CN101280240A - Gear oil composition - Google Patents

Gear oil composition Download PDF

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Publication number
CN101280240A
CN101280240A CNA2008100897026A CN200810089702A CN101280240A CN 101280240 A CN101280240 A CN 101280240A CN A2008100897026 A CNA2008100897026 A CN A2008100897026A CN 200810089702 A CN200810089702 A CN 200810089702A CN 101280240 A CN101280240 A CN 101280240A
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quality
gear oil
composition
oil composition
sulphur
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Granted
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CNA2008100897026A
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Chinese (zh)
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CN101280240B (en
Inventor
真锅义隆
长沼伯之
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Eneos Corp
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Japan Energy Corp
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    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M169/00Lubricating 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
    • C10M169/04Mixtures of base-materials and additives
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M127/00Lubricating compositions characterised by the additive being a non- macromolecular hydrocarbon
    • C10M127/02Lubricating compositions characterised by the additive being a non- macromolecular hydrocarbon well-defined aliphatic
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M137/00Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus
    • C10M137/02Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus having no phosphorus-to-carbon bond
    • C10M137/04Phosphate esters
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/02Pour-point; Viscosity index
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/10Inhibition of oxidation, e.g. anti-oxidants
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/12Inhibition of corrosion, e.g. anti-rust agents or anti-corrosives

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

Abstract

The present invention provides a gear oil composition, which is high level with low-temperature fluidity and shearing stabilizing ability, having moderate extreme pressure property, and having excellent corrosion resistance and oxygenize stabilizing ability.The gear oil composition is characterized in that: lubricating oil basic oil (A) with viscosity index greater or equal 110 containing : at least one phosphorus series extreme pressure agent (B) selecting from families composed by phosphite ester and phosphoric acid esters with phosphorus element 0.05-0.5 wt%, azote series anticorrosion agent (C-1) with 0.005-0.2wt%, azote sulphur series anticorrosion agent (C-2) with 0.005-0.2 wt%, ethylene -alpha -olefin copolymer (D) as viscosity index improver with 1-10wt%, and 0.02-0.2wt% zinc element zinc dialkyl dithiophosphate (E) with sulphur ingredient less than or equal to 1.4wt%.

Description

Gear oil composition
Technical field
The present invention relates to a kind of gear oil composition, particularly relate to a kind of gear oil composition that under high speed, high loading environment, uses.
Background technology
At present, friction, the wearing and tearing of contact surface in various industrial fields, are being used various lubricating oil when touching slip mutually indirectly in order to alleviate metal.Among described lubricating oil, for gear oil, except requiring to have the oilness under the working conditions, also require to have excellent extreme pressure property, oxidation stability, wearability, shear stability etc.In order to satisfy these performances, previous gear oil is to make by allocate various additives such as extreme pressure agent, corrosion inhibitor, antioxidant, viscosity index improver in the base oil that comprises mineral oil and/or synthetic oil.
For example, open in 2002-371291 number (patent documentation 1) the Japanese Patent spy and to have disclosed a kind of lubricating oil composition, this lubricating oil composition has been allocated thiadiazoles derivative with ad hoc structure and the P contained compound with ad hoc structure in the base oil that comprises mineral oil and/or synthetic oil.Oxidation stability and the excellent in wear resistance of this lubricating oil composition under the oily temperature of height improves fatigue lifetime by preventing pitching (pithcing), is suitable as gear oil, automobile gear box oil.
Because the defective that above-mentioned existing lubricant composition exists, the inventor is based on being engaged in this type of product design manufacturing abundant for many years practical experience and expertise, and the utilization of cooperation scientific principle, actively studied innovation, in the hope of founding a kind of gear oil composition of novel texture, can improve general existing lubricant composition, make it have more practicality.Through constantly research, design, and, create the present invention who has practical value finally through after studying sample and improvement repeatedly.
Summary of the invention
But when the device machine start, the whole temperature of device can be identical with outside temperature basically.Therefore, when cold district using appts machine, in order the time not cause the clamping stagnation of gear or move badly that in starting not only employed lubricating oil has performance under the usual conditions in the claimed apparatus machine, and requires lubricating oil to have low-temperature fluidity.Yet, under the situation of keeping the performance under the usual conditions, improve aspect the low-temperature fluidity, there is variety of issue.
For example, using when being used as in the lubricating oil composition employed base oil as the synthetic oil of representative,, having the problem that causes cost to increase substantially though solve easily in the described problem about the part of performance with poly-alpha-olefin (PAO).On the other hand, using mineral oil to make viscosity degradation as base oil, and use when improving viscosity index as the viscosity index improver of representative with polymethacrylate (PMA), though can guarantee low-temperature fluidity, have the problem that fully to guarantee very important shear stability for gear oil.
And, in a part of guaranteeing the extreme pressure agent that extreme pressure property is required, also can there be the material that low-temperature fluidity is worsened.In addition, because extreme pressure agent must select to have reactive compound of the environment for use that is suitable for gear oil, so, so also have the situation that causes corrosion of metal or make the oxidation stability decline of gear oil if too pay attention to extreme pressure property.Therefore, when under low temperature environment, using gear oil, gear oil must be selected to have the required extreme pressure property of environment for use, can not make low-temperature fluidity worsen and can obviously not reduce the compound of the erosion resistance and the oxidation stability of gear oil with the extreme pressure agent that is added in the composition, and must add extreme pressure agent with suitable addition.
The objective of the invention is to solve described problem, and a kind of gear oil composition is provided, this gear oil composition has low-temperature fluidity and shear stability concurrently with high level, and not only has the extreme pressure property of appropriateness, and erosion resistance and oxidation stability are also excellent.
People such as present inventor carry out active research in order to realize described purpose, found that a kind of gear oil composition, this gear oil composition is by adding the ethene-alpha-olefin copolymer as viscosity index improver in more than or equal to 110 lubricant base in viscosity index, and realize having low-temperature fluidity and shear stability concurrently with high level, and be extreme pressure agent by adding phosphorus, nitrogen is corrosion inhibitor, nitrogen sulphur is corrosion inhibitor, and add zinc dialkyl dithiophosphate (ZnDTP) as antioxidant, and make this gear oil composition have the extreme pressure property of appropriateness, and have excellent erosion resistance and oxidation stability, thereby finish the present invention.
That is, gear oil composition of the present invention is characterised in that:
It is to make viscosity index more than or equal to containing in 110 the lubricant base (A):
At least a phosphorus of from the group that phosphorous acid ester and phosphoric acid ester are formed, selecting of counting 0.05~0.5 quality % with the phosphoric quality be extreme pressure agent (B),
0.005 the nitrogen of~0.2 quality % be corrosion inhibitor (C-1),
0.005 the nitrogen sulphur of~0.2 quality % be corrosion inhibitor (C-2),
The ethene-alpha-olefin copolymer of 1~10 quality % (D) as viscosity index improver and
Count the zinc dialkyl dithiophosphate (E) of 0.02~0.2 quality % and form with the zinc element quality,
And the sulphur composition is smaller or equal to 1.4 quality %.In addition, in the gear oil composition of the present invention, sulphur composition/phosphorus composition is preferably smaller or equal to 6.5, and Bu Shi (BF) viscosity under-40 ℃ is preferably smaller or equal to 100,000mPas.
The present invention compared with prior art has tangible advantage and beneficial effect.By technique scheme, gear oil composition of the present invention has following advantage and beneficial effect at least:
Gear oil composition of the present invention, by add the ethene-alpha-olefin copolymer as viscosity index improver (D) of specified quantitative in more than or equal to 110 lubricant base (A) in viscosity index, can realize having low-temperature fluidity and shear stability concurrently with high level.And, by in described lubricant base (A), the phosphorus that adds specified quantitative is that extreme pressure agent (B), nitrogen are that corrosion inhibitor (C-1), nitrogen sulphur are corrosion inhibitor (C-2), and add the zinc dialkyl dithiophosphate as antioxidant (E) of specified quantitative, the extreme pressure property of gear oil composition can be given, and erosion resistance and oxidation stability can be improved significantly with appropriateness.Therefore, according to the present invention, can provide a kind of gear oil composition, this gear oil composition has low-temperature fluidity and shear stability concurrently with high level, and not only has the extreme pressure property of appropriateness, and erosion resistance and oxidation stability are also excellent.
Above-mentioned explanation only is the general introduction of technical solution of the present invention, for can clearer understanding technique means of the present invention, and can be implemented according to the content of specification sheets, and for above-mentioned and other purposes, feature and advantage of the present invention can be become apparent, below especially exemplified by preferred embodiment, and conjunction with figs., be described in detail as follows.
Description of drawings
(nothing)
Embodiment
Reach technique means and the effect that predetermined goal of the invention is taked for further setting forth the present invention, below in conjunction with accompanying drawing and preferred embodiment, to the gear oil composition that foundation the present invention proposes, its embodiment, structure, feature and effect thereof, describe in detail as after.
Employed base oil is a viscosity index more than or equal to 110 lubricant base (A) in the gear oil composition of the present invention.This lubricant base (A) both can be the mineral oil of lubricating oil distillate, also can be synthetic oil, the lubricant base that can use previous conduct to be used as the base oil of the various lubricating oil of representative with gear oil.In addition, this lubricant base (A) requires viscosity index more than or equal to 110, is preferably greater than to equal 120.When using viscosity index smaller or equal to 110 lubricant base, Bu Shi (BF) viscosity under-40 ℃ obviously rises, and can't fully guarantee low-temperature fluidity.And when using viscosity index more than or equal to 120 lubricant base, low-temperature fluidity is especially good.In addition, the viscosity index of common lubricant base (A) is smaller or equal to 180.
Specifically, mineral oil can use: to paraffin (paraffin) is that the air distillation residue of former wet goods carries out underpressure distillation and the cut that obtains, solvent extraction, hydrofinishing by utilizing furfural etc., utilize methyl ethyl ketone (methyl ethyl ketone, MEK)/treatment processs such as solvent dewaxing of toluene etc. are handled the gained cut and the lubricant base that obtains; The residue of described underpressure distillation is carried out diasphaltene (deasphalting) and obtains deasphalted oil, utilize described suitable treatment process to gained deasphalted oil handled and the lubricant base that obtains; Slack wax (slackwax) or Fischer-Tropsch synthetic (FT is synthetic) paraffin etc. is carried out hydroisomerization handle the refining base oil of the height that is obtained; Heavy oil is decomposed and the suitable cut that obtains carries out the dewaxing of MEK/ toluene solvant or the refining base oil of height that hydrodewaxed obtained and the mixture of these base oils through hydrogenation.
In addition, synthetic oil can use: the oligomer of alpha-olefin; By diprotic acid and monohydroxy-alcohol synthetic diester such as hexanodioic acids; Or by polyvalent alcohol and monoprotic acid synthetic polyol esters such as neopentyl glycol, TriMethylolPropane(TMP), tetramethylolmethanes; Alkylbenzene; Polyether polyols; And their mixture.
Consider from the cost aspect, in these base oils, preferred mineral oil, more preferably the mineral oil of gained is decomposed in hydrogenation.
Described lubricant base (A) preferred movement viscosity (100 ℃) is 4~20mm 2/ s.If the kinematic viscosity of lubricant base (A) (100 ℃) is low excessively, must increase the viscosity index improver that adds in order to ensure suitable product viscosity so, so may cause shear stability to descend, perhaps oil film thickness decline the causing wearing and tearing owing to sliding part increase.On the other hand, if the kinematic viscosity of lubricant base (A) (100 ℃) is too high, might fully guarantee low-temperature fluidity so.
Described lubricant base (A) optimization aromatic composition is smaller or equal to 5 quality %.If the aromatic component in the lubricant base (A) smaller or equal to 5 quality %, can further improve the stability to heat or oxidation so.In addition, the aromatic component in the lubricant base (A) can utilize the n-d-M ring analysis of regulation among the ASTMD 3238 and try to achieve.
The preferred sulphur composition of described lubricant base (A) is smaller or equal to 0.01 quality %.If the sulphur composition in the lubricant base (A) smaller or equal to 0.01 quality %, can fully suppress the caused corrosion of sulphur composition so.
Gear oil composition of the present invention contains at least a phosphorus of selecting of counting 0.05~0.5 quality % with the phosphoric quality from the group that phosphorous acid ester and phosphoric acid ester are formed be extreme pressure agent (B), preferably contains (B) of 0.05~0.1 quality %.And, gear oil composition of the present invention preferably contain simultaneously phosphorous acid ester and phosphoric acid ester the two.Phosphorus be extreme pressure agent (B) if content in the phosphoric quality less than 0.05 quality %, extreme pressure property and oxidation stability can be insufficient so, on the other hand, if surpass 0.5 quality % in the phosphoric quality, might cause corrosion or chemical abrasion so, perhaps oxidation stability descends.In addition, by being that the content of extreme pressure agent (B) is made as in the phosphoric quality smaller or equal to 0.1 quality % with phosphorus, can guarantee erosion resistance and oxidation stability well.
Described phosphorous acid ester (B-1) is with the one or more hydroxyl of the phosphorous acid compound that forms of esterification in addition, both can be three esters, also can be diester, also can be monoesters, preferred diester.In addition, described phosphorous acid ester (B-1), dialkyl phosphites such as preferred specifically phosphorous acid two-2-ethylhexyl, phosphorous acid two lauryls, wherein, preferred phosphorous acid two lauryls etc. have the dialkyl phosphite that carbon number is 8~18 alkyl especially.
Described phosphoric acid ester (B-2) is with the one or more hydroxyl of the phosphoric acid compound that forms of esterification in addition, both can be three esters, also can be diester, also can be monoesters, preferred three esters.In addition, described phosphoric acid ester (B-2), tri aromatic ester of phosphic acid such as preferably phosphoric acid triphenylmethyl methacrylate, Tritolyl Phosphate, tricresyl phosphate ethyl phenyl ester, tricresyl phosphate propyl group phenyl ester, tricresyl phosphate butyl phenyl ester, tricresyl phosphate base diphenyl ester, phosphoric acid ethylphenyl diphenyl ester, phosphoric acid propyl group phenyl diphenyl ester, phosphoric acid butyl phenyl diphenyl ester, di(2-ethylhexyl)phosphate tolyl phenyl ester, di(2-ethylhexyl)phosphate ethyl phenyl phenyl ester, di(2-ethylhexyl)phosphate propyl group phenyl phenyl ester, di(2-ethylhexyl)phosphate butyl phenyl ester specifically, wherein, special preferably phosphoric acid front three phenyl ester etc. has the tri aromatic ester of phosphic acid that carbon number is 6~12 aryl.
The nitrogen that gear oil composition of the present invention contains 0.005~0.2 quality % be corrosion inhibitor (C-1) as corrosion inhibitor (C), preferably contain (C-1) of 0.01~0.1 quality %.When nitrogen is that the content of corrosion inhibitor (C-1) is during less than 0.005 quality %, erosion resistance and/or oxidation stability are insufficient, on the other hand, even add the amount that surpasses 0.2 quality %, the effect of oxidation stability and/or corrosion stability can not significantly improve yet, if add superfluously, can cause the oily tackify behind the oxidative degradation so, so preferably in described scope, add.In addition, by being that the content of corrosion inhibitor (C-1) is made as more than or equal to 0.01 quality % with nitrogen, the erosion resistance and the oxidation stability of gear oil composition are increased substantially, on the other hand, by being that the content of corrosion inhibitor (C-1) is made as smaller or equal to 0.1 quality % with nitrogen, can under the situation of tackify not, give the oxidation stability and the corrosion stability of appropriateness.
Among the present invention, nitrogen is that corrosion inhibitor (C-1) is meant the corrosion inhibitor that contains nitrogen, and not containing aspect the sulphur with nitrogen sulphur described later at intramolecularly is that corrosion inhibitor (C-2) is distinguished to some extent.This nitrogen is that corrosion inhibitor (C-1) is that ring contains 3 or 3 above N, and the intramolecularly heterogeneous ring compounds such as triazole derivative of sulfur-bearing not; Or has a not heterogeneous ring compound such as imidazolidine derivatives, pyrimidine derivatives of sulfur-bearing of N-C-N key and intramolecularly; And have>NH, and further has the heterogeneous ring compound of 1 or 1 above nitrogen-atoms; Preferred especially intramolecularly is the compound of sulfur-bearing not.In addition, specifically, nitrogen is that corrosion inhibitor (C-1) can be enumerated N, two (2-ethylhexyl)-(4 or the 5)-methyl isophthalic acid H-benzotriazoles of N--benzotriazole derivatives such as 1-methylamine.
The nitrogen sulphur that gear oil composition of the present invention contains 0.005~0.2 quality % be corrosion inhibitor (C-2) as corrosion inhibitor (C), preferably contain (C-2) of 0.01~0.1 quality %.When nitrogen sulphur is that the content of corrosion inhibitor (C-2) is during less than 0.005 quality %, erosion resistance and/or oxidation stability are insufficient, on the other hand, even add the amount that surpasses 0.2 quality %, the effect of oxidation stability and/or corrosion stability can not show yet and improving, if add superfluously, can cause the oily tackify behind the oxidative degradation so, so preferably in described scope, add.In addition, by being that the content of corrosion inhibitor (C-2) is made as more than or equal to 0.01 quality % with nitrogen sulphur, the erosion resistance and the oxidation stability of gear oil composition are increased substantially, on the other hand, by being that the content of corrosion inhibitor (C-2) is made as smaller or equal to 0.1 quality % with nitrogen sulphur, can be in the oxidation stability and the corrosion stability of also not giving appropriateness behind the oxidative degradation under the situation of tackify.
Among the present invention, nitrogen sulphur is that corrosion inhibitor (C-2) is meant the corrosion inhibitor that contains nitrogen and sulphur, and containing aspect the sulphur with described nitrogen at intramolecularly is that corrosion inhibitor (C-1) is distinguished to some extent.This nitrogen sulphur is the compound that corrosion inhibitor (C-2) preferably contains the N-C-S key, wherein, especially preferably have-N=C (X)-change of S-S-R structure (in the formula, X is NH, O or S, and R is an alkyl) contains thing.And specifically, nitrogen sulphur is that corrosion inhibitor (C-2) can be enumerated thiadiazoles derivative, special preferred alkylization 2, and 5-dimercapto-1,3,4-thiadiazoles etc. has the thiadiazoles derivative of polysulfide structure.
Gear oil composition of the present invention contains the ethene-alpha-olefin copolymer (D) of 1~10 quality % as viscosity index improver.This ethene-alpha-olefin copolymer is to utilize coordination anionic polymerization catalyst etc. to make ethene and alpha-olefin copolymer close the multipolymer that forms, and can adjust viscosity by the polymerization degree.When the content of this ethene-alpha-olefin copolymer (D) during less than 1 quality %, can't fully improve viscosity index, on the other hand, when the content of this ethene-alpha-olefin copolymer (D) surpassed 10 quality %, the raising effect of viscosity index can reach capacity.Moreover when using ethene-alpha-olefin copolymer (D) additive in addition as viscosity index improver, the shear stability meeting of gear oil composition worsens.
The number average molecular weight of described ethene-alpha-olefin copolymer (D) is preferred 1,000~30,000, and more preferably 2,000~10,000.If the number average molecular weight of ethene-alpha-olefin copolymer (D) is more than or equal to 1,000, can obtain sufficient viscosity index improvement effect so, on the other hand, if the number average molecular weight of ethene-alpha-olefin copolymer (D) is smaller or equal to 30,000, can guarantee the shear stability that gear oil is required so.In addition, be 2,000~10,000 ethene-alpha-olefin copolymer (D) by the usage quantity molecular-weight average, can make the balance of viscosity index improvement effect and shear stability reach best.
Gear oil composition of the present invention contain count 0.02~0.2 quality % with the zinc element quality zinc dialkyl dithiophosphate (E) as antioxidant, preferably contain (E) of 0.05~0.1 quality %.When the content of zinc dialkyl dithiophosphate (E) in the zinc element quality during less than 0.02 quality %, oxidation stability can be insufficient, on the other hand, if surpass 0.2 quality % in the zinc element quality, the deterioration thing of this zn cpds also can increase so, this deterioration thing be not scattered in oil in and become greasy filth (sludge), thereby may cause device bad.In addition, if the content of zinc dialkyl dithiophosphate (E) in the zinc element quality more than or equal to 0.02 quality %, oxidation stability is good especially so, on the other hand, if the content of zinc dialkyl dithiophosphate (E) is smaller or equal to 0.2 quality %, the deterioration thing can not become the greasy filth that causes device bad so.
Described zinc dialkyl dithiophosphate (E) is represented with following general formula (I):
[changing 1]
Figure A20081008970200081
[in the formula, R1 is an alkyl, both can be identical also can be different].Wherein, the preferred secondary alkyl of alkyl (sec-) that R1 is represented, preferred especially Sec-Hexyl.In general, the zinc dithiophosphate with secondary alkyl (sec-) is characterised in that: compare with the zinc dithiophosphate with one-level alkyl (n-), the wearability extreme pressure property is very excellent, but oxidation stability is poor; Zinc dithiophosphate with aryl is characterised in that: compare with the zinc dithiophosphate with one-level alkyl (n-), oxidation stability is very excellent, but the wearability extreme pressure property is poor.And gear oil is relatively paid attention to the wearability extreme pressure property, thus preferably have the zinc dithiophosphate of secondary alkyl (sec-), but also can and use the zinc dithiophosphate of other types.Moreover, the carbon number of alkyl R1 preferred 4~10.
Can further suitably add ashless in the gear oil composition of the present invention is additives such as dispersion agent, pour point depressant, defoamer, more particularly, can further suitably add the boracic succimide, sulphur is oiliness improver, phosphorodithioic acid amine, organic amide, nonionic activator etc.Wherein be alkaline components because metal is a sanitising agent, so can be that the acidic components such as phosphorous acid two lauryls of extreme pressure agent (B) react, and generate greasy filth with belonging to described phosphorus, therefore gear oil composition of the present invention preferably not containing metal be sanitising agent.
Gear oil composition of the present invention is characterised in that the sulphur composition smaller or equal to 1.4 quality %, and preferred sulphur composition is 1.0~1.4 quality %.If the sulphur composition of gear oil composition surpasses 1.4 quality %, oxidation stability or low-temperature fluidity can worsen so, on the other hand, when using universal gear oil compounding agent (gear oil package), be difficult to make the sulphur composition of gear oil composition less than 1.0 quality %.In addition, the mass ratio of the preferred sulphur composition/phosphorus composition of gear oil composition of the present invention is smaller or equal to 6.5, and more preferably 4.5~6.5.For balance improves oxidation stability, erosion resistance and extreme pressure property well, preferably the mass ratio with sulphur composition/phosphorus composition is adjusted into described scope.
Bu Shi (BF) viscosity under preferred-40 ℃ of the gear oil composition of the present invention is smaller or equal to 100,000mPas.If the brookfield viscosity under-40 ℃ of gear oil composition is smaller or equal to 100,000mPas, low-temperature fluidity is enough high so, even be used in the device that cold district uses, the clamping stagnation of gear or move bad in the time of also can preventing to start.
[embodiment]
Below, enumerate embodiment and further describe the present invention, but the present invention is not subjected to any qualification of following embodiment.
[preparation of gear oil composition]
According to the allotment ratio shown in the top of table 1 and table 2 (addition is to be the quality % of benchmark with the total composition), use following lubricant base and additive, the gear oil composition of preparation embodiment 1 and comparative example 1~13.
<lubricant base 〉
[A composition: lubricant base]
A-1: mineral oil (100 ℃ kinematic viscosity: 7.6mm 2/ s, viscosity index: 129, aromatic component: 0.0 quality %, sulphur composition: 0.0008 quality %)
A-2: mineral oil (100 ℃ kinematic viscosity: 7.6mm 2/ s, viscosity index: 100, aromatic component: 5.9 quality %, sulphur composition: 0.16 quality %)
<additive 〉
[B composition: extreme pressure agent]
B-1: phosphorous acid two lauryls
B-2: Tritolyl Phosphate
B-3: olefine sulfide and the mixture that vulcanizes ester
B-4: phosphorodithioate
B-5: sulfuration arctic sperm oil
[C composition: corrosion inhibitor]
C-1:N, two (2-ethylhexyl)-(4 or the 5)-methyl isophthalic acid H-benzotriazoles of N--1-methylamine
C-2: alkylation 2,5-dimercapto-1,3,4-thiadiazoles (alkyl is that carbon number is 9 branched structure)
[D composition: viscosity index improver]
D-1: ethene-alpha-olefin copolymer (number average molecular weight: 5,200)
D-2: polymethacrylate (put: 20,000) by non-dispersive type, quantity mean molecule
Addition all is adjusted in embodiment and all comparative examples and makes the viscosity of composition reach 9~11mm 2The amount of/s.
[E composition: antioxidant]
E-1: pentanoic
E-2: hindered phenol (octyl group-3-(3,5-two-tertiary butyl-4-hydroxyphenyl) propionic ester)
E-3: zinc dialkyl dithiophosphate (alkyl: sec-C6)
[other additives]
Contain boracic succimide, sulphur and be extreme pressure agent, phosphorodithioic acid amine, organic amide, nonionic activator gear oil compounding agent, ashless be the additive that dispersion agent, pour point depressant, defoamer combine, in embodiment and all comparative examples, be same composition and allotment amount.
<appraisal procedure 〉
[low-temperature fluidity]
According to ASTM D 2983, Bu Shi (BF) viscosity under measuring-40 ℃.
[shear stability]
According to CEC L-45-T-93, carry out 60 hours KRL shearing tests, the viscosity degradation rate under measuring 100 ℃.
[extreme pressure property]
According to JIS K 2519, carry out Tian Shisi ball rub(bing)test once with 750rpm, measure supporting capacity.
[erosion resistance]
According to JIS K 2513, under 121 ℃, 3 hours condition, carry out copper corrosion test.
[oxidation stability]
Oxidation permanence test according to regulation among the JIS K 2514 is the ISOT method, under 150 ℃, 48 hours condition, and the viscosity increment rate under measuring 100 ℃.
[table 1]
(unit is quality %) Embodiment 1 Comparative example 1 Comparative example 2 Comparative example 3 Comparative example 4 Comparative example 5 Comparative example 6
A-1 mineral oil Remainder Remainder Remainder Remainder Remainder Remainder Remainder
B-1 phosphorous acid two lauryls (in the P amount) B-2 Tritolyl Phosphates (in the P amount) 0.030 0.037 0.030 0.037 0.030 0.037 0.030 0.037 0.030 0.037 0.030 0.037 0.006 0.037
C-1 benzotriazole cpd C-2 thiadiazole compound 0.05 0.02 0.10 0.03 0.10 0.10 0.10 0.05 0.02
The D-1 ethene-alpha-olefin 3.5 3.5 3.5 3.5 3.5 3.5 3.5
E-1 pentanoic e-2 hindered phenol E-3 zinc dialkyl dithiophosphate (in the Zn amount) 0.08 0.08 0.08 0.50 0.08 0.50 0.08 0.25 0.25 0.08 0.08
Other additives 7.3 7.3 7.3 7.3 7.3 7.3 7.3
Sulphur composition % 1.38 1.37 1.38 1.37 1.37 1.37 1.39
Sulphur composition/phosphorus composition 6.1 6.1 6.2 6.1 6.1 6.1 6.9
Viscosity degradation rate (100 ℃) % Ceng Tiansi ball rub(bing)test supporting capacity MPa copper corrosion test after brookfield viscosity (40 ℃) mPas KRL shears (121 ℃, 3h) ISOT viscosity increment rate (100 ℃) % 72200 3.5 0.50 1b 0.7 73600 3.5 0.45 2e 4.6 72800 3.3 0.45 1b 19.6 75300 3.4 0.45 2c 21.5 75000 3.7 0.40 2c 22.0 74400 3.6 0.45 2c 4.2 71100 3.4 0.40 1a 21.3
[table 2]
(unit is quality %) Comparative example 7 Comparative example 8 Comparative example 9 Comparative example 10 Comparative example 11 Comparative example 12 Comparative example 13
A-1 mineral oil a-2 mineral oil Remainder Remainder Remainder Remainder Remainder Remainder Remainder
B-1 phosphorous acid two lauryls (in the P amount) B-2 Tritolyl Phosphates (in the P amount) 0.006 0.037 0.006 0.037 0.006 0.037 0.030 0.037 0.030 0.037 0.030 0.037 0.030 0.037
B-3 mixture of sulfides (in the S amount) b-4 phosphorodithioate (in the S amount) b-5 sulfuration arctic sperm oil (in the S amount) 0.19 0.088 0.19 0.19 0.88
C-1 benzotriazole cpd C-2 thiadiazole compound 0.05 0.02 0.05 0.02 0.05 0.02 0.05 0.02 0.05 0.02 0.05 0.02 0.05 0.02
D-1 ethene-alpha-olefin d-2 polymethacrylate 3.5 3.5 3.5 3.5 3.5 3.5 6.0
E-3 zinc dialkyl dithiophosphate (in the Zn amount) 0.08 0.08 0.08 0.08 0.08 0.08 0.08
Other additives 7.3 7.3 7.3 7.3 7.3 7.3 7.3
Sulphur composition % 1.57 1.47 1.55 1.56 1.46 1.38 1.35
Sulphur composition/phosphorus composition 7.8 6.1 7.9 7.0 5.5 6.1 6.1
Brookfield viscosity (40 ℃) mPas KRL shears back viscosity degradation rate (100 ℃) % Ceng Tiansi ball rub(bing)test supporting capacity MPa copper corrosion test (121 ℃, 3 h) ISOT viscosity increment rates (100 ℃) % 78300 3.1 0.50 1a 19.6 79800 3.3 0.50 1b 13.1 176000 3.7 0.50 1a -0.9 79000 3.2 0.55 1a 25.8 80200 3.5 0.50 1b 22.2 Can't measure 3.6 0.50 1b 3.4 73000 6.2 0.50 1b 2.5
The result of embodiment as can be known, gear oil composition of the present invention has following performance: have low-temperature fluidity and shear stability concurrently with high level, and not only have the extreme pressure property of appropriateness, and erosion resistance and oxidation stability are also excellent.
On the other hand, have only at corrosion inhibitor under any one the situation (comparative example 1~5), a kind of poor-performing in erosion resistance or the oxidation-resistance or this two kinds of performances are all relatively poor.In addition, be the total amount of phosphorus of extreme pressure agent during less than 0.05 quality % (comparative example 6) when deriving from phosphorus, extreme pressure property and oxidation stability are relatively poor.In addition, when the sulphur composition in the gear oil composition integral body surpasses 1.4 quality % (comparative example 7~11), though extreme pressure property than more excellent, oxidation stability or low-temperature fluidity are relatively poor.
And when using the lower base oil of viscosity index (comparative example 12), low-temperature fluidity is relatively poor, and when normally used polymethacrylate is used for viscosity index improver (comparative example 13), shear stability is relatively poor.
As mentioned above, in base oil, the additive one or more are replaced to the gear oil composition of the integrant different with thing of the present invention, perhaps addition is at specialized range gear oil composition in addition, also have at the composition of a certain aspect of performance than thing excellence of the present invention, but other performances are poor, and hence one can see that: the good composition of excellent performance that gear oil composition is required and balance has only thing of the present invention.

Claims (1)

1, a kind of gear oil composition, it is characterized in that: it is to make viscosity index more than or equal to containing in 110 the lubricant base (A): at least a phosphorus of selecting from the group that phosphorous acid ester and phosphoric acid ester are formed of counting 0.05~0.5 quality % with the phosphoric quality is extreme pressure agent (B), 0.005 the nitrogen of~0.2 quality % is corrosion inhibitor (C-1), 0.005 the nitrogen sulphur of~0.2 quality % is corrosion inhibitor (C-2), the ethene-alpha-olefin copolymer of 1~10 quality % (D) as viscosity index improver, and count the zinc dialkyl dithiophosphate (E) of 0.02~0.2 quality % and form with the zinc element quality, and the sulphur composition is smaller or equal to 1.4 quality %.
CN2008100897026A 2007-04-05 2008-03-26 Gear oil composition Expired - Fee Related CN101280240B (en)

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