CN104334696A - Lubricating oil composition - Google Patents

Lubricating oil composition Download PDF

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Publication number
CN104334696A
CN104334696A CN201380028149.4A CN201380028149A CN104334696A CN 104334696 A CN104334696 A CN 104334696A CN 201380028149 A CN201380028149 A CN 201380028149A CN 104334696 A CN104334696 A CN 104334696A
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Prior art keywords
oil
lubricating oil
ester
oil composition
acid ester
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永仮光洋
大塚彩乃
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Shell Internationale Research Maatschappij BV
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Shell Internationale Research Maatschappij BV
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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
    • C10M161/00Lubricating compositions characterised by the additive being a mixture of a macromolecular compound and a non-macromolecular compound, each of these compounds being essential
    • 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
    • C10M145/00Lubricating compositions characterised by the additive being a macromolecular compound containing oxygen
    • C10M145/02Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M145/10Macromolecular 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
    • C10M145/12Macromolecular 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 monocarboxylic
    • C10M145/14Acrylate; Methacrylate
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    • 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
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    • 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
    • C10M2205/00Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/02Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
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    • 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
    • C10M2205/00Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/02Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
    • C10M2205/022Ethene
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    • 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
    • C10M2205/00Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/02Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
    • C10M2205/028Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms
    • C10M2205/0285Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms used as base material
    • 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
    • C10M2205/00Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/17Fisher Tropsch reaction products
    • C10M2205/173Fisher Tropsch reaction products used as base material
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    • 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
    • C10M2207/00Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28Esters
    • C10M2207/283Esters of polyhydroxy compounds
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    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2020/00Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01Physico-chemical properties
    • C10N2020/017Specific gravity or density
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    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2020/00Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01Physico-chemical properties
    • C10N2020/02Viscosity; Viscosity index
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    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2020/00Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01Physico-chemical properties
    • C10N2020/04Molecular weight; Molecular weight distribution
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    • 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
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    • C10N2030/00Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/04Detergent property or dispersant property
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    • 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
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    • C10N2030/00Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/72Extended drain
    • CCHEMISTRY; METALLURGY
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    • C10N2040/00Specified use or application for which the lubricating composition is intended
    • C10N2040/02Bearings
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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    • C10N2040/00Specified use or application for which the lubricating composition is intended
    • C10N2040/04Oil-bath; Gear-boxes; Automatic transmissions; Traction drives
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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    • C10N2040/00Specified use or application for which the lubricating composition is intended
    • C10N2040/06Instruments or other precision apparatus, e.g. damping fluids
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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    • C10N2040/00Specified use or application for which the lubricating composition is intended
    • C10N2040/08Hydraulic fluids, e.g. brake-fluids
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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    • C10N2040/00Specified use or application for which the lubricating composition is intended
    • C10N2040/135Steam engines or turbines
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    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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    • C10N2040/00Specified use or application for which the lubricating composition is intended
    • C10N2040/25Internal-combustion engines
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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    • C10N2040/00Specified use or application for which the lubricating composition is intended
    • C10N2040/30Refrigerators lubricants or compressors lubricants

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

Abstract

The object of this invention is to offer a lubricating oil composition which has superior extreme pressure properties (ability to prevent welding), which generates a small amount of sludge and which also has a high viscosity index. The invention provides a lubricating oil composition to which has been added a copolymer of specified olefins and alkyl methacrylates.

Description

Lubricating oil composition
Technical field
The present invention relates to lubricating oil composition, be specifically related to that there is fabulous extreme pressure property, produce a small amount of mud and also there is the lubricating oil composition of high viscosity index (HVI).
Background technology
Wind energy receives publicity as renewable energy power generation.In wind energy generating plant, the blade utilizing accelerating gear to make slowly to rotate accelerates, thus their power can be utilized to make generator rotation.But in accelerating gearbox, there are many gears and need gear oil to lubricate these gears (GekkanTribology, No.273,50-51 page, in May, 2010).
Especially, increased for wind energy generating plant scale in recent years, owing to needing to utilize accelerating gear device to change at a high speed by large slow motivating force, therefore added the load on wheelwork middle gear, result is the larger ability that gear oil that these gears are lubricated in requirement has tolerance melting loss (extreme pressure property).But when being blended in gear oil, the extreme pressure agent that can tolerate melting loss becomes mud easily through aging and oxidation, the mud of generation like this may cause wearing and tearing and melting loss as impurity by gear of nipping, and also finally can cause problem by blocking filter and obstruction oil-piping.Therefore safeguard before producing too a large amount of mud in oil that it is very important for changing oil as carried out ahead of time.
Meanwhile, be usually located at remote location as mountain area or seashore for wind energy generating plant, thus safeguard it is difficult frequently.And, at the cost that remote location's maintenance requirement is higher, therefore require to extend service intervals and oil change interval for reducing running cost.Therefore in order to reduce gear protection and running cost, required to improve the sludge quantity that gear oil oxidation stability and can minimize generation.
And, run continuously under the temperature condition day and night fluctuated in the response of wide region for wind energy generating plant and weather condition, to require because temperature variation has the gear oil of little viscosity fluctuation (namely having high viscosity index (HVI)) therefore equally.
As above consider, required that the lubricating oil of industrial level has fabulous extreme pressure property (preventing the ability of melting loss), produced a small amount of mud and also there is high viscosity index (HVI).
The problem of process of the present invention is to provide to be had fabulous extreme pressure property (preventing the ability of melting loss), produce a small amount of mud and also has the lubricating oil composition of high viscosity index (HVI).
Summary of the invention
By the investigation of various repetition and research to be reduced in the sludge quantity produced in industrial level lubricating oil, contriver obtains the present invention, the sludge quantity finding to reduce when adding the multipolymer of the specific alkene of the fixed member weight range determined and alkyl methacrylate generation with also improve viscosity index.
Usually, the multipolymer of alkene and alkyl methacrylate is used in lubricating oil composition as viscosity index improver, but still belongs to unknown about reducing the sludge quantity produced.The multipolymer that the invention is intended to by adding alkene and alkyl methacrylate in the lubricant base comprising extreme pressure agent reduces sludge quantity as effective constituent.
Therefore, the invention provides a kind of lubricating oil composition, the at least one of it comprises (A) 50-90wt% is selected from the lubricant base of mineral oil and synthetic oil and the molecular weight of (B) 10-50%wt% is 1200-50, the alkene of 000 and the multipolymer of alkyl methacrylate.
According to present invention obtains, there is fabulous extreme pressure property (preventing the ability of melting loss), produce a small amount of mud and also there is the lubricating oil composition of high viscosity index (HVI).By reducing the sludge quantity that deterioration by oxidation produces, can suppress because impurity infiltrates work-ing life of wearing and tearing and melting loss and the prolongation machine (as gear) caused.And the fact that viscosity index is higher means that low temperature flow feature is fabulous and can keep oil film at relatively high temperatures.
Accompanying drawing explanation
Fig. 1 gives the molecular weight distribution curve figure for additive A 1 and additive A 2.
Embodiment
The present invention relates to a kind of lubricating oil composition, it is characterized in that described lubricating oil composition comprises lubricant base and the alkene of (B) molecular weight in specified range and the multipolymer of alkyl methacrylate that (A) at least one is selected from mineral oil and synthetic oil.Lubrication pockets is containing component (A) and (B), but lubricating oil can comprise component (A) and (B) or can substantially be made up of component (A) and (B) in special embodiment.
For the base oil of lubricating oil composition of the present invention, the mineral oil and synthetic oil that are called height refining base oil can be used, particularly the base oil of the Group II of API (API) basestock classification, Group III and Group IV separately or can be belonged to as mixture use.For base oil used herein, sulphur content is not more than 300ppm, but is preferably not more than 200ppm, more preferably no more than 100ppm, and is most preferably not more than 50ppm.And density is 0.8-0.9g/cm 3, but be preferably 0.8-0.865g/cm 3, and be more preferably 0.81-0.83g/cm 3.Aromaticity content (aromaticity content is determined by n-d-M analysis according to ASTM D3238 in the present invention) is less than 3%, but is preferably less than 2%, and is more preferably less than 0.1%.
As the example of Group II base oil, can mention that passing through appropriate refining process such as hydrofining and the applicable of dewaxing of using for the lubricating oil obtained by crude oil atmospheric distillation combines the alkyl group mineral oil obtained.Be less than 10ppm by the total sulfur content of hydrofinishing process as the Group II base oil of Gulf company method refining and aromaticity content is not more than 5%, and be therefore suitable for the present invention.These base oil viscosities are not particularly limited, but viscosity index (viscosity index is determined according to ASTM D2270 and JIS K2283 in the present invention) for 80-120 and should be preferably 100-120.Kinematic viscosity (kinematic viscosity is determined according to ASTM D445 and JIS K2283 in the present invention) at 40 DEG C should be preferably 2-680mm 2/ s and be even more preferably 8-220mm 2/ s.And total sulfur content should be less than 300ppm, be preferably less than 200ppm and be even more preferably less than 10ppm.Total nitrogen content should be less than 10ppm and preferably be less than 1ppm.In addition, the oil that aniline point (aniline point is determined according to ASTM D611 and JIS K2256 in the present invention) is 80-150 DEG C and preferred 100-135 DEG C should be used.
The Group III be applicable to and II+ group base oil are comprised for the lubricating oil distillate obtained by crude oil atmospheric distillation by the alkyl group mineral oil of highly hydrofining production, by dewaxing and the base oil of isomerization dewaxing process refining of wax and the base oil by the refining of Mobi l wax isomerization process that replace dewaxing process generation with isomerization alkanes.These base oil viscosities are not particularly limited, but viscosity index should be 95-145 and preferred 100-140.Kinematic viscosity at 40 DEG C should be preferably 2-680mm 2/ s and be even more preferably 8-220mm 2/ s.And total sulfur content for 0-100ppm and preferably should be less than 10ppm.Total nitrogen content should be less than 10ppm and preferably be less than 1ppm.In addition, the oil that aniline point is 80-150 DEG C and preferred 110-135 DEG C should be used.
By being that the GTL (gas is to liquid) of Fischer-Tropsch process synthesis of liquid fuel has low-down sulphur content and aromaticity content compared to the mineral oil base oil by crude oil refining and has very high paraffinic components ratio by conversion of natural gas, therefore there is excellent oxidative stability.Because their vaporization losses is also few, so they are suitable as base oil of the present invention.The viscosity characteristics of GTL base oil is not particularly limited, but general viscosity index should be 130-180 and preferred 140-175.And the kinematic viscosity at 40 DEG C should be 2-680mm 2/ s and preferred 5-120mm 2/ s.
General total sulfur content also should be less than 10ppm and total nitrogen content is less than 1ppm.The commercial example of this GTL base oil is Shell XHVI (registered trademark).
As the example of synthetic oil, polyolefine, alkylbenzene, alkylnaphthalene, ester, polyether polyols, polyphenylene ether, dialkyl diphenyl ether, fluorine-containing compound (PFPE, fluorinated polyolefin) and silicone oil or their mixture can be mentioned.
Aforesaid polyolefine comprises polymkeric substance or their hydride of various alkene.Any alkene can be used, and ethene, propylene, butylene can be mentioned as an example and there is the alpha-olefin of 5 or more carbon.When producing polyolefine, can be used alone the one of foregoing alkenes or combinationally use two or more.
Particularly suitable polyolefine is called poly-alpha olefins (PAO).These are base oils of Group IV.Poly-alpha olefins also can be the mixture of two or more synthetic oils.
These synthesis oil viscosities are not particularly limited, but the kinematic viscosity at 40 DEG C should be 2-680mm 2/ s, but preferred 20-500mm 2/ s and more preferably 30-450mm 2/ s.The kinematic viscosity of described synthesis base oil at 100 DEG C should be 2-100mm 2/ s, but preferred 4-70mm 2/ s and more preferably 6-50mm 2/ s.The viscosity index of described synthesis base oil should be 110-170, but preferably 120-160 and more preferably 130-155.The density of described synthesis base oil at 15 DEG C should be 0.8000-0.8600g/cm 3, but preferred 0.8100-0.8550g/cm 3more preferably 0.8250-0.8550g/cm 3.The aniline point of described synthesis base oil should be 110-180 DEG C, but preferably 120-170 DEG C and more preferably 130-165 DEG C.
The amount adding the aforementioned base oil of lubricating oil composition of the present invention is not particularly limited, but with the total amount of lubricating oil composition, typical range can be given as 50-90wt%, but preferably 50-80wt% and more preferably 50-70wt%.With the total amount of lubricating oil composition, the lower limit of the base oil amount added should be selected from any one being not less than 50,51,52,53,54,55,56,57,58 or 59wt%, and the upper limit should be selected from any one being not more than 67,68,69 or 70wt%.
Except the above, described base oil can also comprise carbonate.Relevant these are discussed below.
As the example of the alkene of lubricating oil composition of the present invention and the multipolymer of alkyl methacrylate, can mention that wherein main component monomer is the multipolymer that at least one has that the alkene of 2-20 carbon and at least one have the alkyl methacrylate of the alkyl of 1-20 carbon.
Foregoing alkenes comprises various olefin polymer or their hydride.Can use any alkene, but the example that can mention is ethene, propylene, butylene, amylene, hexene, heptene, octene, nonene, decene, undecylene, dodecylene, tridecylene, tetradecene, 15 carbenes, cetene, heptadecene, vaccenic acid, 19 carbenes and eicosylene.Also may use foregoing alkenes independent one or both or more plant combination for being included in the alkene in element monomers.
As the aforementioned object lesson with the alkyl methacrylate of the alkyl of 1-20 carbon, can mention:
(1) there is the alkyl methacrylate of the alkyl of 1-4 carbon: such as, methyl methacrylate, β-dimethyl-aminoethylmethacrylate, n propyl methacrylate or isopropyl ester, n-BMA, isobutyl ester or secondary butyl ester;
(2) there is the alkyl methacrylate of the alkyl of 8-20 carbon: such as, methacrylic acid n-octyl ester, methacrylic acid-2-(ethyl hexyl) ester, the positive decyl ester of methacrylic acid, the positive isodecyl ester of methacrylic acid, methacrylic acid n-undecane base ester, methacrylic acid dodecyl ester, methacrylic acid-2-methylundecyl ester, methacrylic acid n-tridecane base ester, methacrylic acid-2-methyl dodecyl ester, methacrylic acid n-tetradecane base ester, methacrylic acid 2-methyltridec base ester, methacrylic acid Pentadecane base ester, methacrylic acid-2-methyltetradecylphosphine base ester, methacrylic acid n-hexadecyl ester and methacrylic acid Octadecane base ester, methacrylic acid NSC 62789 base ester, methacrylic acid n-docosane base ester, the methacrylic ester of Dobanol23 (mixture of C-12/C-13 oxo alcohol prepared by Mitsubishi Chemical (Ltd.)) and the methacrylic ester of Dobanol 45 (mixture of C-13/C-14 oxo alcohol prepared by Mitsubishi Chemical Company Ltd.),
(3) there is the alkyl methacrylate of the alkyl of 5-7 carbon: such as, methacrylic acid n-pentyl ester and methacrylic acid n-hexyl ester.
In aforementioned monomer (1) ~ (3), preferably belong to the monomer of (1) and (2), and the monomer of more preferably (2).And from the angle of viscosity index, the preferred monomers of aforementioned (1) is those of the alkyl with 1-2 carbon.Viewed from the angle of solubleness base oil and low temperature feature, the preferred monomers of aforementioned (2) is those of the alkyl with 10-20 carbon, and more preferably has those of alkyl of 12-14 carbon.
The molecular weight of the multipolymer of foregoing alkenes and alkyl methacrylate is 1,200-80,000, but preferably 1,200-50,000 and more preferably 2,000-50,000.Weight-average molecular weight is 5,000-30,000, but preferably 7,000-20,000 and more preferably 9,000-16,000.Number-average molecular weight is 2,000-12,000, but preferably 4,000-10,000 and more preferably 5,000-9,000.With regard to these molecular weight, weight-average molecular weight (Mw) and number-average molecular weight (Mn) utilize gel permeation chromatography (GPC) to determine, and obtain, using polystyrene as standard by transforming.
Foresaid weight average molecular weight can utilize the temperature in polymerization, monomer concentration (solvent strength), the amount of catalyzer or the amount of chain-transfer agent to regulate.
The dispersity (Mw/Mn) of the multipolymer of foregoing alkenes and alkyl methacrylate is 1-2.5, but preferably 1.3-2.2 and particularly 1.7-1.9.
The viscosity of the multipolymer of foregoing alkenes and alkyl methacrylate is not particularly limited, but viscosity index should be 100-250, but preferably 130-220 and more preferably 160-200.The kinematic viscosity of described multipolymer at 40 DEG C should be 1,000-12,000mm 2/ s, but preferably 2,000-10,000mm 2/ s and more preferably 2,500-9,000mm 2/ s.The kinematic viscosity of described multipolymer at 100 DEG C should be 50-600mm 2/ s, but preferred 100-500mm 2/ s and more preferably 150-450mm 2/ s.The density of described multipolymer at 15 DEG C should be 0.900-0.950g/cm 3, but preferred 0.910-0.940g/cm 3more preferably 0.925-0.935g/cm 3.
Multipolymer of the present invention easily can be obtained by any common method, does not therefore limit production method.Such as, they can utilize the alkene of thinner, selected kind and amount and alkyl methacrylate, polymerization initiator and chain-transfer agent to be obtained by radical polymerization.They also can utilize thinner to be obtained by the alkene of selected kind and amount and the thermopolymerization of alkyl methacrylate.The use of thinner is optional, but uses thinner more easily to control the molecular weight of multipolymer.Therefore usually also problem to be processed may be solved, because multipolymer has viscous characteristics.Can use any thinner into unreactive hydrocarbons, but it must have the characteristic of dissolving multipolymer and lubricating oil.As the example of the polymerization initiator be applicable to, can mention by thermal degradation and the initiator producing free radical, such as peroxide compound is as Benzoyl Peroxide, peroxidation acid tertiary butyl ester and cumene hydroperoxide, with azo-compound as azobis isobutyronitrile and 2,2'-azo two (-2-methylbutyronitrile).As the example of the chain-transfer agent be applicable to, those chain-transfer agents being generally used for this area can be mentioned, as α-styrene dimer, lauryl mercaptan and ethanethio.The use of chain-transfer agent is optional, but usage chain transfer agent more easily controls the molecular weight of multipolymer.
In lubricating oil composition of the present invention, the amount (amount of the foregoing alkenes in previous molecular weight range and the multipolymer of alkyl methacrylate) of the multipolymer of foregoing alkenes and alkyl methacrylate is not particularly limited, but with the total amount of lubricating oil composition, typical scope can be given as 10-50wt%, but preferably 10-45wt% and more preferably 15-40wt%.With the total amount of lubricating oil composition, the lower limit of the amount of the multipolymer of alkene and alkyl methacrylate should be selected from any one being not less than 10,11,12,13,14 or 15wt%, and the upper limit of the amount adding base oil should be selected from any one being not more than 40,41,42,43,44,45,46,47,48,49 or 50wt%.Determine that the method for the amount of described multipolymer within the scope of certain molecular weight is not particularly limited in this case, and can be the value from molecular weight distribution curve theoretical conversion.Such as, when use comprise described multipolymer additive as starting material (comprising multipolymer and the thinner of the multipolymer of alkene and alkyl methacrylate, the alkene not in described specialized range and alkyl methacrylate in aforementioned specialized range (applicable scope or particularly suitable scope relevant with it)) time, molecular weight distribution curve (see such as Fig. 1) can be obtained by analyzing described additive.In described molecular weight distribution curve the molecular weight component of specialized range (as 1200-50000) be estimated to be " as described in the multipolymer of alkene in specialized range and alkyl methacrylate " and based on as described in molecular weight distribution curve calculate in total additive as described in the amount of component in specialized range.
When lubricating oil composition of the present invention, aforementioned lubricant base can comprise carbonate.
As the example of carbonate, polyol ester can be mentioned.As the example of polyol ester, the ester of the ester of trihydroxy methyl propyl group Triolein (CAS No.11138-60-6), TMP (TriMethylolPropane(TMP)) and carboxylic acid, PE (tetramethylolmethane) and carboxylic acid, dicarboxylic ester and trimellitate can be mentioned.The carbon number of the carboxylic acid residues of ester molecule should also preferred 4-20, but more preferably 6-18.
The amount adding aforementioned carboxylic acid's ester of lubricating oil composition of the present invention is not particularly limited, but with the total amount of lubricating oil composition, typical range can be given as 5-15wt%, but preferably 7-13wt% and more preferably 8-12wt%.With the total amount of lubricating oil composition, the carboxylicesters amount added should be selected from any one of 5,6,7,8,9,10,11,12,13,14 or 15wt%.
In order to improve performance further, except aforesaid ingredients, can suitably use various additive where necessary.As an example, antioxidant, metal passivator, extreme pressure agent, oiliness improver, defoamer, viscosity index improver, pour point depressant, purification agent-dispersion agent, rust-preventive agent, emulsion splitter and other lubricating oil additive known in the art can be mentioned.
For the antioxidant that the present invention uses, for the antioxidant being preferred for lubricating oil practical application, amine-based antioxidant, thio-based antioxidants, phenol-based anti-oxidants and phosphorus base antioxidant can be mentioned.In the base oil of 100 weight parts, these antioxidants can independent or multiple combination use in the scope of 0.01-5 weight part.
As the example of aforementioned amine-based antioxidant, can mention that dialkyl group-pentanoic is as p, p'-dioctyl-pentanoic (Nonflex OD-3 is prepared by Seiko Chemical Ltd), p, p'-bis--Alpha-Methyl phenmethyl-pentanoic and N-p-butyl phenyl-N-p'-octyl group aniline; Monoalkyl pentanoic is as single tert-butyl diphenylamine and single octyl diphenylamine; Two (dialkyl phenyl organic) amine is as two (2,4-diethyl phenyl) amine and two (2-ethyl-4-nonyl phenyl) amine; Alkyl phenyl-naphthalidine is as Octyl-phenyl-naphthalidine and N-t-dodecylphenyl-naphthalidine; Naphthalidine; Aryl-naphthylamines is as phenyl-1-naphthylamine, phenyl-2-naphthylamine, N-hexyl phenyl-2-naphthylamine and N-octyl phenyl-2-naphthylamines; Phenylenediamine as Ν, Ν '-di-isopropyl-p-PDA and N, N'-phenylbenzene-p-PDA, and thiodiphenylamine is as fen thiophene (being prepared by Hodogaya Chemical Ltd.) and 3,7-dioctyl thiodiphenylamine.
As the example of thio-based antioxidants, can mention that dialkyl sulfide is as two dodecyl sulfide and two octadecyl sulfide; Thiodipropionate is as two dodecyl thiodipropionate, two octadecyl thiodipropionate, two tetradecyl thiodipropionate and dodecyl octadecyl thiodipropionate; And 2-mercaptobenzimidazole.
Phenol-based anti-oxidants comprises: 2-TBP; 2-tert-butyl-4-methyl-Phenol; The 2-tertiary butyl-5-methylphenol; 2,4-DTBP; 2,4 dimethyl 6 tert butyl phenol; The 2-tertiary butyl-4-methoxyphenol; The 3-tertiary butyl-4-methoxyphenol; 2,5 di tert butyl hydroquinone (Antage DBH is prepared by Kawaguchi Chemical Indus try Co.Ltd.); 2,6 di t butyl phenol; 2,6-di-t-butyl-4-alkylphenol is as 2,6 di tert butyl 4 methyl phenol and 2,6-di-t-butyl-4-ethylphenol; With 2,6-di-t-butyl-4-alkoxy phenol as 2,6-di-t-butyl-4-methoxyphenol and 2,6-di-t-butyl-4-thanatol.
In addition, 3,5-di-t-butyl-4-hydroxyphenylmethyl mercapto-acetic acid monooctyl ester is also had; Alkyl-3-(3,5-di-t-butyl-4-hydroxyphenyl) propionic ester is as Octadecane base-3-(3,5-di-t-butyl-4-hydroxyphenyl) propionic ester (Yoshinox SS, prepared by Yoshi tomi Fine Chemicals Ltd.), dodecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl) propionic ester and 2'-ethylhexyl-3-(3,5-di-t-butyl-4-hydroxyphenyl) propionic ester; Two (1,1-the dimethyl-ethyI)-4-hydroxyl-C7 ~ C9 pendant alkyl group ester (Irganox L135 is prepared by Ciba Specialty Chemicals Ltd.) of phenylpropionic acid 3,5-; 2,6-di-t-butyl-alpha-alpha-dimethyl amino-p-cresol; With 2,2'-methylene-bis (4-alkyl-6-tert.-butyl phenol) is as 2,2'-methylene-bis (4-methyl-6-tert-butylphenol) (Antage W-400, prepared by Kawaguchi Chemical Industry Ltd.) and 2,2'-methylene-bis(4-ethyl-6-t-butyl phenol) (Antage W-500 is prepared by Kawaguchi Chemical Industry Ltd.).
In addition, also has bis-phenol as 4, 4'-butylidene-bis(3-methyl-6-t-butyl phenol) (Antage W-300, prepared by Kawaguchi Chemical Industry Ltd.), 4, 4'-methylene-bis (2, 6-DI-tert-butylphenol compounds) (Ionox220AH, prepared by Shel l Japan Ltd.), 4, 4'-two (2, 6-DI-tert-butylphenol compounds), 2, 2-(di-p oxyphenyl) propane (dihydroxyphenyl propane, by preparation Shel l Japan Ltd.), 2, 2-two (3, 5-di-t-butyl-4-hydroxyphenyl) propane, 4, 4'-cyclohexylene two (2, 6-tert.-butyl phenol), two [the 3-(3 of hexamethylene glycol, 5-di-t-butyl-4-hydroxyphenyl) propionic ester] (Irganox L109, prepared by Ciba Special ty Chemicals Ltd.), two [3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) the propionic ester] (Tominox 917 of triethylene glycol, prepared by Yoshitomi Fine Chemicals Ltd.), 2, 2'-sulfo-[diethyl-3-(3, 5-di-t-butyl-4-hydroxyphenyl) propionic ester (Irganox L115, prepared by Ciba Specialty Chemicals Ltd.), 3, 9-two { 1, 1-dimethyl-2-[3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionyloxy] ethyl } 2, 4, 8, 10-tetra-oxaspiro [5, 5] undecane (Sumilizer GA80, prepared by Sumitomo Chemicals), 4, 4'-thiobis (3 methy 6 tert butyl phenol) (Antage RC, prepared by Kawaguchi Chemical Industry Ltd.) and 2, 2'-thiobis (4, 6-di-t-butyl-Resorcinol).
Also can mention that polyphenyl phenol is as four [methylene radical-3-(3, 5-di-t-butyl-4-hydroxyphenyl) propionic ester] methane (Irganox L101, prepared by Ciba Special ty Chemicals Ltd.), 1, 1, 3-tri-(2-methyl-4-hydroxyl-5-tert-butyl-phenyl) butane (Yoshinox 930, prepared by Yoshi tomi Fine Chemicals Ltd.), 1, 3, 5-trimethylammonium-2, 4, 6-tri-(3, 5-di-t-butyl-4-hydroxyphenylmethyl) benzene (Ionox 330, prepared by Shell Japan Ltd.), two-[3, 3'-pair-(4'-hydroxyl-3'-tert-butyl-phenyl) butyric acid] glycol ester, 2-(3', 5'-di-t-butyl-4-hydroxyphenyl) methyl-4-(2 ", 4 "-di-t-butyl-3 "-hydroxyphenyl) methyl-6-tert-butylphenol and 2, 6,-bis-(the 2'-hydroxyl-3'-tertiary butyl-5'-Metfayl-benzyl)-4-methylphenol, with phenol-aldehyde condensation products as p-tert-butylphenol and the condensation product of formaldehyde and the condensation product of p-tert-butylphenol and acetaldehyde.
As the example of phosphorus base antioxidant, can mention that triarylphosphite is as triphenyl phosphite and trimethylphenyl phosphorous acid ester; Trialkyl phosphite is as three (octadecyl) phosphorous acid esters and three decyl phosphorous acid esters; With three (dodecyl) trithiophosphite.
The metal passivator that can use together with composition of the present invention comprises benzotriazole and benzotriazole derivatives and benzoglyoxaline and benzimidizole derivatives, and described benzotriazole derivatives is that 4-alkyl-benzotriazole is as 4-methyl-benzotriazole and 4-ethyl-benzotriazole; 5-alkyl-benzotriazole is as 5-methyl-benzotriazole and 5-ethyl-benzotriazole; 1-alkyl-benzotriazole is if 1-dioctylamino methyl-2,3-benzotriazole and 1-alkyl-azimido-toluene are as 1-dioctylamino methyl-2,3-azimido-toluene; Described benzimidizole derivatives be 2-(alkyl dithio)-benzoglyoxaline as 2-(octyl group dithio)-benzoglyoxaline, 2-(decyl dithio)-benzoglyoxaline and 2-(molybdenum didodecyl dithiophosphate)-benzoglyoxaline, and 2-(alkyl dithio) first benzoglyoxaline is as 2-(octyl group dithio)-first benzoglyoxaline, 2-(decyl dithio)-first benzoglyoxaline and 2-(molybdenum didodecyl dithiophosphate) first benzoglyoxaline.
In addition, indazole, indazole derivatives, benzothiazole and benzothiazole derivant can also be mentioned, described indazole derivatives is that tolyl indazole is as 4-alkyl-indazole and 5-alkyl-indazole, described benzothiazole derivant is that 2-mercaptobenzothiazole derivative (Thiolite B-3100 is prepared by Chiyoda Chemical Indus tr ies Ltd.), 2-(alkyl dithio) benzothiazole are as 2-(hexyl dithio) benzothiazole and 2-(octyl group dithio) benzothiazole; 2-(alkyl dithio) tolyl thiazole is as 2-(hexyl dithio) tolyl thiazole and 2-(octyl group dithio) tolyl thiazole; 2-(N, N-dialkyldithiocarbamoyl)-benzothiazole is as 2-(N, N-diethyl-dithio formamyl)-benzothiazole, 2-(N, N-dibutyl dithio formamyl)-benzothiazole and 2-(N, N-dihexyl Dithiocarbamyl)-benzothiazole; With 2-(N; N-dialkyldithiocarbamoyl)-benzothiazole is as 2-(N; N-diethyl-dithio formamyl)-tolyl thiazole, 2-(N; N-dibutyl dithio formamyl)-tolyl thiazole and 2-(N, N-dihexyl Dithiocarbamyl)-tolyl thiazole.
In addition, benzo can be mentioned oxazole derivatives, thiadiazoles derivative and triazole derivative, described benzo oxazole derivatives is 2-(alkyl dithio) benzo azoles is as 2-(octyl group dithio) benzo azoles, 2-(decyl dithio) benzo azoles and 2-(molybdenum didodecyl dithiophosphate) benzo azoles, or 2-(alkyl dithio) tolyl azoles is as 2-(octyl group dithio) tolyl azoles, 2-(decyl dithio) tolyl azoles and 2-(molybdenum didodecyl dithiophosphate) tolyl azoles; Described thiadiazoles derivative is two (the alkyl dithio)-1,3 of 2,5-, 4-thiadiazoles (heptyl dithio)-1,3 as two in 2,5-, 4-thiadiazoles, 2,5-two (nonyl dithio)-1,3,4-thiadiazoles, 2,5-two (molybdenum didodecyl dithiophosphate)-1,3,4-thiadiazoles and 2, two (octadecyl dithio)-1,3, the 4-thiadiazoles of 5-; Two (N, the N-dialkyldithiocarbamoyl)-1 of 2,5-, 3,4-thiadiazoles (N as two in 2,5-, N-diethyl-dithio formamyl)-1,3,4-thiadiazoles, 2, two (N, the N-dibutyl dithio formamyl)-1,3 of 5-, 4-thiadiazoles and two (N, the N-dioctyl Dithiocarbamyl)-1 of 2,5-, 3,4-thiadiazoles; And 2-N, N-dialkyldithiocarbamoyl-5-sulfydryl-l, 3,4-thiadiazoles is as 2-N, N-dibutyl dithio formamyl-5-sulfydryl-1,3,4-thiadiazoles and 2-N, N-dioctyl Dithiocarbamyl-5-sulfydryl-1,3,4-thiadiazoles; Described triazole derivative is that such as 1-alkyl-2,4-triazole is as 1-dioctylamino methyl-2,4-triazole.In the base oil of 100 weight parts, these metal passivators can independent or multiple combination use in the scope of 0.01-0.5 weight part.
Phosphorus compound can also be added to give antiwear characteristic and extreme pressure property in lubricating oil composition of the present invention.As the example being suitable for phosphorus compound of the present invention, ester and their derivative of the amine salt of phosphoric acid ester, acid phosphoric acid ester, acid phosphoric acid ester, alkaline phosphate ester, phosphorous acid ester, thiophosphatephosphorothioate, zinc dithiophosphate, phosphorodithioic acid and alkanol or polyether-type alcohol can be mentioned and comprise the carboxylic acid of phosphorus and comprise the carboxylicesters of phosphorus.In the base oil of 100 weight parts, these phosphorus compounds can independent or multiple combination use in the scope of 0.01-2 weight part.
As the example of aforementioned phosphate ester, Tributyl phosphate ester can be mentioned, three pentyl, three hexyl phosphoric acid ester, three heptyl phosphoric acid ester, trioctyl phosphate, three nonyl phosphoric acid ester, three decyl phosphoric acid ester, three (undecyl) phosphoric acid ester, three (dodecyl) phosphoric acid ester, three (tridecyl) phosphoric acid ester, three (tetradecyl) phosphoric acid ester, three (pentadecyl) phosphoric acid ester, three (hexadecyl) phosphoric acid ester, three (heptadecyl) phosphoric acid ester, three (octadecyl) phosphoric acid ester, three oleyl phosphate, triphenyl, three (isopropyl phenyl) phosphoric acid ester, triallyl phosphoric acid ester, tricresyl phosphate, three (xylyl) phosphoric acid ester, cresyl diphenyl phosphate and xylyl diphenyl phosphoester.
As the special case of aforementioned acid phosphoric acid ester, monobutyl acid phosphoric acid ester can be mentioned, single amyl group acid phosphoric acid ester, single hexyl acid phosphoric acid ester, single heptyl acid phosphoric acid ester, single octyl group acid phosphoric acid ester, single nonyl acid phosphoric acid ester, single decyl acid phosphoric acid ester, single (undecyl) acid phosphoric acid ester, single (dodecyl) acid phosphoric acid ester, single (tridecyl) acid phosphoric acid ester, single (tetradecyl) acid phosphoric acid ester, single (pentadecyl acid) phosphoric acid ester, single (hexadecyl) acid phosphoric acid ester, single (heptadecyl) acid phosphoric acid ester, single (octadecyl) acid phosphoric acid ester, single oleyl acid phosphoric acid ester, dibutyl acid phosphoric acid ester, diamyl acid phosphoric acid ester, dihexyl acid phosphoric acid ester, diheptyl acid phosphoric acid ester, dioctyl acid phosphoric acid ester, dinonyl acid phosphoric acid ester, didecyl acid phosphoric acid ester, two (undecyl) acid phosphoric acid ester, two (dodecyl) acid phosphoric acid ester, two (tridecyl) acid phosphoric acid ester, two (tetradecyl) acid phosphoric acid ester, two (pentadecyl) acid phosphoric acid ester, two (hexadecyl) acid phosphoric acid ester, two (heptadecyl) acid phosphoric acid ester, two (octadecyl) acid phosphoric acid ester and two oleyl acid phosphoric acid esters.
As the example of the amine salt of aforementioned acid phosphoric acid ester, the methylamine salt of aforementioned acid phosphoric acid ester, ethylamine salt, propylamine salt, butylamine salt, amylamine salt, hexylamine salt, heptyl amice salt, octylamine salt, dimethylamine salt, diethylamine salt, dipropyl amine salt, dibutylamine salt, diamyl amine salt, dihexylamine salt, two heptyl amice salt, Di-Octyl amine salt, front three amine salt, triethylamine salt, tripropyl amine salt, Tributylamine salt, triamylamine salt, trihexylamine salt, three heptyl amice salt and trioctylamine salt can be mentioned.
As the example of foregoing phosphites, dibutyl phosphorous acid ester can be mentioned, diamyl phosphorous acid ester, dihexyl phosphorous acid ester, diheptyl phosphorous acid ester, dioctyl phosphito ester, dinonyl phosphorous acid ester, didecyl phosphite, two (undecyl) phosphorous acid ester, two (dodecyl) phosphorous acid ester, two oleyl phosphorous acid esters, diphenylphosphite, xylyl phosphorous acid ester, tributyl phosphorous acid ester, three amyl group phosphorous acid esters, three hexyl phosphorous acid esters, three heptyl phosphorous acid esters, trioctylphosphite, three nonyl phosphorous acid esters, three decyl phosphorous acid esters, three (undecyl) phosphorous acid ester, three (dodecyl) phosphorous acid ester, three oleyl phosphorous acid esters, triphenyl phosphite and trimethylphenyl phosphorous acid ester.
As the example of aforementioned thiophosphatephosphorothioate, can specifically mention tributyl thiophosphatephosphorothioate, three pentylthio phosphoric acid ester, three hexyl thiophosphatephosphorothioates, three heptyl thiophosphatephosphorothioates, trioctylphosphine thiophosphatephosphorothioate, three nonyl thiophosphatephosphorothioates, three decyl thiophosphatephosphorothioates, three (undecyl) thiophosphatephosphorothioate, three (dodecyl) thiophosphatephosphorothioate, three (tridecyl) thiophosphatephosphorothioate, three (tetradecyl) thiophosphatephosphorothioate, three (pentadecyl) thiophosphatephosphorothioate, three (hexadecyl) thiophosphatephosphorothioate, three (heptadecyl) thiophosphatephosphorothioate, three (octadecyl) thiophosphatephosphorothioate, three oleyl thiophosphatephosphorothioates, triphenylphosphorothionate, trimethylphenyl thiophosphatephosphorothioate, three (xylyl) thiophosphatephosphorothioate, tolyl phenylbenzene thiophosphatephosphorothioate, xylyl phenylbenzene thiophosphatephosphorothioate, three (n-propyl phenyl) thiophosphatephosphorothioate, three (isopropyl phenyl) thiophosphatephosphorothioate, three (n-butylphenyl) thiophosphatephosphorothioate, three (isobutyl phenenyl) thiophosphatephosphorothioate, three (secondary butyl phenenyl) thiophosphatephosphorothioates and three (tert-butyl-phenyl) thiophosphatephosphorothioate.Also the mixture of these compounds can be used.
As the example of aforementioned zinc dithiophosphate, zinc dialkyl dithiophosphate, zinc diaryl dithiophosphates and arylalkyl zinc dithiophosphate generally can be mentioned.Such as, the alkylaryl that the alkyl in operable zinc dialkyl dithiophosphate has the uncle of 3 ~ 22 carbon or secondary alkyl or replaces with the alkyl of 3 ~ 18 carbon.As the special case of zinc dialkyl dithiophosphate, can mention that dipropyl disulfide is for zinc phosphate, zinc dibutyldithiophosphate, diamyl disulfide is for zinc phosphate, dihexyl zinc dithiophosphate, diisoamyl zinc dithiophosphate, diethylhexyl zinc dithiophosphate, dioctyl zinc dithiophosphate, dinonyl zinc dithiophosphate, didecyl zinc dithiophosphate, two (dodecyl) zinc dithiophosphate, dipropyl phenyl zinc dithiophosphate, diamyl phenyl zinc dithiophosphate, dipropyl aminomethyl phenyl zinc dithiophosphate, dinonylphenyl zinc dithiophosphate, two (dodecyl) phenyl zinc dithiophosphate and two (dodecyl) phenyl zinc dithiophosphate.
The fatty acid ester that can add polyvalent alcohol in lubricating oil composition of the present invention improves oiliness.Such as, polyvalent alcohol can be used as the partial ester with the saturated of 1-24 carbon or unsaturated fatty acids of glycerine, sorbyl alcohol, aklylene glycol, neopentyl glycol, TriMethylolPropane(TMP), tetramethylolmethane and Xylitol or full ester.The material utilizing and prepare with the different types of compound of aforementioned carboxylic acid's ester cpds can also be added.
The example of glyceryl ester comprises glyceryl monolaurate, Zerol, glycerol monopalmitate, glyceryl monooleate, Lauric acid, diester with glycerol, Stearic diglyceride, dipalmitin and glycerol dioleate.For sorbitol ester, sorbitan monolaurate, sorbyl alcohol monopalmitate, sorbitol monostearate, sorbitol monooleate, sorbyl alcohol dilaurate, sorbyl alcohol dipalmitate, sorbyl alcohol SUNSOFT Q-182S, sorbyl alcohol dioleate, sorbyl alcohol tristearate, sorbyl alcohol trilaurin, sorbitol olein and sorbyl alcohol four oleic acid ester can be mentioned.
Alkylidene diol ester comprises ethylene glycol monolaurate, ethylene glycol monostearate, ethylene glycol monoleate, ethylene glycol dilaurate, Unister E 275, ethylene glycol bisthioglycolate oleic acid ester, Rikemal PL 100, propylene glycol monostearate, propylene glycol mono-oleate, propandiol dilaurate, propanediol distearate and Rikemal PO 200.For DOPCP, neopentyl glycol mono-laurate, neopentyl glycol monostearate, neopentyl glycol monoleate, neopentyl glycol dilaurate, neopentyl glycol SUNSOFT Q-182S and neopentyl glycol dioleate can be mentioned.
Trihydroxymethylpropanyl ester comprises TriMethylolPropane(TMP) mono-laurate, TriMethylolPropane(TMP) monostearate, TriMethylolPropane(TMP) monoleate, TriMethylolPropane(TMP) dilaurate, TriMethylolPropane(TMP) SUNSOFT Q-182S and TriMethylolPropane(TMP) dioleate.Pentaerythritol ester comprises pentaerythritol monostearate, pentaerythritol monooleate, tetramethylolmethane dilaurate, pentaerythritol stearic acid ester 2, tetramethylolmethane dioleate and Dipentaerythritol monoleate.For the fatty acid ester of these polyvalent alcohols, preferably use the partial ester of polyvalent alcohol and unsaturated fatty acids.
In order to improve low temperature flow characteristic sum viscosity characteristics, also pour point depressant and viscosity index improver can be added lubricating oil composition of the present invention.As the example of viscosity index improver, can mention that non-dispersive type viscosity index improvers is if polymethacrylate and olefin polymer are as ethylene-propylene copolymer, styrenic-diene multipolymer, polyisobutene and polystyrene, with dispersant type viscosity index improving agent, wherein nitrogen containing monomer copolymerization with it, and they can utilize and prepare with the different types of material of multipolymer of foregoing alkenes and alkyl methacrylate.About the amount added, in the base oil of 100 weight parts, they can use in the scope of 0.05-20 weight part.
As the example of pour point depressant, polymethacrylate based polyalcohol can be mentioned.About the amount added, in the base oil of 100 weight parts, they can use in the scope of about 0.01-5 weight part.
Also defoamer can be added to give froth breaking feature in lubricating oil composition of the present invention.As the example being suitable for this defoamer of the present invention, can mention that organosilicon acid esters is as dimethyl polysiloxane, diethyl silicon ester and fluorosilicone, and non-organic silicon type defoamer is as polyalkyl acrylate.About the amount added, in the base oil of 100 weight parts, they can independent or multiple combination use in the scope of 0.0001-0.1 weight part.
As the example being suitable for emulsion splitter of the present invention, can mention in known art usually used as additive those emulsion splitters for lubricating oil.About the amount added, in the base oil of 100 weight parts, they can use in the scope of 0.0005-0.5 weight part.
The viscosity of lubricating oil composition of the present invention is not particularly limited, but viscosity index should be not less than 130, is preferably not less than 140 and be more preferably not less than 150.The kinematic viscosity of described lubricating oil composition at 40 DEG C should be 140-320mm 2/ s, but preferred 140-200mm 2/ s and more preferably 140-160mm 2/ s.In the Dry TOST of described lubricating oil composition tests, the amount of mud should be not more than 1500mg/kg, but is preferably not more than 1300mg/kg and more preferably no more than 1200mg/kg.At the green oil of described lubricating oil composition and the test oil after Dry TOST tests, the remaining rate of RPVOT in RPVOT test should be not less than 40%, but is preferably not less than 50% and be more preferably not less than 60%.
Lubricating oil composition of the present invention is used as machine oil, hydraulic efficiency oil, turbine oil, compressor oil, wheel tooth oil, oily, the bearing oil of sliding surface or calibration oil.Lubricating oil composition of the present invention is used as long row's gear oil ideally." long row's gear oil " is the technical grade gear oil with long oil change interval in the present invention.Oil change interval is not particularly limited, but typical example is not for being shorter than 1 year and not preferably being shorter than 2 years or not more preferably being shorter than 3 years.Especially, lubricating oil composition of the present invention is ideally for the wheel of accelerating gear device in wind energy generating plant.
embodiment
Further illustrate below by way of the embodiment of application implementation scheme and comparative example and of the present invention there is fabulous extreme pressure property (preventing the ability of melting loss), produce a small amount of mud and also there is the lubricating oil composition of high viscosity index (HVI), but the present invention limits by these embodiments never in any form.
Composite material is below for preparing embodiment and the comparative example of embodiment.
1, base oil
Poly-alpha olefins (PAO) synthetic oil, is divided into Group IV according to API (API) basestock classification.
(1-1) base oil 1: (popular name: PAO6, is characterized as poly-alpha olefins: the kinematic viscosity at 40 DEG C: 35.4mm 2/ s; Kinematic viscosity at 100 DEG C: 6.44mm 2/ s; Viscosity index 136; Density at 15 DEG C: 0.8291g/cm 3; Aniline point: 130 DEG C)
(1-2) base oil 2: (popular name: PAO40, is characterized as poly-alpha olefins: the kinematic viscosity at 40 DEG C: 401mm 2/ s; Kinematic viscosity at 100 DEG C: 40.3mm 2/ s; Viscosity index 151; Density at 15 DEG C: 0.8491g/cm 3; Aniline point: 161 DEG C)
2, additive
(2-1) additive A 1: the multipolymer (popular name: Viscobase 11-570, is prepared by Evonik Ltd.) of alkene and alkyl methacrylate
Molecular weight: 1200-25,000 (Fig. 1)
Number-average molecular weight: 5400
Weight-average molecular weight: 9400
Molecular weight distribution: 1.7
Kinematic viscosity at 40 DEG C: 2,500mm 2/ s
Kinematic viscosity at 100 DEG C: 150mm 2/ s
Viscosity index: 160
Density at 15 DEG C: 0.926g/cm 3
(2-2) additive A 2: the multipolymer (popular name: Viscobase 11-574, is prepared by Evonik Ltd.) of alkene and alkyl methacrylate
Molecular weight: 1200-50,000 (Fig. 1)
Number-average molecular weight: 8000
Weight-average molecular weight: 15000
Molecular weight distribution: 1.9
Kinematic viscosity at 40 DEG C: 9,000mm 2/ s
Kinematic viscosity at 100 DEG C: 450mm 2/ s
Viscosity index: 200
Density at 15 DEG C: 0.934g/cm 3
(2-3) additive A 3: olefin copolymer (popular name: Lucant HC-1100 is prepared by Mitsui Chemicals Ltd.)
Number-average molecular weight: 6,000
Kinematic viscosity at 40 DEG C: 18,900mm 2/ s
Kinematic viscosity at 100 DEG C: 1,100mm 2/ s
Viscosity index: 270
Density at 15 DEG C: 0.850g/cm 3
(2-4) additive A 4: polyisoolefines (popular name: Nisseki polybutene HV300 is prepared by JX Nippon Oil & Energy Corp.)
Number-average molecular weight: Isosorbide-5-Nitrae 00
Kinematic viscosity at 40 DEG C: 26,000mm 2/ s
Kinematic viscosity at 100 DEG C: 590mm 2/ s
Viscosity index: 155
Density at 15 DEG C: 0.898g/cm 3
(2-5) additive B: gear oil additive bag (popular name: Anglamo199 is prepared by Lubrizol Corp.)
Kinematic viscosity at 40 DEG C: 68mm 2/ s
Kinematic viscosity at 100 DEG C: 8.2mm 2/ s
Density at 15 DEG C: 1.07g/cm 3
Sulphur content: 29.8-33.8wt%
Phosphorus content: 1.55-1.89wt%
Nitrogen content: 0.85-1.03wt%
Additive B: Anglamo is known gear oil additive bag, will meet API GL-4 standard if describe this bag of 3.25-3.9% to be mixed in lubricating oil in Lubrizol catalogue.API GL-4 standard is divided into 6 classes, and the ratio of additive is larger with the increase of numerical value, because this increasing extreme pressure property.In the embodiment of embodiment, in formulation, the amount of this additive B is set to 2.0% to meet API GL-3 standard (having the extreme pressure property of at least medium level), but the amount of additive B is not particularly limited in formulation.
(2-6) addition of C: trihydroxy methyl propyl group trioleate (popular name: Unister H327R, is prepared by NOF Corp.)
Prepared by the aforesaid ingredients material provided in the embodiment 1-4 of embodiment and the lubricating oil composition utilization table of comparative example 1-4 and composition.
Dry TOST and RPVOT test as described below is carried out to observe their performance to the embodiment 1-4 of embodiment and the lubricating oil composition of comparative example 1-4.
Dry TOST
According in JIS K2514 for the testing method of turbine oil oxidative stability, the test oil of 360ml is poured in container, any water or catalyzer need not be added, in the thermostatic bath of 120 DEG C, be blown into 3 liters of oxygen by every 1 hour heat 336 hours.Complete latter 24 hours of test, utilize the film filter in 1 μm of aperture to filter test oil, measure the sludge quantity produced.
RPVOT
According in JIS K2514 for the testing method of rotating missile oxidative stability test, the test oil of 50g is poured in container, under the common existence of 5ml distilled water and copper catalyst, places it at room temperature 25 DEG C and be forced into 6.3kgf/cm with oxygen 2bullet in.In 150 DEG C of thermostatic baths, per minute rotates 100 times.Pressure in record bullet.After bullet is introduced thermostatic bath by measurement, from reached peak pressure until observe that pressure reduces to 1.75kgf/cm 2time, this value is as RPVOT value.RPVOT is carried out for green oil and the test oil (before filtration) after completing TOST.
As shown in table 1 below, the embodiment 1 and 2 of embodiment that wherein multipolymer of alkene and alkyl methacrylate is used as viscosity index improver demonstrates the high viscosity index (HVI) being greater than 150, and after Dry TOST tests, sludge quantity is less than 1,100mg/kg.On the contrary, the comparative example 1 of olefin copolymer is used to have high viscosity index (HVI) but sludge quantity is large.The mud of the comparative example 2 of use polyisobutene is few but viscosity index is low.
Table 2 gives and trihydroxy methyl propyl group trioleate (addition of C) is added the embodiment 1 and 2 of embodiment and the result of comparative example 1 and 2.By adding trihydroxy methyl propyl group trioleate, the multipolymer of alkene and alkyl methacrylate is used to improve larger with the sludge quantity reduced more greatly as the embodiment 3 of the embodiment of viscosity index improver and the embodiment 4 of embodiment than the viscosity index of the embodiment 1 of embodiment or the embodiment 2 of embodiment.From the difference of comparative example 3 and comparative example 1 and comparative example 4 and comparative example 2 result, owing to adding trihydroxy methyl propyl group trioleate, the good results are evident, but compared to the embodiment 3 and 4 of embodiment, the sludge quantity of comparative example 3 is still comparatively large, can find out that the viscosity index of comparative example 4 is lower.
For the remaining rate of RPVOT, be preferably not less than the value of 40%, but be more preferably not less than the value of 50%.

Claims (7)

1. lubricating oil composition, the at least one of it comprises (A) 50-90wt% is selected from the lubricant base of mineral oil and synthetic oil and the molecular weight of (B) 10-50wt% is 1200-50, the alkene of 000 and the multipolymer of alkyl methacrylate.
2. lubricating oil composition according to claim 1, wherein said lubricant base is poly-alpha olefins or GTL (gas is to liquid) oil.
3., according to the lubricating oil composition of claim 1 or 2, the weight-average molecular weight of wherein said multipolymer is 7000-20000.
4., according to the lubricating oil composition of any one of claim 1-3, wherein said lubricant base comprises (C) carbonate accounting for described lubricating oil composition total amount 5-15wt%.
5., according to the lubricating oil composition of any one of claim 1-4,40 DEG C of kinematic viscosity of wherein said lubricating oil composition are 140-320mm 2/ s, viscosity index be not less than 150 and in dry TOST test sludge quantity be not more than 1200mg/kg.
6. the purposes of, bearing oil oily as machine oil, hydraulic efficiency oil, turbine oil, compressor oil, wheel tooth oil, sliding surface according to the lubricating oil composition of any one of claim 1-5 or calibration oil.
7. according to the lubricating oil composition of any one of the claim 1-5 purposes as long row's gear oil.
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