CN108291173A - Lubricant oil composite - Google Patents

Lubricant oil composite Download PDF

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Publication number
CN108291173A
CN108291173A CN201680069819.0A CN201680069819A CN108291173A CN 108291173 A CN108291173 A CN 108291173A CN 201680069819 A CN201680069819 A CN 201680069819A CN 108291173 A CN108291173 A CN 108291173A
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CN
China
Prior art keywords
copper
lubricant oil
oil composite
oil
mass ppm
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Pending
Application number
CN201680069819.0A
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Chinese (zh)
Inventor
八木下和宏
吉田俊男
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Jxtg Energy Corp
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Jxtg Energy Corp
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Publication of CN108291173A publication Critical patent/CN108291173A/en
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
    • C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
    • C10M129/26—Carboxylic acids; Salts thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M133/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen
    • C10M133/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of less than 30 atoms
    • C10M133/04—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M133/12—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to a carbon atom of a six-membered aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M135/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
    • C10M135/12—Thio-acids; Thiocyanates; Derivatives thereof
    • C10M135/14—Thio-acids; Thiocyanates; Derivatives thereof having a carbon-to-sulfur double bond
    • C10M135/18—Thio-acids; Thiocyanates; Derivatives thereof having a carbon-to-sulfur double bond thiocarbamic type, e.g. containing the groups
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
    • C10M169/04—Mixtures of base-materials and additives

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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 present invention provides a kind of lubricant oil composite, contains：Lube base oil, alkylated diphenylamine and at least one kind of copper-containing compound in the group being made of copper carboxylate and aminodithioformic acid copper, the content of copper are more than 0 mass ppm and for 30 mass ppm or less on the basis of lubricant oil composite total amount, in terms of copper atom conversion.

Description

Lubricant oil composite
Technical field
The present invention relates to lubricant oil composites.
Background technology
Various uses of the lubricating oil in engine oil, driving system lubricating oil, turbine oil, hydraulic oil, lubricating grease etc. It is middle to be used.For lubricating oil, it is desirable that be not easy to deteriorate (inoxidizability) because of oxidation.
It is disclosed in example Patent Documents 1 to 4 described as follows：Oil-soluble cupric is added to improve inoxidizability Close the lubricant oil composite of the combination of object and sulfur-bearing metal complex.
Existing technical literature
Patent document
Patent document 1：Clear No. 55-111568 of Japanese Patent Application
Patent document 2：Clear No. 63-121649 of Japanese Patent Application
Patent document 3：Japanese Unexamined Patent Application 62-181397 bulletins
Patent document 4：Japanese Unexamined Patent Publication 2004-149779 bulletins
Invention content
Problems to be solved by the invention
However, the research according to the inventors of the present invention is distinguished：Even if as the lubricating oil group described in Patent Documents 1 to 4 Object is closed, there is also further rooms for improvement in terms of being such as difficult to maintain the inoxidizability such as inoxidizability for a long time.
The present invention has been made in view of such circumstances, and its purpose is to provide can remain adequately anti-oxidant for a long time The lubricant oil composite of property.
The solution to the problem
In order to solve the above problems, the present invention provides a kind of lubricant oil composite, contains：Lube base oil, alkyl Diphenylamines and at least one kind of copper-containing compound in the group being made of copper carboxylate and aminodithioformic acid copper, copper contain Amount is more than 0 mass ppm and for 30 mass ppm or less on the basis of lubricant oil composite total amount, in terms of copper atom conversion.
In above-mentioned lubricant oil composite, the content of sulphur on the basis of lubricant oil composite total amount, in terms of sulphur atom conversion Preferably 100 mass ppm or less.
The effect of invention
According to the present invention, it is possible to provide sufficient antioxidative lubricant oil composite can be maintained for a long time.In turn, of the invention Lubricant oil composite inhibit sludge generation in terms of be also it is excellent.
Specific implementation mode
The suitable embodiment of the present invention is described in detail below.
The lubricant oil composite of embodiments of the present invention contains：Lube base oil, alkylated diphenylamine and selected from by At least one kind of copper-containing compound in copper carboxylate and the group of aminodithioformic acid copper composition.In the lubricant oil composite, copper contains Amount is more than 0 mass ppm and for 30 mass ppm or less on the basis of lubricant oil composite total amount, in terms of copper atom conversion.
It as lube base oil, is not particularly limited, the substance for common lubricating oil can be used.Such as it can arrange It enumerates：Mineral oil system lube base oil, synthetic oil system lube base oil or their miscella.
As mineral oil system lube base oil, can specifically enumerate：To normal pressure obtained from air-distillation crude oil Residual oil, which is evaporated under reduced pressure, obtains lube cut, which is carried out the primary above solvent deasphalting, solvent Extract, be hydrocracked, solvent dewaxing, the processing such as hydrofinishing and the substance being refined into；Or wax isomerization mineral oil；Using pair GTL waxes (gas-to-liquid wax) carry out the base oil etc. manufactured by the method for isomerization.From maintaining sufficient antioxygen for a long time Change property from the perspective of so that from the viewpoint of inhibit sludge generation, it is preferable to use highly purified base oil.
As synthetic oil system lubricating oil, can specifically enumerate：Polybutene or its hydride；1- octene oligomers, 1- The poly-alpha-olefins such as decylene oligomer or its hydride；It is double tridecyl glutarate, two -2- ethyl hexyl adipates, two different The diester such as decyl adipate ester, ditridecyl adipate, two -2- ethylhexyl sebacates；Trimethylolpropane octanoic acid The polyol esters such as ester, trimethylolpropane pelargonate, pentaerythrite -2 ethyl hexanoic acid ester, pentaerythrite pelargonate；Alkylnaphthalene, The aromatic systems such as alkylbenzene synthetic oil or their mixture etc..
The kinematic viscosity and viscosity index (VI) of lube base oil are not particularly limited, for example, lube base oil is at 40 DEG C Under kinematic viscosity can be set as 5~500mm2/ second, 20~100mm2/ second or 30~60mm2/ the second.In addition, lube base oil Kinematic viscosity at 100 DEG C can be set as 2~30mm2/ second, 4~20mm2/ second or 6~10mm2/ the second.In addition, lubrication oil base The viscosity index (VI) of plinth oil can be set as 90 or more, 105 or more or 120 or more.
" kinematic viscosity at 40 DEG C " so-called in the present invention, " kinematic viscosity at 100 DEG C " and " viscosity index (VI) " Refer to respectively according to JIS K2283：2000 values measured.
The all aromatic component content of lube base oil is not particularly limited, preferably 20 mass % or less, more preferably For 10 mass % or less, further preferably 1 mass % or less.The all aromatic content of lube base oil be 5 mass % with When lower, there is the antioxidative tendency that can further increase lubricant oil composite.
" all aromatic component content " so-called in the present invention refers to the aromatic fraction measured according to ASTM D2549 (aromatic fraction) content.Other than alkylbenzene, alkylnaphthalene, in the aromatic fraction can include anthracene, phenanthrene and it Alkylates, compound or pyridines, quinolines, phenol, aphthols etc. have made of four or more phenyl ring are condensed The compound etc. of heteroaromatic.
As alkylated diphenylamine, such as the following general formula (1) compound represented can be enumerated.
[in formula (1), R1And R2Hydrogen atom or alkyl, R are indicated respectively1And R2At least one of be alkyl, R1And R2The two For alkyl when, R1And R2It can be the same or different.]
As R1And R2Shown in alkyl, can specifically enumerate：Methyl, ethyl, propyl, butyl, amyl, hexyl, heptan (these such as base, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, myristyl, pentadecyl, cetyl It can also be branched that a little alkyl, which can be straight-chain).Wherein, from the viewpoint of maintaining inoxidizability for a long time, preferred carbon number 3 ~16 branched alkyl, more preferable carbon number 3 or 4 alkene or its oligomer derived from carbon number 3~16 branched alkyl.As carbon The alkene of number 3 or 4 can specifically enumerate：Propylene, 1- butylene, 2- butylene and isobutene etc., from can maintain to longer-term From the perspective of inoxidizability at high temperature, preferably propylene or isobutene.In addition, from further excellent antioxygen can be obtained From the aspect of the property changed, still more preferably：By the isopropyl of propylene derived, the tertiary butyl derived from isobutene, by the two of propylene Branch nonyl derived from branched octyl, the tripolymer by propylene derived from branched hexyl, the dimer by isobutene derived from aggressiveness Branched dodecyl derived from branched dodecyl, the tetramer by propylene derived from base, the tripolymer by isobutene or by third Branch pentadecyl derived from the pentamer of alkene, most preferably derived from tertiary butyl, the dimer by propylene derived from isobutene Branched nonyl derived from branched octyl, the tripolymer by propylene derived from branched hexyl, the dimer by isobutene, by isobutene Tripolymer derived from branched dodecyl derived from branched dodecyl or the tetramer by propylene.
R in general formula (1)1And R2Both preferably alkyl.R1And R2The two is the compound and R of alkyl1And R2Middle one It is compared for the compound of hydrogen atom, has the tendency that being difficult to due to the oxidation of the compound itself and cause to generate sludge.
Alkyl diphenylamine shown in general formula (1) can use commercially available substance, can also use synthetic.Synthetic can be with It is easily synthesized in the following way：Using Fu Lide-Crafts catalyst, progress diphenylamines is halogenated with carbon number 1~16 Hydride compounds are reacted with diphenylamines；Or carry out the alkene of diphenylamines and carbon number 2~16 or the alkene of carbon number 2~16 or they Oligomer reaction.As Fu Lide-Crafts catalyst, specifically can be used for example：Aluminium chloride, zinc chloride, The metal halides such as iron chloride；Acidic catalysts such as sulfuric acid, phosphoric acid, five phosphorous oxides, boron fluoride, Emathlite, atlapulgite etc..
Alkylated diphenylamine can be used alone, the mixture of more than two kinds that structure can also be used different.
From the viewpoint of inoxidizability, the content of alkylated diphenylamine is preferably on the basis of lubricant oil composite total amount 0.05 mass % or more, more preferably 0.3 mass % or more, further preferably 0.5 mass % or more.In addition, from inhibiting dirty From the perspective of mud generates, content preferably 5 mass % or less on the basis of lubricant oil composite total amount of alkylated diphenylamine, More preferably 3 mass % or less, further preferably 1 mass % or less.
As the carboxylic acid for constituting copper carboxylate, can enumerate：Aliphatic carboxylic acid, ester ring type carboxylic acid and aromatic carboxylic acid.These Carboxylic acid can be unsubstituted, furthermore it is also possible to have substituent group.
As aliphatic carboxylic acid, can enumerate：Caproic acid, enanthic acid, octanoic acid, n-nonanoic acid, capric acid, hendecanoic acid, dodecanoic acid, ten Three alkanoic acids, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid (palmitic acid), Heptadecanoic acide, octadecanoid acid (stearic acid), oleic acid etc..
It can be unsubstituted to constitute the aminodithioformic acid of aminodithioformic acid copper, furthermore it is also possible to taking Dai Ji.
As aminodithioformic acid copper, such as the following general formula (2) compound represented can be enumerated.
(R3R4NCSS)nCu (2)
[in formula (2), n is 1 or 2, R3And R4It can be the same or different, indicate alkyl respectively.]
As R3And R4Shown in alkyl, can enumerate：Alkyl, alkenyl, aryl, naphthenic base, cycloalkenyl group.Wherein, from oxidation From the perspective of service life is further excellent, the preferred alkyl of carbon number 2~8.As the alkyl of carbon number 2~8, can specifically enumerate Go out：Ethyl, propyl, butyl, amyl, hexyl, heptyl, octyl etc..These alkyl can be that straight-chain can also be branched.
From the viewpoint of the oil-soluble of aminodithioformic acid copper shown in above-mentioned formula (2), preferably R3And R4Shown in hydrocarbon The sum of carbon atom possessed by base is 4 or more.
In present embodiment, any one of copper carboxylate or aminodithioformic acid copper can be used, carboxylic can also be used Both sour copper and aminodithioformic acid copper.In turn, copper carboxylate and aminodithioformic acid copper can use individually 1 Kind, the mixture of more than two kinds that structure can also be used different.
The lubricant oil composite of present embodiment is the composition containing above-mentioned copper-containing compound, but maintains antioxygen from long-term From the perspective of the property changed, the content of copper on the basis of lubricant oil composite total amount, in terms of copper atom conversion more than 0 mass ppm, excellent It is selected as 1 mass ppm or more, more preferably 5 mass ppm or more, additionally, it is preferred that for 30 mass ppm or less, more preferably 20 mass Ppm or less, further preferably 15 mass ppm or less.
From the viewpoint of inhibiting sludge creation, the content of sulphur is changed on the basis of lubricant oil composite total amount, with sulphur atom Calculate preferably 100 mass ppm or less, more preferably 50 mass ppm or less, further preferably 10 mass ppm or less.According to Same reason, the sulphur ingredient of lube base oil contained in lubricant oil composite on the basis of lube base oil total amount, By sulphur atom conversion in terms of preferably 10 mass ppm or less, more preferably 7 mass ppm or less, further preferably 5 mass ppm with Under.
" copper content " so-called in the present invention and " sulfur content " refer to the content (unit measured by ICP elemental microanalysis methods： Quality ppm).
The kinematic viscosity and viscosity index (VI) of lubricant oil composite are not particularly limited.For example, lubricant oil composite is at 40 DEG C Under kinematic viscosity can be set as 5~500mm2/ second, 20~100mm2/ second or 30~60mm2/ the second.In addition, lubricant oil composite Kinematic viscosity at 100 DEG C can be set as 2~30mm2/ second, 4~20mm2/ second or 6~10mm2/ the second.In addition, lubricating oil group 90 or more, 105 or more or 120 or more can be set as by closing the viscosity index (VI) of object.
Other than above-mentioned alkylated diphenylamine and copper-containing compound, the lubricant oil composite of present embodiment can be with Further contain other additives.As above-mentioned lube oil additive, can specifically enumerate：Antioxidant (phenol system antioxygen Amine antioxidant etc. other than agent, alkylated diphenylamine), ashless dispersant, metal system cleaning agent, extreme pressure agent, antiwear additive, It is viscosity index improver, pour-point depressant, friction modifier, oiliness improver, preservative, antirust agent, anti emulsifier, metal deactivator, close Seal sweller, antifoaming agent, colorant etc..These additives can be used alone, furthermore it is also possible to be applied in combination 2 kinds with On.In addition, as long as the lubricant oil composite of present embodiment does not damage the effect of the present invention, can also contain comprising sulphur as structure At the additive of element.
The lubricant oil composite of present embodiment can use in the extensive field in lubricating oil field.As lubricating oil The purposes of composition can enumerate：Driving system lubricating oil, the hydraulic pressure of engine oil, automatic transmission or manual transmission etc. Working oil, turbine oil, compressor oil etc..
Embodiment
The present invention is further illustrated following with embodiment and comparative example, but the present invention is not limited to below Embodiment.
[Examples 1 to 6, comparative example 1~10]
For Examples 1 to 6 and comparative example 1~10, it is prepared for respectively using base oil and additive as shown below With the lubricant oil composite formed shown in table 1~3.The copper content and sulfur content of lubricant oil composite are shown simultaneously in table 1~3 (being element scaled value).
[base oil]
Base oil 1：Hydrorefined mineral oils (all aromatic component content：0.3 mass %, sulphur ingredient：Less than 10 mass Ppm, 40 DEG C of kinematic viscosity：35mm2/ second, viscosity index (VI)：120)
[alkylated diphenylamine]
A-1：Octylated/butylated diphenylamines (IRGANOX (registered trademark) L57, BASF AG's system)
A-2：Bis- (nonyl phenyl) amine (IRGANOX (registered trademark) L67, BASF AG's system)
[copper-containing compound]
B-1：Copper oleate (II) (DIC corporations, copper content：5.3 mass %)
B-2：Copper diethyl dithiocarbamate (CuDTC) (copper content：13.56 mass %, sulfur content：27.12 matter Measure %)
[sulfur-containing additive]
C-1：Dialkylthiophosphate esters (IRGALUBE (registered trademark) 353, BASF AG's system, sulfur content：18.9 matter Measure %, phosphorus content：9.45 mass %)
C-2：Tetra-n-butyl thiuram-disulfide (sulfur content：31.4 mass %)
[other additives]
D-1：Octyl phenyl-Alpha-Naphthyl amine (IRGANOX (registered trademark) L06, BASF AG's system)
D-2：2,6- di-t-butyls-paracresol (DBPC)
[oxidation stability test]
For the RPVOT values of each lubricant oil composite of Examples 1 to 6 and comparative example 1~10, according to JIS K2514 " profits " the 6. rotation gas storage pot type oxidation stability test method " of lubricating oil-oxidation stability test method " is determined.RPVOT Value indicates that oxidation stability can be maintained for a long time greatly.Show the result in table 1~3.
[table 1]
[table 2]
[table 3]
[evaluation of the presence or absence of sludge creation]
For each lubricant oil composite of Examples 1 to 6, the RPVOT values determined in above-mentioned oxidation stability test exist Sludge creation amount when reaching 90% of the RPVOT values before experiment (when reaching the remaining service life 90%).As a result, embodiment 1~ 4,6 lubricant oil composite does not observe the generation of sludge when reaching the remaining service life 90%.In addition, the profit of embodiment 5,7~8 Sludge creation of the sliding oil composition when reaching the remaining service life 90% is denier.

Claims (2)

1. a kind of lubricant oil composite, contains：
Lube base oil,
Alkylated diphenylamine and
At least one kind of copper-containing compound in the group being made of copper carboxylate and aminodithioformic acid copper,
The content of copper is more than 0 mass ppm and for 30 mass ppm on the basis of lubricant oil composite total amount, in terms of copper atom conversion Below.
2. lubricant oil composite according to claim 1, wherein the content of sulphur on the basis of lubricant oil composite total amount, It is calculated as 100 mass ppm or less with sulphur atom conversion.
CN201680069819.0A 2015-12-28 2016-12-21 Lubricant oil composite Pending CN108291173A (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP2015-257268 2015-12-28
JP2015257268A JP6480323B2 (en) 2015-12-28 2015-12-28 Lubricating oil composition
PCT/JP2016/088164 WO2017115703A1 (en) 2015-12-28 2016-12-21 Lubricating oil composition

Publications (1)

Publication Number Publication Date
CN108291173A true CN108291173A (en) 2018-07-17

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WO (1) WO2017115703A1 (en)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06313183A (en) * 1993-04-30 1994-11-08 Tonen Corp Lubricant composition
JPH07228882A (en) * 1994-02-17 1995-08-29 Cosmo Sogo Kenkyusho:Kk Gas turbine oil composition
US5994277A (en) * 1993-09-13 1999-11-30 Exxon Chemical Patents, Inc. Lubricating compositions with improved antioxidancy comprising added copper, a molybdenum containing compound, aromatic amine and ZDDP
JP2007238720A (en) * 2006-03-07 2007-09-20 Nippon Oil Corp Lubricating oil composition, anti-oxidant composition and method for inhibiting viscosity increase of the lubricating oil
CN101646757A (en) * 2007-03-28 2010-02-10 出光兴产株式会社 lubricating oil composition

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB8704682D0 (en) * 1987-02-27 1987-04-01 Exxon Chemical Patents Inc Low phosphorus lubricants
GB9409756D0 (en) * 1994-05-16 1994-07-06 Exxon Chemical Patents Inc Lubricating compositions
JP3370829B2 (en) * 1995-04-21 2003-01-27 株式会社日立製作所 Lubricating grease composition
US5906969A (en) * 1998-05-01 1999-05-25 Exxon Research And Engineering Company High fuel economy passenger car engine oil

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06313183A (en) * 1993-04-30 1994-11-08 Tonen Corp Lubricant composition
US5994277A (en) * 1993-09-13 1999-11-30 Exxon Chemical Patents, Inc. Lubricating compositions with improved antioxidancy comprising added copper, a molybdenum containing compound, aromatic amine and ZDDP
JPH07228882A (en) * 1994-02-17 1995-08-29 Cosmo Sogo Kenkyusho:Kk Gas turbine oil composition
JP2007238720A (en) * 2006-03-07 2007-09-20 Nippon Oil Corp Lubricating oil composition, anti-oxidant composition and method for inhibiting viscosity increase of the lubricating oil
CN101646757A (en) * 2007-03-28 2010-02-10 出光兴产株式会社 lubricating oil composition

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WO2017115703A1 (en) 2017-07-06
JP6480323B2 (en) 2019-03-06

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