic variation in I group, II group and the III group oil.This composition generally is to be determined by refining degree and the source that produces the used crude oil of this oil.
Component of the present invention (B) comprises and is selected from least a in vinyl-arene-diene copolymer, olefin copolymer and composition thereof.
Be particularly suitable for vinyl-arene-diene copolymer of the present invention and comprise hydrogenant diolefine/vinyl-arene diblock and triblock copolymer.These multipolymers are generally at first by a kind of vinyl aromatic monomer preparation.The aromatic hydrocarbons part can comprise single aromatic ring, condensed ring or many aromatic rings in this monomer.Condensed ring or many aromatic rings examples of substances comprise: the naphthalene of vinyl substituted, anthracene, phenanthrene and biphenyl.Substantially keep at comonomer under the situation of its aroma properties and non-affect polymer properties, the aromatic hydrocarbons comonomer also can comprise one or more heteroatomss in aromatic ring.Suitable hetero-aromatic ring material comprises thiophene, 2-vinyl pyridine, 4-vinylpridine, N-vinylcarbazole and the N-Yi Xi Ji oxazole of vinyl substituted.Monomer be preferably styrenic such as vinylbenzene, alpha-methyl styrene, neighbour-vinyl toluene ,-vinyl toluene and p-methylstyrene.Vinyl aromatic monomer is vinylbenzene most preferably.In vinyl aromatic monomer, vinyl group is preferably a unsubstituted vinyl group (as CH 2=CH-) or an equivalent group, the character that this equivalent group has can provide suitable way for the aromatic hydrocarbons comonomer is incorporated in the homopolymer block mode in the polymer chain, and making this block have high aromaticity content, described homopolymer block has the even repeating unit of many successive.
The diolefine that is suitable for preparing segmented copolymer of the present invention comprises two two keys, generally is in 1,3 conjugate relation.Contain alkene, refer to polyene hydrocarbon sometimes, also can be considered to be within the range of definition of diolefine used herein more than two two keys.The example of this diolefinic monomer comprises the divinyl that 1,3-butadiene and alkyl replace, as isoprene and 2, and the 3-dimethylbutadiene.Also can use the mixture of this class conjugated diene.
Vinyl aromatic content in the multipolymer in the about 70wt% scope of about 20wt%-, is preferably the about 60wt% of about 40wt%-usually.The content of remaining comonomer is generally the about 80wt% of about 30wt%-in these multipolymers, is preferably the about 60wt% of about 40wt%-.Also can there be other monomer, in general consumption smaller relatively (5%-about 20% according to appointment).These other monomers comprise C 2-10Alkene oxide, decalactone and butyrolactone.
Be used for of the present invention pair of block and triblock copolymer and preferably prepare by anionoid polymerization, in the polymerization with various technology and different reaction conditionss so that the multipolymer that is obtained has needed characteristic.The hydrogenation of unsaturated block polymer can produce oxidative stability and the better polymkeric substance of thermostability.Hydrogenation is usually as the part of polymerization process, carries out in the presence of the nickel catalyzator of finely divided or load.Also can finish this conversion with other transition metal.In the common semi-reduction original polymer of hydrogenation at least about 94% alkene degree of unsaturation.Generally speaking, based on the reason of oxidative stability, the residual olefin degree of unsaturation that these multipolymers comprise preferably is no more than and is present in the about 5% of olefinic double bonds total amount in the hydrogenation prepolymer, more preferably no more than 0.5%.This degree of unsaturation can be measured with known certain methods of those skilled in the art such as infrared or NMR (Nuclear Magnetic Resonance) spectrum.These multipolymers more preferably do not comprise can be by the distinguishable degree of unsaturation of aforementioned analytical procedure mensuration.
In a preferred embodiment, polymkeric substance, especially the phenylethylene-dialkene multipolymer is a segmented copolymer, wherein the part of block is made up of homopolymer or equal-oligopolymer segment of vinyl aromatic monomer, and another part of block is made up of homopolymer or equal-oligopolymer segment of diolefinic monomer.The number-average molecular weight of polymkeric substance is generally at least 50000, is preferably at least 100000.Generally speaking, the number-average molecular weight of polymkeric substance is should exceed 500000 not, preferably is no more than 300000.The number-average molecular weight of these polymkeric substance is measured by gel permeation chromatography (GPC).The molecular weight of used polymkeric substance and the selection of consumption should make processed oil when the conical bearing that stood 20 hours is sheared (CEC-L45-T-93) test, are not trimmed to and do not meet the grade that SAEJ306 requires.
The suitable regular diblock copolymer of styrene/isoprene hydrogenation can be commercially available from ShellChemical Co. company, and its commodity are called Shellvis TM40 and Shellvis TM50.Suitable vinylbenzene/1,3-butadiene hydrogenation statistic copolymer can be commercially available from BASF AG, and its commodity are called Glissoviscal TM
Be specially adapted to vinyl-arene-diene copolymer of the present invention and also comprise star-type polymer.Star-type polymer is the polymkeric substance that comprises a nuclear and a plurality of polymerization arms.Common nuclear comprises polyenic compounds, and this compounds has at least two non-conjugated thiazolinyls usually, and this non-conjugated thiazolinyl is typically connected on electron-withdrawing group such as the aromatic hydrocarbons nuclear.The polymerization arm is the multipolymer of conjugated diene and vinyl aromatic (co) hydrocarbon compound.
Star-type polymer is hydrogenated usually so that 80% at least, and preferred at least 95% covalency carbon-carbon double bond becomes saturated.Example such as the polyene-based aromatic hydrocarbons of forming many vinyl compounds of nuclear, for example, Vinylstyrene and many vinyl fat compounds of group.Star-type polymer is commercially available, as the Shellvis of ShellChemical Co. company TM200.
Being specially adapted to olefin copolymer of the present invention is ethene-alpha-olefin copolymer, comprises ethene and one or more alpha-olefins, and its molecular formula is H 2C=CHR, wherein R is the alkyl that contains 1-10 carbon atom.The monomer that forms multipolymer can randomly comprise a kind of unconjugated polyene.Preferred alpha-olefin comprises propylene, 1-butylene, 1-amylene, 1-hexene, 3-methylpentene, 1-heptene, 1-octene and 1-decene.Optional unconjugated polyene comprises the aliphatics diolefine, as 1, and 4-hexadiene, 1,5-hexadiene, 1,4-pentadiene, 2-methyl isophthalic acid, 4-pentadiene, 3-methyl isophthalic acid, 4-hexadiene, 4-methyl isophthalic acid, 3-hexadiene, 1, outside the 9-decadiene reaches-and interior-dicyclopentadiene; Outward-and interior-alkenyl norbornene, as 5-propenyl, 5-(butene-2-alkane) and 5-(2-methyl butene-[2 '] alkane) norbornylene; The alkyl alkenyl norbornene is as 5-methyl-6-propenyl norbornylene; The alkylidene group norbornylene is as 5-methylene radical, 5-ethylidene and 5-isopropylidene-2-norbornylene, vinyl norbornene and cyclohexyl norbornylene; Alkyl norbornadiene such as methyl-, ethyl-and the propyl group norbornadiene; And cyclodiene is as 1,5-cyclooctadiene hydrocarbon and 1,4-cyclooctadiene hydrocarbon.
The content of ethene is generally the about 65wt% of about 35wt%-in the olefin copolymer, most preferably from about the about 60wt% of 40wt%-.When unconjugated polyene existed, its content was generally the about 1wt% of about 0.01wt%-, was preferably the about 0.5wt% of about 0.05wt%-, most preferably was the about 0.3wt% of about 0.1wt%-.For reaching total amount is weight percentage 100%, and this multipolymer surplus is made up of the alpha-olefin except that ethene.
Olefin copolymer can form with Ziegler-Natta catalyst or metallocene catalysts according to well-known method.It is about 50000 that the number-average molecular weight of olefin copolymer (Mn) is generally about 250-, is preferably about 1000-about 30000.The molecular weight of used polymkeric substance and the selection of consumption should make processed oil when the conical bearing that carried out 20 hours is sheared (CEC-L45-T-93) test, are not trimmed to and do not meet the grade that SAE J306 requires.
Component (C) comprises at least a high viscosity poly-alpha olefins, under 100 ℃, measures according to ASTMD-445, and its kinematic viscosity (Kv) is at least 40cSt, is preferably 40-3000cSt.This high viscosity poly-alpha olefins can prepare with any series methods of describing in the document, and catalyst system therefor comprises that those are commonly referred to as the catalyzer of Friedel-Crafts.These catalyzer cause alpha-olefin, as the reaction of the cationic oligomeric of 1-octene and 1-decene, and different according to used catalyzer and polymerizing condition, the molecular weight that obtains can be up to several thousand.
Z-type catalyst, for example, those catalyzer that Sun Oil company is described in United States Patent (USP) 3 179 711 also can be used to prepare the oligopolymer in described molecular weight ranges that the present invention adopts.
Equally, poly-alpha olefins can be used peroxide catalyst, BF 3Prepare for the catalyzer on basis with the thermopolymerization method.Yet these methods can only obtain low-molecular-weight oligomer usually.
High viscosity poly-alpha olefins of the present invention preferably is hydrogenated to reduce its degree of unsaturation and therefore to increase its stability to oxidation.
The alpha-olefin that is used to make high viscosity oligopolymer of the present invention can be C 3-C 14Alkene or its be mixture arbitrarily, but preferably uses the oligopolymer of octene-1, decylene-1 and laurylene-1, because their viscosity index height, pour point is low.
In one or more inert diluents or solvent, introduce with the form of solution by for example a kind of thinning oil with solubilization of active ingredient for some binder components.Unless mention the opposite meaning especially, the amount of each binder component and concentration are represented with the amount of active additive, that is to say, in the solvent relevant with this active ingredient or the amount of thinner are not included in.
The gear composite additive that is used as component among the present invention (D) comprises one or more additives usually, and it is selected from friction properties-correcting agent and the fluorescent colorant that comprises outside dispersion agent, inhibiter, extreme pressure additive, wear preventive additive, rust-preventive agent, oxidation inhibitor, reodorant, defoamer, deemulsifying agent, dyestuff, the component (B).The gear composite additive can for example, satisfy the composite additive that API GL-5 and/or API MT-1 and/or MIL-PRF-2105E and/or AGMA9005-D94 require, although do not need so for a kind of fully by the gear composite additive of formulated.Be present in the type of the component in the gear composite additive and the expection end-use that consumption will depend on product.
Generally, the consumption of gear composite additive is the about 25wt% of about 2wt%-of lubricating oil composition gross weight.
Be used for the ashless dispersant that dispersion agent of the present invention comprises that at least a oil is molten, contain a basic nitrogen and/or at least one alkyl in its molecule.The dispersion agent that is fit to comprises allyl butyrate imide, alkenyl succinic acid ester, alkenyl succinic acid esteramides, mannich base, alkyl polyamine, or the polymerization polyamine.
The allyl butyrate imide, wherein the Succinic Acid group comprises a hydrocarbyl substituent that contains at least 30 carbon atoms, and this is for example making description in the United States Patent (USP) 3 172 892,3 202 678,3 216 936,3 219 666,3 254 025,3 272 746 and 4 234 435.The allyl butyrate imide can make as heating enetutanedioic acid anhydride, acid, acid-ester, carboxylic acid halides or lower alkyl ester with a kind of polyamine that contains at least one primary amine group with conventional method.Enetutanedioic acid anhydride can be by for example, and about 180-220 ℃ is heated the mixture of alkene and maleic anhydride down and easily make.Alkene is preferably the polymkeric substance or the multipolymer of rudimentary monoolefine such as ethene, propylene, 1-butylene, iso-butylene etc. and composition thereof.Thiazolinyl more preferably derives from polyisobutene, and its gel permeation chromatography (GPC) number-average molecular weight is up to 10000 or higher, and it is about 2500 to be preferably about 500-, more preferably about 800-about 1500.
As used herein; term " succimide " means that it includes by the Succinic Acid of one or more polyamine reagents and the replacement of a kind of alkyl or whole reaction product of acid anhydrides (or similar Succinic Acid acylting agent) reaction; may contain acid amides in the compound products that expection comprises, amidine and/or sat linkage and the imine linkage that obtains by primary amine groups and the reaction of acid anhydrides segment.
Above-mentioned various types of ashless dispersant can carry out phosphorylization with the method for describing in United States Patent (USP) 3 184 411,3 342735,3 403 102,3 502 607,3 511 780,3 513 093,4 615 826,4 648 980,4 857 214 and 5 198 133.
Dispersion agent of the present invention can be by boration.The method of above-mentioned various types of ashless dispersant borations is described in United States Patent (USP) 3 087 936,3 254 025,3 281 428,3 282 955,2 284 409,2 284 410,3 338 832,3 344 069,3 533 945,3 658836,3 703 536,3 718 663,4 455 243 and 4 652 387.
The preferred method of phosphorylization as mentioned above and boration ashless dispersant is listed in United States Patent (USP) 4 857 214 and 5 198 133.
The consumption of ashless dispersant, when existing, it is in activeconstituents (promptly not comprising impurity and the thinner that is used in combination with ashless dispersant usually and the weight of solvent), be generally the about 7.5wt% of about 0.5-of processed oil gross weight, be generally about 0.5-5.0wt%, be preferably the about 3.0wt% of about 0.5-, most preferably be the about 3.0wt% of about 2.0-.
Lubricating oil composition of the present invention contains some inhibitor usually.Inhibitor component plays a different role, and comprises antirust, inhibition and resistance bubble.Inhibitor can be introduced with the form of the composite additive for preparing in advance, and this composite additive may comprise one or more other components that are used for the present composition in addition.Perhaps, these inhibitor component can be introduced separately or with the form of various auxiliary combinations.Although consumption can change in reasonable range, in the processed oil of the present invention the total amount of inhibitor usually in the about 10wt% scope of about 0-, in activeconstituents, promptly do not comprise inert substance as the solvent that is used in combination with it or the weight of thinner.
Foam inhibiting agent forms a class and is suitable in composition of the present invention comprising silicone, polyacrylic ester, tensio-active agent etc. as the inhibitor of inhibitor component.
Copper inhibitor forms the another kind of additive that is suitable for inserting the present composition.These compounds comprise thiazole, triazole and thiadiazoles.The example of these compounds comprises benzotriazole, azimido-toluene, octyl group triazole, decyl triazole, dodecyl triazole, 2-mercaptobenzothiazole, 2,5-dimercapto-1,3,4-thiadiazoles, 2-sulfydryl-5-alkyl sulphur-1,3,4-thiadiazoles, 2-sulfydryl-5-alkyl two sulphur-1,3,4-thiadiazoles, 2, two (the alkyl sulphur)-1,3 of 5-, 4-thiadiazoles and 2, two (alkyl two sulphur)-1,3 of 5-, the 4-thiadiazoles.Preferred compound is 1,3, the 4-thiadiazole compound, and wherein chemical compound lot is the commercial goods, also can be triazole species such as azimido-toluene and 1,3, the 5-thiadiazoles is as 2,5-pair of (alkyl two sulphur)-1,3, the combination of 4-thiadiazoles.Can be to disclose this commercially available class material, comprise Cobratec TMTT-100 and HiTEC 314 additives and HiTEC 4313 additives (Ethyl Petroleum Additives, Inc.).1,3, the 4-thiadiazole generally is synthetic with known method by hydrazine and dithiocarbonic anhydride, for example, and referring to United States Patent (USP) 2,765 289,2 749 311,2 760 933,2 850 453,2 910 439,3 663 561,3 862 798 and 3 840 549.
Rust-preventive agent or inhibiter are configured for the inhibitor class additive of another kind of type of the present invention.These materials comprise monocarboxylic acid and polycarboxylic acid.The example of suitable monocarboxylic acid is sad, capric acid and ten dicarboxylic acid.Suitable polyprotonic acid comprises the dimer and the tripolymer of acid, as the dimer and the tripolymer of the acid for preparing as ready denier oil acid, oleic acid, linolic acid etc. from acid.This series products can obtain from various commercial channel at present, dimeracid and the trimer acid sold with trade mark EMPOL with Henkel company sold with trade mark HYSTRENE as the Humko chemistry branch office of Witco chemical company.The another kind of useful rust-preventive agent that can be used for actual procedure of the present invention is made up of alkenyl succinic acid and enetutanedioic acid anhydride inhibiter, for example, tetrapropylene base Succinic Acid, tetrapropylene base Succinic anhydried, four decene base Succinic Acid, four decene base Succinic anhydrieds, six decene base Succinic Acid, six decene base Succinic anhydrieds etc.The alkenyl succinic acid that contains 8-24 carbon atom in thiazolinyl also is suitable for as the half ester that polyoxyethylene glycol generates with alcohol.Rust-preventive agent that other are suitable or inhibiter comprise ether amine; The acid phosphoric acid ester; Amine; Many ethoxylated compound such as ethoxylated amine, ethoxylated phenol and ethoxylated alcohol; Tetrahydroglyoxaline; Amino-succinic acid or derivatives thereof etc.This class material is the commercial goods.These mixtures antirust or inhibiter also can use.
Also can comprise oxidation inhibitor in the lubricating oil composition of the present invention.Suitable oxidation inhibitor is comprising phenol oxidation inhibitor, aromatic amine oxidation inhibitor, sulfurized phenolic oxidation inhibitor and organic phosphine compound.The example of phenolic antioxidant comprises, 2, the liquid form mixt of 6-two-tert-butyl phenol, tert-butylation phenolic compound, 2,6-two-tertiary butyl-4-sylvan, 4,4 '-methylene-bis (2,6-two-tert-butyl phenol), 2,2 '-methylene-bis (4-methyl-6-tert butyl phenol), the many alkylphenols of blended methylene radical-bridge and 4,4 '-sulphur two (2-methyl-6-tert butyl phenol).N, the pentanoic of N '-di-sec-butyl-p-phenyl enediamine, 4-sec.-propyl aminodiphenylamine, nonox and cycloalkylation can be used as the example of aromatic amine oxidation inhibitor.Be preferably sterically hindered tert-butyl phenol, pentanoic of cycloalkylation and composition thereof.
The consumption of inhibitor component depends on the composition of component and the result of use in final product composition having thereof to a certain extent.Yet in general, processed oil will comprise the inhibitor component (activeconstituents) of following concentration (weight percentage) usually:
Inhibitor Common scope Preferred range
Foam inhibiting agent 0-0.2 0.01-0.08
Copper inhibitor 0-3 0.01-1
Rust-preventive agent 0-3 0.01-0.3
Oxidation inhibitor 0-2 0-0.6
Wear-resistant and/or the extreme pressure additive of various types of sulfur-bearings can be used in the actual procedure of the present invention.Example comprises, dialkyl polysulfide, olefine sulfide, natural and synthetic sulfide aliphatic acid ester, connects three thioketones, sulfuration thienyl derivative, sulfuration terpenes, C 2-C 8The sulfuration oligopolymer of monoolefine and sulfurized Diels-Alder affixture are as those affixtures of issuing patent Re27331 announcement again of the U.S..Concrete example comprises sulfuration polyisobutene, sulfide isobutene, sulfuration diisobutylene, sulfuration triisobutene, dicyclohexyl polysulfide, phenylbenzene polysulfide, dibenzyl polysulfide, dinonyl polysulfide and the mixture of di-t-butyl polysulfide such as the mixture of di-t-butyl trisulphide, di-t-butyl tetrasulfide and di-t-butyl three pentasulfides.This class sulfur-bearing mixture wear-resistant and/or extreme pressure additive also can use, as the mixture of sulfide isobutene and di-t-butyl trisulphide, and the mixture of the mixture of sulfide isobutene and dinonyl trisulphide sulfuration Yatall MA and dibenzyl polysulfide.
For purposes of the invention, the component that contains p and s in chemical structure simultaneously is considered to phosphorous wear-resistant and/or extreme pressure additive, rather than sulfur-bearing is wear-resistant and/or extreme pressure additive.
The molten wear-resistant and/or extreme pressure additive of the oleum phosphoratum of many types can use, and is dissolved with machine phosphoric acid ester, organophosphite, Organophosphonate, organic phosphinate etc. and sulphur homologue thereof as oil.Can comprise that also those contain phosphorus and nitrogen compound simultaneously as the phosphorous wear-resistant and/or extreme pressure additive of the present invention.Be used for the molten wear-resistant and/or extreme pressure additive of oleum phosphoratum of the present invention and comprise those at United States Patent (USP) 5 464 549, the compound of instruction in 5 500 140 and 5 573 696, its disclosure is hereby incorporated by.
Can be used for phosphorous and wear-resistant and/or extreme pressure additive nitrogen of a class of actual procedure of the present invention and be the composition of the phosphorous and nitrogen type described among GB 1 009 913, GB 1 009 914, US 3 197 405 and the US 3 197 496.Generally speaking, three esters that these preparation of compositions will the hydroxyl by even phosphorus thioic acid sulfoacid replace form a kind of acid intermediate with a kind of inorganic phosphorous acid, phosphorous oxides or phosphorus halide reaction, and with the amine of amine or hydroxyl replacement the essential part of described acid intermediate are neutralized and to obtain.Wear-resistant and/or the extreme pressure additive of phosphorous and nitrogen that can be used for the other types of the present composition comprises the amine salt of the part ester of the amine salt of the amine salt of hydroxyl substituted alkyl phosphine (phosphetanes) or the alkyl phosphine sulfide (thiophosphetanes) that hydroxyl replaces and phosphoric acid and sulphur phosphoric acid.
Some binder components are dissolved in inert diluent or the solvent with active ingredient, as thinning oil, with the form adding of solution.Unless mention the opposite meaning especially, the amount of each binder component and concentration are represented with the amount of active additive, that is to say, in the solvent that is used in combination with this active ingredient or the amount of thinner are not included in.
The commercially available gear composite additive that can be used for the present composition comprises the HiTEC that Ethyl company is commercially available 381 performance additive, HiTEC 385 performance additive and HiTEC 388 performance additive.When the selection of determining additive and consumption, the factor that needs to consider comprises that shaft efficiency requires, the sliding capability of afterbody traction wearing quality, GL 5 tests, deposition control, seal compatibility, bearing life and qualification.
Lubricating oil composition of the present invention can further comprise a kind of sealing swelling agent of 0-20wt%.The sealing swelling agent that is fit to comprises polyol ester and the oil-soluble diester that is obstructed.Preferred diester comprises C 8-C 13Adipic acid ester, azelate, sebate and the C of alkyl alcohol (or its mixture) 4-C 13The phthalic acid ester of alkyl alcohol (or its mixture), also can be with the mixture of two or more dissimilar esters (as hexanodioic acid dialkyl and dialkyl azelate, or the like).These examples of substances comprise n-octyl, 2-ethylhexyl, isodecyl and the tridecyl diester of hexanodioic acid, nonane diacid and sebacic acid, and the normal-butyl of phthalic acid, isobutyl-, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, undecyl, dodecyl and tridecyl diester.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.
For some application, can in the gear oil preparation, add pour point reducer.If present, gear oil composition can comprise the pour point reducer of as many as 5wt% usually.
The friction conditioning agent also can be included in the gear oil composition of the present invention.The use of friction conditioning agent can improve the performance of elastohydrodynamics performance, mixing and the boundary lubrication condition of gear oil.The consumption of friction conditioning agent is preferably in the scope of 0-10wt% in the gear oil composition of the present invention, and more preferably 0-5wt% most preferably is 0-1.5wt%.The suitable friction conditioning agent that is used for gear oil composition of the present invention comprises, but be not limited to, as aliphatic amide, oxyalkylated aliphatic amide, the alkoxylated fats amine of boracic, the fat epoxide of boracic, aliphatic fatty amide, the fatty ether amine of ethoxylation, aliphatic carboxylic acid, aliphatic carboxylic acid esters,-acid amides, the aliphatic phosphonic acids ester, aliphatic phosphate ester, the analiphatic sulphur phosphonic acid ester, the analiphatic sulphur phosphoric acid ester, the fat tetrahydroglyoxaline, fat tertiary amine, fat phosphorous acid ester or the like, wherein aliphatic group comprises at least 8 carbon atoms usually so that compound is fit to be dissolved in the oil.
Also be fit to use the succimide as the aliphatics replacement of US 5 021 176,5 190 680 and RE-34 459 descriptions, its relevant disclosure is incorporated by reference here.These succimides are by one or more aliphatics Succinic Acid or acid anhydrides and ammonia or the generation of other primary amine reaction.
The fatty acid ester of glycerine can be used as friction conditioning agent of the present invention as glyceryl monooleate and glycerine tallate.These fatty acid esters can be with known prepared in various methods.The fatty acid ester of glycerine is generally the mixture of the diester of the monoesters of 45wt%-55wt% and 55wt%-45wt%.
Other conditioning agents that preferably rub comprise at least a C 5-C 60Aliphatic carboxylic acid and the reaction product of at least a amine, described amine is selected from guanidine, aminoguanidine, urea, thiocarbamide and the salt thereof as instruction in US 4 948 523, the relevant disclosure that this patent comprises is incorporated by reference here.Be preferred for the inorganic salt of aminoguanidine compound that are of the present invention, wherein negatively charged ion is halogen, carbonate, nitrate radical, phosphate radical, ortho-phosphoric acid root etc.The representational carboxylic acid that can here use comprises commercially available lipid acid or its mixture, derives from as Semen Maydis oil, soybean oil, plam oil, tung oil, sunflower seed oil, cotton seed oil, palmit seed oil, olive wet goods.Particularly preferred is mono carboxylic unsaturated fatty acids such as oleic acid.Here and in the claims the term " carboxylic acid " that uses comprises its response derivative such as acid anhydrides.
Other conditioning agents that preferably rub comprise the diethanolamine of N-aliphatic alkyl replacement and the trimethylene diamines that the N-aliphatic alkyl replaces, and wherein N-aliphatic alkyl substituting group contains the straight chain aliphatic alkyl of the no alkynes unsaturated link(age) of 14-20 carbon atom at least one; Two (hydroxyalkyl) aliphatic tertiary amine, hydroxyalkyl wherein can be identical or different, and each includes about 4 carbon atoms of 2-, and fatty group wherein is the have an appointment alkyl of about 25 carbon atoms of 10-of acyclic containing; Hydroxyalkyl aliphatics tetrahydroglyoxaline, wherein hydroxyalkyl contains about 4 carbon atoms of 2-, and fatty group wherein is the have an appointment alkyl of about 25 carbon atoms of 10-of acyclic containing; And the mixture of these friction conditioning agents.The further detailed explanation of relevant these friction conditioning agents is referring to by US incorporated by reference 5 344 579; 5 372 735 and 5 441 656.
Multi-stage gear oil of the present invention is specially adapted to automobile gear and uses, as the main transmission of light-duty or heavy vehicle, and power distribution device or axle, or the manual driving system of truck or heavy equipment and industrial gear application.
The finished lube that is used for automobile gear preferably uses the component that matches so that the SAE viscosity grade of lubricating oil preparation according to SAE J306 JUL98, is preferably SAE 70W at least, more preferably 75W at least.Preferred multistage rated value comprises SAE 75W-80,7 5W-90 and 80W-140.The components selection key that is used to prepare lubricating oil preparation of the present invention is to make the oil of preparation,, be not trimmed to and is not meeting the grade that SAE J306 requires when (CEC-L45-T-93) through 20 hours conical bearing shearing tests.Preferably, this lubricating oil composition in 20 hours conical bearing shearing tests the viscosity loss 100 ℃ the time less than about 15%.
Finished product gear oil of the present invention preferably uses the component that matches so that the kinematic viscosity of composition in the time of 100 ℃, according to ASTM D-445, be 7.0cSt at least, and Brookfield viscosity (measuring down at-55 ℃) is for being lower than 150 000cP.
The finished product gear oil that is suitable for the industrial gear application preferably uses the component that matches so that the viscosity classification of lubricating oil preparation according to AGMA 9005-D94, is ISO 32 or higher.
In one embodiment, the present invention relates to a kind of reduction shafting oil groove method of temperature, comprise the lubricant that comprises component (B) and lubricating oil preparation (C) as described axle with a kind of, wherein, with used at least a in not containing described component (B) and (C) under the same operation mode the shafting oil groove temperature of all the other all identical lubricating oil compare, used the shafting oil groove temperature of described lubricating oil preparation lower.
The present invention also relates to a kind of method that improves shaft efficiency, comprise the lubricant that comprises component (B) and lubricating oil preparation (C) as described axle with a kind of, wherein, with used at least a in not containing described component (B) and (C) under the same operation mode the axle of all the other all identical lubricating oil preparations compare, used the shaft efficiency of described lubricating oil preparation to be improved.
Embodiment
Gear oil composite additive with a kind of API of satisfying GL-5 that contains 8.25wt% and MIL-PRF-2105E requirement, a kind of diester sealing swelling agent of 15wt%, remaining component preparation of listing in a kind of rub conditioning agent and the following table of 2wt% is based on the SAE 80W-90 gear oil of mineral oil.All gear oil preparations all comprise a kind of hydrogenant 70N mineral oil, and its add-on makes the total amount of all components reach 100%.
This lubricant carries out a kind of alternately test with the various conditions that the simulation gear oil may experience, and the results are shown in table 1.Come ordering by speed and/or to the difference of the moment of torsion of axle.Simulate the turnpike driving condition with high speed and low load, come simcity and harsh riving condition with low speed/high capacity and middling speed/high capacity respectively.To each order measuring shaft oil sump temperature and reference axis efficient.Ideal results is to have low shafting oil groove temperature and high shaft efficiency value.
Table 1
1* 2* 3 4
PIB1 20 4.5
OCP 11.5 4 17 3 11.5 4
PAO 2 10 10 10
Motorway T ()/Eff. DNT 130/87.27 143/89.78 140/89.87
City T ()/Eff. DNT 206/96.22 181/97.38 179/97.30
Severe condition T ()/Eff. 223/97.37 215.8/97.21 198/98.19 198/98.20
* Comparative Examples
DNT does not carry out the test of axle temperature degree or shaft efficiency to sample
1 number-average molecular weight is about 2145 polyisobutene
The hydrogenation poly-alpha olefins of 2 100cSt
3 ethylene content are the ethylene-propylene copolymer of about 55mol%, and the kinematic viscosity in the time of its 100 ℃ is about 500cSt
4 ethylene content are the ethylene-propylene copolymer of about 43mol%, and the kinematic viscosity in the time of its 100 ℃ is about 2100cSt
Test according to last table can be clear that, with respect to the composition based on mineral oil outside the scope of the invention (Comparative Examples 1 and 2), composition of the present invention (embodiment 3 and 4) demonstrates the axle temperature that has improved (reduction) and has improved the shaft efficiency of (raising).
The present invention is easy to carry out suitable variation in actual procedure.Therefore, the present invention is not limited to above-mentioned concrete giving an example, and is the essence and the scope of appended claim to comprise its Equivalent as legal entity.
Applicant's intention does not also lie in any to public's disclosed embodiment, the scope that does not also lie in any disclosed modification or the change degree within the scope that does not fall within its claim of may literally looking like, they are considered to Equivalent and as a part of the present invention.

Claims (23)

1. lubricating oil composition, it comprises:
(A) be as the criterion a kind of mineral oil of 40-70wt% in the lubricating oil composition gross weight;
(B) be as the criterion in the lubricating oil composition gross weight, 2-20wt%, have at least a in vinyl-arene-diene copolymer, olefin copolymer and composition thereof of being selected from of 50000 to 500000 molecular weight;
(C) be as the criterion in the lubricating oil composition gross weight, at least a poly-alpha olefins of 2-20wt%, its kinematic viscosity under 100 ℃ is 40cSt at least; With
(D) be as the criterion a kind of gear composite additive of 3-20wt% in the lubricating oil composition gross weight;
Wherein lubricating oil composition is a viscosity index greater than 140 automobile or industrial gear lubricant.
2. the lubricating oil composition of claim 1, component wherein (B) is a kind of vinyl-arene-diene copolymer.
3. the lubricating oil composition of claim 2, component wherein (B) is for vinylbenzene and be selected from the multipolymer of at least a conjugated diene in divinyl and the isoprene.
4. the lubricating oil composition of claim 3, multipolymer wherein is hydrogenated.
5. the lubricating oil composition of claim 1, component wherein (B) is a kind of olefin copolymer.
6. the lubricating oil composition of claim 5, component wherein (B) is ethene and at least a C 3-C 12The multipolymer of alpha-olefin.
7. the lubricating oil composition of claim 6, multipolymer wherein (B) further comprises a kind of unconjugated polyene hydrocarbon.
8. the lubricating oil composition of claim 1, gear composite additive wherein comprise and are selected from least a in dispersion agent, inhibiter, extreme pressure additive, wear preventive additive, rust-preventive agent, oxidation inhibitor, reodorant, defoamer, emulsion splitter, dyestuff, friction conditioning agent and the fluorescent colorant.
9. the lubricating oil composition of claim 1, it further comprises based on the be as the criterion at least a sealing swelling agent of meter 0-20wt% of gear oil composition gross weight.
10. the lubricating oil composition of claim 1, it further comprises based on the gear oil composition gross weight meter that is as the criterion, a kind of pour point depressant additives of 0-5wt%.
11. the lubricating oil composition of claim 1, gear composite additive wherein comprise the gear composite additive that a kind of API of satisfying GL-5 requires.
12. the lubricating oil composition of claim 1, gear composite additive wherein comprise the gear composite additive that a kind of API of satisfying MT-1 requires.
13. the lubricating oil composition of claim 1, gear composite additive wherein comprise the gear composite additive that a kind of MIL-PRF-2105E of satisfying requires.
14. the lubricating oil composition of claim 1, gear composite additive wherein comprise the gear composite additive that a kind of AGMA of satisfying 9005-D94 requires.
15. the lubricating oil composition of claim 1, the viscosity index of its mineral oil in fluid is greater than 80 and contain the sulphur that is lower than 0.03wt%.
16. the lubricating oil composition of claim 15, the viscosity index of its mineral oil in fluid is at least 110.
17. comprising, the lubricating oil composition of claim 15, mineral oil wherein be selected from least a in II group oil, III group oil and composition thereof.
18. the lubricating oil composition of claim 1, wherein the SAE viscosity grade of lubricating oil composition is 70W or higher according to SAE J306 JUL98.
19. the lubricating oil composition of claim 1, wherein the ISO viscosity grade of lubricating oil composition is 32 or higher according to AGMA 9005-D94.
20. the lubricating oil composition of claim 1, wherein component (B) and selection (C) will make the oil of being prepared when standing 20 hours conical bearing shearing tests, are not trimmed to not conform with the grade that SAE J306 requires.
21. one kind is reduced shafting oil groove method of temperature, it comprises the lubricant that the lubricating oil composition of claim 1 is used as described axle, wherein, with used at least a in not containing described component (B) and (C) under the same operation mode the shafting oil groove temperature of all the other all identical lubricating oil compositions compare, use the shafting oil groove temperature of described lubricating oil composition to be reduced.
22. method that improves shaft efficiency, it comprises the lubricant that the lubricating oil composition of claim 1 is used as described axle, wherein, with used at least a in not containing described component (B) and (C) under the same operation mode the shaft efficiency of all the other all identical lubricating oil compositions compare, use the shaft efficiency of described lubricating oil composition to be improved.
23. the method for oilgear or transmission mechanism, it is included in the lubricating oil composition that adds claim 1 in wheel casing, differential mechanism or the transmission mechanism.
CNB011331569A 2000-09-19 2001-09-19 Gear oil composition capable of raising performance of main drive system Expired - Lifetime CN1206331C (en)

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WO2003089390A2 (en) 2002-04-22 2003-10-30 Chevron Phillips Chemical Company Lp Method for manufacturing high viscosity polyalphaolefins using ionic liquid catalysts
US6884855B2 (en) * 2003-01-30 2005-04-26 Chevron Oronite Company Llc Sulfurized polyisobutylene based wear and oxidation inhibitors
US7396450B2 (en) 2003-09-18 2008-07-08 Afton Chemical Corporation Method of reducing amount of peroxides, reducing fuel sediments and enhancing fuel system elastomer durability, fuel stability and fuel color durability
JP2007509750A (en) 2003-10-31 2007-04-19 シェブロン フィリップス ケミカル カンパニー エルピー Method and system for providing high shear to improve ionic liquid catalytic chemistry
US7615085B2 (en) 2003-11-04 2009-11-10 Afton Chemical Corporation Composition and method to reduce peroxides in middle distillate fuels containing oxygenates
WO2012119974A1 (en) 2011-03-08 2012-09-13 Cognis Ip Management Gmbh High viscosity lubricant compositions
FR2984348B1 (en) 2011-12-16 2015-02-27 Total Raffinage Marketing LUBRICATING COMPOSITIONS FOR TRANSMISSIONS

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JPH086113B2 (en) * 1986-07-11 1996-01-24 三井石油化学工業株式会社 hydraulic oil
ZA97222B (en) * 1996-01-16 1998-02-18 Lubrizol Corp Lubricating compositions.
US6713438B1 (en) * 1999-03-24 2004-03-30 Mobil Oil Corporation High performance engine oil

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