CN107304379B - A kind of combustion gas turbine oil composition and preparation method thereof - Google Patents
A kind of combustion gas turbine oil composition and preparation method thereof Download PDFInfo
- Publication number
- CN107304379B CN107304379B CN201610238057.4A CN201610238057A CN107304379B CN 107304379 B CN107304379 B CN 107304379B CN 201610238057 A CN201610238057 A CN 201610238057A CN 107304379 B CN107304379 B CN 107304379B
- Authority
- CN
- China
- Prior art keywords
- weight
- oil
- dosage
- tert
- combustion gas
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
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
- C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
- C10M169/04—Mixtures of base-materials and additives
- C10M169/044—Mixtures of base-materials and additives the additives being a mixture of non-macromolecular and macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- 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
- C10M133/38—Heterocyclic nitrogen compounds
- C10M133/44—Five-membered ring containing nitrogen and carbon only
-
- 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
- C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
- C10M2201/04—Elements
- C10M2201/05—Metals; Alloys
-
- 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
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/22—Heterocyclic nitrogen compounds
- C10M2215/223—Five-membered rings containing nitrogen and carbon only
-
- 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
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/22—Heterocyclic nitrogen compounds
- C10M2215/223—Five-membered rings containing nitrogen and carbon only
- C10M2215/224—Imidazoles
-
- C—CHEMISTRY; METALLURGY
- 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
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
- C10M2219/082—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
- C10M2219/084—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Derivatives 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
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/10—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring
- C10M2219/104—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring containing sulfur and carbon with nitrogen or oxygen in the ring
- C10M2219/106—Thiadiazoles
-
- 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
- C10M2229/00—Organic macromolecular compounds containing atoms of elements not provided for in groups C10M2205/00, C10M2209/00, C10M2213/00, C10M2217/00, C10M2221/00 or C10M2225/00 as ingredients in lubricant compositions
- C10M2229/04—Siloxanes with specific structure
- C10M2229/046—Siloxanes with specific structure containing silicon-oxygen-carbon bonds
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/10—Inhibition of oxidation, e.g. anti-oxidants
Landscapes
- 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 invention discloses a kind of combustion gas turbine oil compositions, on the basis of the weight of lubricant oil composite, the lubricant oil composite contains following components: the lube base oil of 85-99 weight %, the antioxygen multipurpose additive of 0.01-10 weight %, the %2 of 0.01-5 weight, 2 '-thiobis [3- (3, 5- di-tert-butyl-hydroxy phenyl) ethyl propionate, the Zinc oxide nanoparticle of 0.05-5 weight %, the matal deactivator of 0.01-5 weight %, the steam turbine oil that the composition is mixed into, with excellent oxidation stability, high-temperature stability and liquid phase rust-preventing characteristic, divide aqueous energy.The antioxygen multipurpose additive is the compound of structure shown in formula (I).The present invention also provides the preparation methods of combustion gas turbine oil composition.Combustion gas turbine oil composition of the invention has excellent abrasion resistance and antioxygenic property, can be widely applied to combustion gas steam-turbine lubrication field.
Description
Technical field
The present invention relates to lubricating oil fields, and in particular, to a kind of combustion gas steam turbine oil combination containing special additive
Object and preparation method thereof.
Background technique
Steam turbine oil is the bearing lubrication and cooling use of the turbine and generator such as electric power supply plant.Fire the height of vapour Steam Turbine
Hold temperature up to 200 DEG C, the mean temperature of oil export is 70 DEG C or so.At such temperatures, steam turbine oil change easy to oxidize
Matter.And steam turbine oil dosage is big, and replacement is inconvenient, is up to 10-15 using the time, the service life for increasing steam turbine oil is
The direction of this field research staff effort always.The oil mass that steam turbine oil supplements consumption every year is the 5%-10% of internal circulating load.?
It in time long in this way, is influenced by air and moisture, steam turbine oil, which can aoxidize, generates acidic materials or other oxides and molten
In oil or with Precipitation.When acidic materials accumulation is excessive, metal parts can be corroded, lubricating oil can be accelerated to continue to aoxidize,
The generation of oxide precipitate can pollute lubricating system and the efficiency that lubrication device is greatly reduced.Therefore steam turbine oil requires to have
Excellent anti-oxidative stability.The bearing of gas turbine and reducer gear are main motion parts simultaneously.Starting and is stopping
When be often possible in boundary lubrication condition.It in this case, can if the lubricity of steam turbine oil is bad, wear resistence is poor
Adhesive wear, abrasive wear and fatigue wear occurs, causes the reduction of the component capabilities such as gear, the lost of life, system production failure.
Therefore, combustion gas steam turbine oil oil needs to have good abrasion-resistance and anti-extreme pressure energy.With the rapid development of technology, to combustion
Gas steam turbine oil constantly proposes new requirement, and load is increasingly heavier, and to the wear resistence of oil product, more stringent requirements are proposed;Develop phase
There is the novel gas steam turbine oil oil of more preferable antioxygen abrasion-resistance to become this field scientific research personnel current existing product
The direction of effort.
It mainly includes phenols and aminated compounds that the lube oil additive of antioxidation can be effectively played by, which being currently known,.
Phenolic compound contains one or more and is obstructed phenol functional group, and aminated compounds then contains one or more nitrogen-atoms, these are special
Different functional group can capture the free radical compounds of oxidation process generation, so that oxidation process be prevented to continue to occur.Due to
The operating condition of Current mechanical equipment tends to strongly, often accelerated oxidation rate, shortens the service life of lubricating oil, therefore right
More stringent requirements are proposed for the efficiency and economy of antioxidant.
United States Patent (USP) US4824601A reports diphenylamine and diisobutylene in the alkaline-earth metal catalyst of acid activation
The lower alkylated amines mixture formed of (earth catalyst) effect, its anti-oxidant energy in lubricating oil and other functional fluids
Power is excellent in.
United States Patent (USP) US2005230664A1 reports a kind of antioxidant 9 of following general formula, the synthesis of 10- acridan
Method, it is to be condensed preparation under acidic catalyst effect using alkylated diphenylamine and aldehydes or ketones.
Using the tert-butyl phenols that is obstructed, aldehyde, carbon disulfide and dialkylamine condensation preparationization occurs for patent CN1191340C
Object is closed, which has the stronger ability for capturing free radical and peroxynitrite decomposition compound, can provide to oil oxidation stability
More effectively protection, may also function as wear-resistant effect.
Patent US4225450A report it is a kind of by the tert-butyl phenols that is obstructed with Diethyldithiocarbamate the system of reacting
Standby polysulfide phenolic antioxidant has preferable antioxidation and wear-resistant effect.
Summary of the invention
The purpose of the invention is to meet anti-oxidant, abrasion-resistance the high request to combustion gas steam turbine oil, one is provided
Kind combustion gas turbine oil composition and preparation method thereof.
The present inventor has found that lubricant oil composite contains the compound of structure shown in formula (I) under study for action:
And the compound and 2,2 '-thiobis [3- (3,5- di-tert-butyl-hydroxy phenyl) ethyl propionate] type antioxygen
Agent combination can make combustion gas turbine oil composition have the excellent performances such as anti-oxidant and wear-resistant.
Therefore, to achieve the goals above, on the one hand, the present invention provides a kind of combustion gas turbine oil compositions, with profit
On the basis of the weight of sliding oil composition, the lubricant oil composite contains following components: the lube base of 85-99 weight %
Quality %2,2 '-thiobis [3- (3,5- di-t-butyl -4- of oil, the antioxygen multipurpose additive of 0.01-10 weight %, 0.01-5
Hydroxy phenyl) ethyl propionate], the Zinc oxide nanoparticle of 0.05-5 weight %, 0.01-5 mass % matal deactivator, institute
State the compound that antioxygen multipurpose additive is structure shown in formula (I):
Preferably, on the basis of the weight of lubricant oil composite, the lubricant oil composite contains following components: 90-98
The lube base oil of weight %, the antioxygen multipurpose additive of 0.1-4 weight %, 0.01-5 quality %2,2 '-thiobis
[3- (3,5- di-tert-butyl-hydroxy phenyl) ethyl propionate], the Zinc oxide nanoparticle of 0.1-3 weight %, 0.05-2 matter
Measure the matal deactivator class compound of %.
On the other hand, the present invention provides a kind of preparation methods of combustion gas turbine oil composition, which comprises will
Contain lube base oil, antioxygen multipurpose additive, 2,2 '-thiobis [3- (3,5- di-tert-butyl-hydroxy phenyl) propionic acid second
Ester] type antioxidant, Zinc oxide nanoparticle, organic carboxyl acid class compound raw material be uniformly mixed obtain lubricant oil composite,
In, on the basis of the weight of lubricant oil composite, the dosage of lube base oil is 85-99 weight %, antioxygen multipurpose additive
Dosage be 0.01-10 weight %, 0.01-5 quality %2,2 '-thiobis [3- (3,5- di-tert-butyl-hydroxy phenyl)
Ethyl propionate], the Zinc oxide nanoparticle of 0.05-5 weight %, 0.01-5 mass % matal deactivator, the antioxygen multiple-effect
Additive is the compound of structure shown in formula (I):
Preferably, on the basis of the weight of lubricant oil composite, the dosage of lube base oil is 90-99 weight %, resists
The dosage of oxygen multipurpose additive is 0.1-4 weight %, 2,2 '-thiobis [3- (3,5- di-tert-butyl-hydroxy phenyl) propionic acid
Ethyl ester] antioxidant dosage be 0.1-3 weight %, the dosage of Zinc oxide nanoparticle is 0.1-3 weight %, matal deactivator
Dosage be 0.05-2 weight %.
Combustion gas turbine oil composition of the invention has excellent abrasion resistance and antioxygenic property, can be widely applied
In combustion gas steam turbine oil lubricating area.
Other features and advantages of the present invention will the following detailed description will be given in the detailed implementation section.
Detailed description of the invention
Fig. 1 is the reaction equation of (a) the step of preparing antioxygen multipurpose additive.
Fig. 2 is the reaction equation of (b) the step of preparing antioxygen multipurpose additive.
Fig. 3 is the reaction equation of (c) the step of preparing antioxygen multipurpose additive.
Fig. 4 is the hydrogen spectrum spectrogram of the antioxygen multipurpose additive of preparation example preparation.
Fig. 5 is the carbon spectrum spectrogram of the antioxygen multipurpose additive of preparation example preparation.
Fig. 6 is the mass spectrogram of the antioxygen multipurpose additive of preparation example preparation.
Specific embodiment
Detailed description of the preferred embodiments below.It should be understood that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
On the one hand, the present invention provides a kind of combustion gas turbine oil compositions, on the basis of the weight of lubricant oil composite,
Lubricant oil composite contains following components: the lube base oil of 85-99 weight %, the antioxygen multiple-effect of 0.01-10 weight % add
Add agent, quality %2,2 '-thiobis [3- (3,5- di-tert-butyl-hydroxy phenyl) ethyl propionate] of 0.01-5,0.05-5 weight
The Zinc oxide nanoparticle of %, the matal deactivator of 0.01-5 mass % are measured, antioxygen multipurpose additive is structure shown in formula (I)
Compound:
In the present invention, on the basis of the weight of lubricant oil composite, the content of lube base oil is preferably 90-98 weight
Measure %;The content of antioxygen multipurpose additive is preferably 0.02-5 weight %, more preferably 0.1-4 weight %;2,2 '-thiobis
The content of [3- (3,5- di-tert-butyl-hydroxy phenyl) ethyl propionate] antioxidant is preferably 0.1-3 weight %;Zinc oxide nano
The content of rice grain is preferably 0.05-4 weight %, more preferably 0.1-3 weight %;The content of matal deactivator is preferably
0.01-4 weight %, more preferably 0.05-2 weight %.
The present invention is directed to tie by the compound containing structure shown in formula (I) in lubricant oil composite, and shown in formula (I)
The compound of structure and 2,2 '-thiobis [3- (3,5- di-tert-butyl-hydroxy phenyl) ethyl propionate] type antioxidant are combined and reality
Existing goal of the invention, even if lubricant oil composite has the excellent performances such as wear-resistant and anti-oxidant.Therefore, for lubricant oil composite
In each conventional constituents selection, do not limit specifically.
In the present invention, lube base oil can be lube base oil commonly used in the art, such as can be mine
Object lubricating oil and/or synthetic lubricant fluid.
Mineral lubricating oil in viscosity can from light fraction mineral oil to heavy distillat mineral oil, including saxol and plus
That hydrogen refines, the processed alkane of solvent, cycloalkanes and mixing par-affinic-naphthenic types mineral lubricating oil, are generally divided into I, II, Group III
Base oil, common trade names include I class 150SN, 600SN, II class 100N, 150N, 350N etc..
Synthetic lubricant fluid may include polymerization hydrocarbon ils, alkyl benzene and its derivative, polymerization hydrocarbon ils specific example include but
It is not limited to polybutene, polypropylene, propylene-isobutylene copolymers, the polybutene of chlorination, poly- (1- hexene), poly- (1- octene), gathers
(1- decene), common trade names include PAO4, PAO6, PAO8, PAO10 etc., alkyl benzene and its derivative specific example
Including but not limited to detergent alkylate, Tetradecylbenzene, dinonyl benzene, two (2- ethylhexyl) benzene, alkyl benzene derivate packet
Include alkylated diphenyl ether and alkylated diphenyl sulfide and its derivative, analog and homologue etc..
Another suitable type of synthetic lubricant fluid can be Esters oil, including dicarboxylic acids (such as phthalic acid, succinic acid, alkane
Base succinic acid and alkenyl succinic acid, maleic acid, azelaic acid, suberic acid, decanedioic acid, fumaric acid, adipic acid, linoleic acid dimerization
Object, malonic acid, alkyl malonic acid, alkenyl malonic) with various alcohol (such as butanol, hexanol, dodecyl alcohol, 2- ethylhexyl alcohol,
Ethylene glycol, propylene glycol) ester or complex ester that condensation reaction generates occurs.The specific example of these esters includes but is not limited to adipic acid
Dibutyl ester, decanedioic acid two (2- ethylhexyl) ester, the just own ester of fumaric acid acid two, dioctyl sebacate, azelaic acid two are different pungent
Ester, two different decayl esters of azelaic acid, dioctyl phthalate, didecyl phthalate, decanedioic acid two (larane base) ester, linoleic acid
2- ethylhexyl diester of dimer etc..
Another suitable type of synthetic lubricant fluid can be for fischer tropsch process synthetic hydrocarbon oil and to this synthetic hydrocarbon oil by adding
Hydrogen isomery such as is hydrocracked, dewaxes at the lube base oil that process obtain.
In the present invention, lube base oil preferred viscosities index is greater than 80, saturated hydrocarbon content and is greater than 90 weight %, sulfur content
Less than the lube base oil of 0.03 weight %.
In the present invention, Zinc oxide nanoparticle is the single or composite nanoparticle of the ingredient containing Zinc oxide nanoparticle.Add
Adding the high-temperature chain lubricating oil of Zinc oxide nanoparticle has preferable high temperature wear resistance, and the abrasion resistance of oil product obtains after addition
To improvement.The partial size of nanoparticle is 3-150nm.
In the present invention, metal deactivator can be 2,5- bis- (tert- molybdenum didodecyl dithiophosphate) -1,3,4- thiadiazoles, four benzene
Methylbenzotrazole, 2-mercaptobenzothiazole, at least one of alkyl thiadiazoles.Such as Yantai Heng Nuo chemical industry section can be selected
Skill Co., Ltd 2,5- bis- (tert- molybdenum didodecyl dithiophosphate) -1,3,4- thiadiazoles.Such as Yantai perseverance promise chemical science and technology can be selected
The T561 etc. of Co., Ltd.
Lubricant oil composite of the invention can also contain at least one of antirust agent, pour-point depressant and anti-foaming agent.Antirust
Agent can be selected from imidazoles and/or alkenyl succinic acid esters, preferably 4,5- glyoxalidine, alkenyl imidazoline succinate and alkene
At least one of base succinate, for example, can select Jinzhou Kangtai Lube Additive Co., Ltd. produce T746,
T703,T747.It is C8-C18's that pour-point depressant, which can be selected from poly alpha olefin, the dialkyl fumarate that alkyl be C8-C18, alkyl,
At least one of poly- alkylmethacrylate, alkylnaphthalene that alkyl is C8-C18, such as Wuxi south petroleum can be selected
The V385 etc. of T803, Run Yinglian company of additive company.Anti-foaming agent can select polysiloxane type anti-foaming agent, such as can be
Dimethyl silicone polymer.For antirust agent, pour-point depressant and anti-foaming agent content without particular/special requirement, can contain for this field is conventional
Amount, this is known to those skilled in the art, and details are not described herein.
In the present invention, the preparation method of the compound of structure shown in formula (I) is preferably included:
(a) 2,6- DI-tert-butylphenol compounds, formaldehyde and benzene are subjected to condensation reaction, generate intermediate M shown in formula (II),
(b) the intermediate M that step (a) obtains is contacted with bromide reagent and carries out bromo-reaction, generated shown in formula (III)
Bromination product,
(c) bromination product for obtaining step (b) is contacted with formula (IV) compound represented carries out coupling reaction, production
(I) antioxidant shown in,
In step (a) of the present invention, the condition of condensation reaction is preferably included: under an inert atmosphere, in the first solvent,
In the presence of one catalyst, 15- is risen to after 2,6- DI-tert-butylphenol compounds, formaldehyde and benzene are reacted 0.5-1.5h at -20-0 DEG C
30 DEG C, it is then heated to 70-80 DEG C of reaction 1-3h.
In the present invention, inert atmosphere can be the inert atmosphere of this field routine, such as can be by gases such as nitrogen, argon gas
It provides.
It will be understood by those skilled in the art that reacting 0.5- at -20-0 DEG C to carry out stable reaction
15-30 DEG C is risen to after 1.5h, it should 15-30 DEG C is to slowly warm up to, for example, after can reacting 0.5-1.5h at -20-0 DEG C
System be placed under 15-30 DEG C of environment temperature, so that reaction system itself is to slowly warm up to 15-30 DEG C.
In the present invention, the first solvent is preferably selected from least one in methanol, ethyl alcohol, n,N-Dimethylformamide and acetonitrile
Kind, more preferably methanol and/or acetonitrile, are still more preferably methanol.
In the present invention, the first catalyst can be inorganic acid or organic acid, be preferably selected from acetic acid, p-methylbenzoic acid and benzene
At least one of sulfonic acid, more preferably acetic acid.
In the present invention, the dosage of 2,6- DI-tert-butylphenol compounds, formaldehyde and benzene is substantially equimolar amounts, but formaldehyde and benzene can
With appropriate excessive.The molar ratio of 2,6 di t butyl phenol, formaldehyde and benzene is preferably 0.9-1.5:0.9-10:0.9-10.
In step (a) of the present invention, the dosage of the first catalyst can be catalytic amount, with mole of 2,6- DI-tert-butylphenol compounds
On the basis of number, the dosage of the first catalyst is preferably 5-100 moles of %, more preferably 10-30 moles of %.
It will be understood by those skilled in the art that purer intermediate M, goes back in order to obtain in step (a) of the present invention
It needing to post-process the system after reaction, the mode of post-processing may include that solvent is removed under reduced pressure, then diluted through solvent,
Washing, dry, decompression remove solvent again, for example, the system after reaction is removed into solvent at 0.01-0.05MPa, 40-60 DEG C,
It is subsequently poured into the ethyl acetate (or methylene chloride) of 1-10 times of volume, uses distilled water and saturated common salt water washing respectively, then
The desiccant such as anhydrous calcium chloride or anhydrous sodium sulfate are added at 15-30 DEG C, keep 10-60min.It is filtered to remove desiccant
Afterwards, solvent is removed at 0.01-0.05MPa, 40-60 DEG C, to obtain intermediate M.
In step (a) of the present invention, 2,6- DI-tert-butylphenol compounds, formaldehyde and benzene carry out the reaction equation of condensation reaction as schemed
Shown in 1, in Fig. 1, the first solvent is using methanol, and the first catalyst is using acetic acid, purpose by way of example only, no
The scope of the present invention is construed as limiting.
In step (b) of the present invention, the condition of bromo-reaction is preferably included: under an inert atmosphere, in the second solvent,
In the presence of two catalyst, under the conditions of being protected from light, the intermediate M that step (a) obtains is reacted at 15-30 DEG C with bromide reagent
Then 1-2h is quenched with quencher.
" inert atmosphere " is as previously mentioned, details are not described herein.
It will be understood by those skilled in the art that more stably being carried out to react, preferably into intermediate M slowly
Brominated reagent is added.
In the present invention, the second solvent is preferably selected from least one of tetrahydrofuran, methylene chloride, chloroform and ether, more
Preferably tetrahydrofuran.
In the present invention, the second catalyst is preferably selected from ammonium nitrate, benzoyl peroxide (BPO) and azodiisobutyronitrile
At least one of (AIBN).
In the present invention, bromide reagent is preferably N-bromosuccinimide (NBS) and/or Br2, more preferably NBS.
In step (b) of the present invention, it is quenched with quencher, quencher can be quencher commonly used in the art, such as
It can be saturated salt solution.
In step (b) of the present invention, the dosage of intermediate M and bromide reagent is substantially equimolar amounts, but bromide reagent one
As can be suitably excessive, reach 1.1-3 times of equivalent of reaction substrate.Intermediate M and bromide reagent molar ratio are preferably 0.9-
1.2:0.9-3.0。
In step (b) of the present invention, the dosage of the second catalyst can be catalytic amount, on the basis of the molal quantity of intermediate M,
The dosage of second catalyst is preferably 10-100 moles of %, more preferably 40-60 moles of %.
In the method for the present invention step (b), intermediate M contacts the reaction equation for carrying out bromo-reaction with bromide reagent as schemed
Shown in 2, in Fig. 2, bromide reagent is using NBS, and purpose by way of example only is not construed as limiting the scope of the present invention.
In step (b) of the present invention, other than generating bromination product shown in formula (III), there are also the bromos at micro ortho position to produce
Object generates, and the bromination product of meta position does not generate, but the amount of the bromination product at ortho position very pettiness, to subsequent reactions without substantive shadow
It rings, can be ignored.
It will be understood by those skilled in the art that in step (b) of the present invention, purer bromination product in order to obtain,
It also needs to post-process the system after being quenched, the mode of post-processing may include washing, drying, solvent, example be removed under reduced pressure
Such as, the system after being quenched is washed with distilled water, it is dry that anhydrous calcium chloride or anhydrous sodium sulfate etc. is then added at 15-30 DEG C
Drying prescription keeps 10-60min.After being filtered to remove desiccant, solvent is removed at 0.01-0.05MPa, 40-60 DEG C, to obtain bromine
For product.
In step (c) of the present invention, the condition of coupling reaction is preferably included: under an inert atmosphere, in third solvent,
In the presence of three catalyst, the bromination product that step (b) obtains is reacted at 80-100 DEG C with formula (IV) compound represented
4-8h。
" inert atmosphere " is as previously mentioned, details are not described herein.
In the present invention, in order to carry out stable reaction, it is preferably gradually heated to 80-100 DEG C, then at 80-100 DEG C
React 4-8h.
In the present invention, third solvent is preferably selected from least one of methylene chloride, chloroform, toluene and tetrahydrofuran, more
Preferably methylene chloride.
In the present invention, third catalyst preferably includes palladium salt, ligand and alkali.Palladium salt is preferably selected from palladium acetate and/or palladium-two
BENZYLIDENE ACETONE complex compound [Pd2(dba)3];Ligand is preferably selected from tri-tert-butylphosphine, dinaphthol (BINAP) and bis- (diphenylphosphines
At least one of base) ferrocene (dppf);Alkali is preferably selected from sodium tert-butoxide, potassium tert-butoxide, cesium carbonate and sodium carbonate extremely
Few one kind.
In step (c) of the present invention, the dosage of bromination product and formula (IV) compound represented that step (b) obtains is substantially
For equimolar amounts, but formula (IV) compound represented can be suitably excessive.The bromination product and formula (IV) institute that step (b) obtains
The molar ratio of the compound shown is preferably 0.9-1.5:0.9-2.5.
In step (c) of the present invention, the dosage of catalyst can be catalytic amount, on the basis of the molal quantity of bromination product, palladium
The dosage of salt is preferably 5-50 moles of %, more preferably 5-20 moles of %, is still more preferably 5-10 moles of %;The use of ligand
Amount is preferably 5-50 moles of %, more preferably 10-30 moles of %;The dosage of alkali is preferably 5-50 moles of %, more preferably 10-30
Mole %.
In step (c) of the present invention, the bromination product that step (b) obtains is contacted with formula (IV) compound represented to be coupled
The reaction equation of reaction is as shown in figure 3, in Fig. 3, and palladium salt is using palladium acetate, purpose by way of example only, not to this
The range of invention is construed as limiting.
It will be understood by those skilled in the art that purer final product in order to obtain, i.e., resist shown in formula (I)
Oxygen agent, for the method for the present invention it is also preferable to include post-processing to the system after reaction, the mode of post-processing may include filtering, being molten
Washing, drying, solvent is removed under reduced pressure in dilution agent, for example, the filtered filtrate of system after reaction is poured into 1-10 times of volume
It in ethyl acetate (or methylene chloride), is then washed with distilled water, anhydrous calcium chloride or anhydrous is then added at 15-30 DEG C
The desiccant such as sodium sulphate keep 10-60min.After being filtered to remove desiccant, removed at 0.01-0.05MPa, 40-60 DEG C molten
Agent, to obtain antioxidant shown in formula (I).
Each step that the method for the compound of structure shown in formula (I) is prepared in the present invention preferably carries out under stiring, for
Mixing speed can be the mixing speed of this field routine, for example, mixing speed can be 100-800rpm without particular/special requirement.
The present invention is prepared in the method for the compound of structure shown in formula (I), molten for the first solvent, the second solvent and third
The amount of agent can be the solvent usage of this field routine, this is known to those skilled in the art, herein no longer without particular/special requirement
It repeats.
As described above, the present invention is directed to the compound by containing structure shown in formula (I) in lubricant oil composite, and formula
(I) compound of structure shown in and 2,2 '-thiobis [3- (3,5- di-tert-butyl-hydroxy phenyl) ethyl propionate] type antioxygen
Agent is combined and realizes goal of the invention, even if lubricant oil composite has the excellent performances such as wear-resistant and anti-oxidant.Therefore, for profit
The preparation method of sliding oil composition can use method commonly used in the art without particular/special requirement, for example, second aspect, this
Invention additionally provides a kind of preparation method of combustion gas turbine oil composition, this method comprises: will contain lube base oil, resist
Oxygen multipurpose additive, 2,2 '-thiobis [3- (3,5- di-tert-butyl-hydroxy phenyl) ethyl propionate] type antioxidant, zinc oxide
Nano particle, organic carboxyl acid class compound raw material be uniformly mixed obtain lubricant oil composite, wherein with lubricant oil composite
On the basis of weight, the dosage of lube base oil is 85-99 weight %, the dosage of antioxygen multipurpose additive is 0.01-10 weight
Measure %, the dosage of 2,2 '-thiobis [3- (3,5- di-tert-butyl-hydroxy phenyl) ethyl propionate] type antioxidant is 0.01-5
Weight %, Zinc oxide nanoparticle dosage be 0.1-5 weight %, the dosage of metal deactivator is 0.01-5 weight %, described
Antioxygen multipurpose additive is the compound of structure shown in formula (I):
In the method for the present invention, on the basis of the weight of lubricant oil composite, the dosage of lube base oil is preferably 90-98
Weight %, antioxygen multipurpose additive dosage be preferably 0.02-5 weight %, more preferably 0.1-4 weight %, 2,2 '-is thio
The dosage of bis- [3- (3,5- di-tert-butyl-hydroxy phenyl) ethyl propionate] type antioxidant is preferably 0.1-3 weight %, oxidation
The dosage of zinc nanoparticles is preferably 0.05-4 weight %, more preferably 0.1-3 weight %, and the dosage of metal deactivator is preferably
0.02-4 weight %, more preferably 0.05-2 weight %.
As previously mentioned, raw material can also contain at least one in antirust agent, pour-point depressant and anti-foaming agent in the method for the present invention
Kind.
In the method for the present invention, for mixed mode without particular/special requirement, such as each original of lube base oil can will be removed
Material component is added separately in lube base oil, can also will be mixed and made into concentrate again except each component of lube base oil
It is added in lube base oil.
In the method for the present invention, mixed condition is preferably included: temperature is 40-90 DEG C, time 1-6h.
Lube base oil, antioxygen multipurpose additive, 2,2 '-thiobis [3- (3,5- di-tert-butyl-hydroxy phenyl) third
Acetoacetic ester] type antioxidant, Zinc oxide nanoparticle, metal deactivator, antirust agent, pour-point depressant and anti-foaming agent be as previously mentioned, herein
It repeats no more.
Embodiment
The present invention is further illustrated for embodiment below, but is not intended to limit the present invention.
In the following Examples and Comparative Examples:
The physico-chemical analysis method of product: constituent content is measured by inductively coupled plasma body ion emission spectroscopy method.
Structure characterization methods: nuclear magnetic resonance method (1H hydrogen spectrum,13C carbon spectrum), high resolution mass spectrum.
Preparation example
It is filled with nitrogen protection in the 500mL flask with electromagnetic agitation sub (mixing speed 200rpm), 150mL is added
Methanol and 0.01mol acetic acid, after being fully cooled in ice-water bath, be then respectively adding 2, the 6- di-tert-butyl of 0.1mol
Phenol, the formaldehyde of 0.2mol and the benzene of 0.3mol.Reaction moves back ice-water bath in 1 hour, and 75 DEG C are heated to after rising to 25 DEG C and is persistently returned
Stream stops reaction after 2 hours, the system after reaction is steamed solvent at 0.03MPa, 50 DEG C, and 250mL acetic acid second is then added
Ester, and be transferred in separatory funnel, 100mL distilled water (twice) and 50mL saturated common salt water washing are used respectively, and it is anhydrous that 10g is added
Calcium chloride dry 20min, filtered filtrate at 25 DEG C are evaporated off solvent at 40 DEG C, 0.03MPa, obtain midbody product
M1。
It is filled with nitrogen protection in the 500mL flask with electromagnetic agitation sub (mixing speed 200rpm), 150mL is added
Dry tetrahydrofuran, then dissolve in midbody product M1, and the ammonium nitrate of 0.05mol is added, under the conditions of being protected from light slowly plus
Enter 0.1mol brominated reagent NBS.It is stirred to react 1.5h at 25 DEG C, is then quenched with saturated salt solution, is then distilled with 100mL
Water (twice) washing, and 10g anhydrous sodium sulfate dry 20min at 25 DEG C is added.Filtered filtrate is in 40 DEG C, 0.03MPa
Under solvent is evaporated off, obtain bromination product.
It is filled with nitrogen protection in the 500mL flask with electromagnetic agitation sub (mixing speed 200rpm), 150mL is added
Methylene chloride as solvent, be separately added into above-mentioned bromination product and the benzotriazole compound of 0.12mol, then be added
The tri-tert-butylphosphine of 0.02mol, the sodium tert-butoxide of 0.02mol and the Pd (OAc) of 0.005mol2.90 DEG C are gradually heated to, is held
Continuous stirring 6h.Then 250mL ethyl acetate is added in the filtered filtrate of system after reaction, and be transferred in separatory funnel, used
100mL distilled water (twice) washing, and 10g anhydrous sodium sulfate dry 20min at 25 DEG C is added.Filtered filtrate is 40
DEG C, solvent is evaporated off under 0.03MPa, obtain final product S1.
The physico-chemical analysis data of S1 are as follows: nitrogen content, and 11.2%.
S1 is subjected to structural characterization, respectively obtain hydrogen spectrum, carbon spectrum and high resolution mass spec spectrogram, see respectively Fig. 4, Fig. 5 and
Fig. 6.
It can be seen that S1 with knot shown in formula (I) from the physico-chemical analysis data of above-mentioned preparation example, Fig. 4, Fig. 5 and Fig. 6
Structure.
Embodiment 1
The present embodiment is for illustrating lubricant oil composite and preparation method thereof of the invention.
By the S1 of 0.1 parts by weight, 2,2 '-thiobis [3- (3,5- di-tert-butyl-hydroxy phenyl) propionic acid of 1 parts by weight
Ethyl ester], 2,5- bis- (tert- molybdenum didodecyl dithiophosphate) -1,3,4- thiadiazoles of 0.5 parts by weight (be purchased from Yantai perseverance promise chemical science and technology
Co., Ltd, T561), the single Zinc oxide nanoparticle (Shandong Turner rice Materials Co., Ltd) of 0.11 parts by weight, 0.3 weight
The 4,5- glyoxalidine of part and the dimethyl silicone polymer (being purchased from Hubei xinsihai Chemical Co., Ltd.) of 0.02 parts by weight
Being added to the 600SN lube base oils of 97.88 parts by weight, (viscosity index (VI) 87, saturated hydrocarbon content are 92 weight %, and sulphur contains
Amount is 0.02 weight %) in, 3h is stirred at 60 DEG C, is uniformly mixed and obtains lubricant oil composite A1.
Embodiment 2
The present embodiment is for illustrating lubricant oil composite and preparation method thereof of the invention.
By the S1 of 0.6 parts by weight, the 2,2 '-thiobis [3- (3,5- di-tert-butyl-hydroxy phenyl) third of 0.1 parts by weight
Acetoacetic ester], the single Zinc oxide nanoparticle (Shandong Turner rice Materials Co., Ltd) of 0.15 parts by weight, 0.1 parts by weight 2,
5- bis- (tert- molybdenum didodecyl dithiophosphate) -1,3,4- thiadiazoles (being purchased from Yantai Heng Nuo Chemical Industry Science Co., Ltd, T561), 0.3 weight
The dimethyl silicone polymer of the 4,5- glyoxalidine and 0.02 parts by weight of measuring part (is purchased from the new limited public affairs of four seas chemical industry share in Hubei
Department) it is added in the mixed lubrication oil base oil (PAO8 is 68 parts by weight, and PAO40 is 30.68 parts by weight) of PAO8 and PAO40,
6h is stirred at 40 DEG C, is uniformly mixed and obtains lubricant oil composite A2.
Embodiment 3
The present embodiment is for illustrating lubricant oil composite and preparation method thereof of the invention.
By the S1 of 1 parts by weight, 2,2'- thiobis [3- (3,5- di-tert-butyl-hydroxy phenyl) propionic acid of 0.1 parts by weight
Ethyl ester], the single Zinc oxide nanoparticle (Shandong Turner rice Materials Co., Ltd) of 0.25 parts by weight, 0.5 parts by weight 2,5-
Two (tert- molybdenum didodecyl dithiophosphates) -1,3,4- thiadiazoles (being purchased from Yantai Heng Nuo Chemical Industry Science Co., Ltd, T561), 0.3 weight
The 4,5- glyoxalidine of part and the dimethyl silicone polymer (being purchased from Hubei xinsihai Chemical Co., Ltd.) of 0.02 parts by weight
It is added in the dibutyl adipate of 97.58 parts by weight, stirs 1h at 90 DEG C, be uniformly mixed and obtain lubricant oil composite A3.
Comparative example 1
Lubricant oil composite is prepared according to the method for embodiment 2, unlike, S1 is replaced with etc. the 2,2'- of parts by weight
Thiobis [3- (3,5- di-tert-butyl-hydroxy phenyl) ethyl propionate], obtains lubricant oil composite D1.
Comparative example 2
Lubricant oil composite is prepared according to the method for embodiment 2, unlike, by 2,2'- thiobis [3- (3,5- bis- uncles
Butyl -4- hydroxy phenyl) ethyl propionate] S1 that the parts by weight such as replaces with, obtain lubricant oil composite D2.
Comparative example 3
Lubricant oil composite is prepared according to the method for embodiment 2, unlike, by S1 and 2,2'- thiobis [3- (3,5-
Di-tert-butyl-hydroxy phenyl) ethyl propionate] zinc dibutyl dithiocarbamate that the parts by weight such as replaces with, it is lubricated
Fluid composition D3.
Comparative example 4
Lubricant oil composite is prepared according to the method for embodiment 2, unlike, by S1 and 2,2'- thiobis [3- (3,5-
Di-tert-butyl-hydroxy phenyl) ethyl propionate] the trimethylphenyl zinc phosphite that the parts by weight such as replaces with, obtain lubricating oil composition
Object D4.
Comparative example 5
Lubricant oil composite is prepared according to the method for embodiment 2, unlike, by S1 and 2,2'- thiobis [3- (3,5-
Di-tert-butyl-hydroxy phenyl) ethyl propionate] the fourth octyl diphenylamine that the parts by weight such as replaces with, obtain lubricant oil composite D5.
Test case
Lubricant oil composite A1-A3, D1-D5 are tested as follows respectively:
The measurement of initial oxidation temperature is carried out using TA5000-DSC2910 differential thermal analyzer;
The measurement of oxidation induction period is carried out using high pressure differential scanning amount method (PDSC);
Using tetra-ball machine test method, PB, PD value are measured by GB/T3142;
Wear scar diameter is measured using SH/T 0189.It the results are shown in Table 1.
Table 1
A1 | A2 | A3 | D1 | D2 | D3 | D4 | D5 | |
Initial oxidation temperature, DEG C | 215 | 219 | 225 | 203 | 207 | 208 | 197 | 191 |
Oxidation induction period, min | 47.2 | 48.1 | 55.8 | 32.5 | 39.6 | 21.0 | 21.9 | 31.2 |
PB, kgf | 95 | 100 | 100 | 40 | 60 | 50 | 65 | 45 |
PD, kgf | 270 | 280 | 295 | 205 | 230 | 210 | 210 | 195 |
Wear scar diameter d60 40, mm | 0.55 | 0.55 | 0.53 | 0.68 | 0.65 | 0.70 | 0.71 | 0.75 |
It will be understood by those skilled in the art that initial oxidation temperature is higher, the thermal stability of lubricating oil is better;Oxidation
Induction period is longer, and the antioxygenic property of lubricating oil is better;PB, PD value are bigger, and the wear resistance of lubricating oil is better;Wear scar diameter
Smaller, the wear resistance of lubricating oil is better.
A2 is compared with D1-D5 respectively as can be seen that lubricant oil composite of the invention is with preferably anti-oxidant
Property and abrasion resistance.
Combustion gas turbine oil composition of the invention has excellent abrasion resistance and antioxygenic property, can be widely applied
In combustion gas steam turbine oil lubricating area.
It is described the prefered embodiments of the present invention in detail above in conjunction with attached drawing, still, the present invention is not limited to above-mentioned realities
The detail in mode is applied, within the scope of the technical concept of the present invention, a variety of letters can be carried out to technical solution of the present invention
Monotropic type, these simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance
In the case where shield, can be combined in any appropriate way, in order to avoid unnecessary repetition, the present invention to it is various can
No further explanation will be given for the combination of energy.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should also be regarded as the disclosure of the present invention.
Claims (12)
1. a kind of combustion gas turbine oil composition, which is characterized in that on the basis of the weight of lubricant oil composite, the lubricating oil
Composition contains following components: the lube base oil of 85-99 weight %, 0.01-10 weight % antioxygen multipurpose additive,
Weight %2,2 '-thiobis [3- (3,5- di-tert-butyl-hydroxy phenyl) ethyl propionate], the 0.05-5 weight % of 0.01-5
Zinc oxide nanoparticle, 0.01-5 weight % matal deactivator, the antioxygen multipurpose additive is structure shown in formula (I)
Compound:
2. composition according to claim 1, wherein on the basis of the weight of lubricant oil composite, the lubricating oil group
It closes object and contains following components: antioxygen multipurpose additive, the 0.1-3 of the lube base oil of 90-99 weight %, 0.1-4 weight %
2,2 '-thiobis [3- (3,5- di-tert-butyl-hydroxy phenyl) ethyl propionate] antioxidant of weight %, 0.1-3 weight %
The metal deactivator of Zinc oxide nanoparticle, 0.05-2 weight %.
3. composition according to claim 1 or 2, wherein the lube base oil is mineral lubricating oil and/or synthesis
Lubricating oil.
4. composition according to claim 1 or 2, wherein the Zinc oxide nanoparticle is containing Zinc oxide nanoparticle
The nanoparticle of ingredient, the partial size of nanoparticle are 3-150nm.
5. composition according to claim 1 or 2, wherein the matal deactivator is (the tert- dodecyl two of 2,5- bis-
It is thio) -1,3,4- thiadiazoles, four benzyl benzotriazole, 2-mercaptobenzothiazole, at least one of alkyl thiadiazoles.
6. composition according to claim 1 or 2, wherein the lubricant oil composite also contain antirust agent, pour-point depressant and
At least one of anti-foaming agent.
7. composition according to claim 6, wherein the antirust agent is selected from imidazoles and/or alkenyl succinic acid esters.
8. composition according to claim 6, wherein the pour-point depressant is selected from poly alpha olefin, alkyl is C8-C18 two
Poly- alkylmethacrylate, the alkyl that alkyl fumarate, alkyl are C8-C18 are at least one in the alkylnaphthalene of C8-C18
Kind.
9. composition according to claim 6, wherein the anti-foaming agent is polysiloxane type anti-foaming agent.
10. a kind of preparation method of combustion gas turbine oil composition, which is characterized in that the described method includes: lubricating oil will be contained
Base oil, antioxygen multipurpose additive, 2,2 '-thiobis [3- (3,5- di-tert-butyl-hydroxy phenyl) ethyl propionate], oxidation
Zinc nanoparticles, metal deactivator raw material be uniformly mixed obtain lubricant oil composite, wherein with the weight of lubricant oil composite
On the basis of, the dosage of lube base oil is 85-99 weight %, the dosage of antioxygen multipurpose additive is 0.01-10 weight %, 2,
The dosage of 2 '-thiobis [3- (3,5- di-tert-butyl-hydroxy phenyl) ethyl propionate] is weight %, the zinc oxide of 0.01-5
The dosage of nano particle is 0.05-5 weight %, the dosage of matal deactivator is 0.01-5 mass %, the antioxygen multiple-effect addition
Agent is the compound of structure shown in formula (I):
11. according to the method described in claim 10, wherein, on the basis of the weight of lubricant oil composite, lube base oil
Dosage be 90-99 weight %, the dosage of antioxygen multipurpose additive is 0.1-4 weight %, 2,2 '-thiobis [3- (bis- uncle of 3,5-
Butyl -4- hydroxy phenyl) ethyl propionate] antioxidant dosage be 0.1-3 weight %, the dosage of Zinc oxide nanoparticle is
0.1-3 weight %, the dosage of matal deactivator are 0.05-2 weight %.
12. method described in 0 or 11 according to claim 1, wherein the mixed condition includes: that temperature is 40-90 DEG C, when
Between be 1-6h.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201610238057.4A CN107304379B (en) | 2016-04-18 | 2016-04-18 | A kind of combustion gas turbine oil composition and preparation method thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201610238057.4A CN107304379B (en) | 2016-04-18 | 2016-04-18 | A kind of combustion gas turbine oil composition and preparation method thereof |
Publications (2)
Publication Number | Publication Date |
---|---|
CN107304379A CN107304379A (en) | 2017-10-31 |
CN107304379B true CN107304379B (en) | 2019-08-16 |
Family
ID=60152066
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201610238057.4A Active CN107304379B (en) | 2016-04-18 | 2016-04-18 | A kind of combustion gas turbine oil composition and preparation method thereof |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN107304379B (en) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114806684A (en) * | 2022-03-28 | 2022-07-29 | 龙蟠润滑新材料(天津)有限公司 | Turbine oil composition and preparation method thereof |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101528668A (en) * | 2006-10-17 | 2009-09-09 | 雅宝公司 | Macromolecular amine-phenolic antioxidant compositions, process technology thereof, and uses thereof |
CN102757847A (en) * | 2012-07-25 | 2012-10-31 | 江苏龙蟠石化有限公司 | Anhydrous albany grease and preparation method thereof |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20080090743A1 (en) * | 2006-10-17 | 2008-04-17 | Mathur Naresh C | Compounds and methods of making the compounds |
-
2016
- 2016-04-18 CN CN201610238057.4A patent/CN107304379B/en active Active
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101528668A (en) * | 2006-10-17 | 2009-09-09 | 雅宝公司 | Macromolecular amine-phenolic antioxidant compositions, process technology thereof, and uses thereof |
CN102757847A (en) * | 2012-07-25 | 2012-10-31 | 江苏龙蟠石化有限公司 | Anhydrous albany grease and preparation method thereof |
Non-Patent Citations (1)
Title |
---|
润滑油抗氧剂的研究现状与进展;薛卫国等;《合成润滑材料》;20130620;第40卷(第2期);第7-13页 |
Also Published As
Publication number | Publication date |
---|---|
CN107304379A (en) | 2017-10-31 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN107304380B (en) | A kind of air compressor oil composition and preparation method thereof | |
CN107304379B (en) | A kind of combustion gas turbine oil composition and preparation method thereof | |
CN106318519B (en) | A kind of gasoline engine oil lubricant oil composite and preparation method thereof | |
CN105586134B (en) | Excellent calcium base grease composition of a kind of Wear vesistance and preparation method thereof | |
CN106318522B (en) | A kind of gas engine lubricant oil composite and preparation method thereof | |
CN106318557B (en) | A kind of methanol-fueled engine lubricant oil composite and preparation method thereof | |
CN106318518B (en) | A kind of automatic transmission fluid lubricant oil composite and preparation method thereof | |
CN107304378B (en) | A kind of high-temperature chain oil composition and preparation method thereof | |
CN105586133B (en) | A kind of lubricant composition with excellent antioxidant performance | |
CN106318555B (en) | A kind of Metalworking lubricating oil composition and preparation method thereof | |
CN107304382B (en) | A kind of air compressor oil composition and preparation method thereof | |
CN105524698B (en) | Excellent composite barium-base grease composition of a kind of Wear vesistance and preparation method thereof | |
CN107304377B (en) | A kind of high-temperature chain oil composition and preparation method thereof | |
CN106318534B (en) | A kind of Metalworking lubricating oil composition and preparation method thereof | |
CN106318553B (en) | A kind of automatic transmission fluid lubricant oil composite and preparation method thereof | |
CN106318536B (en) | A kind of hydrodynamic lubrication fluid composition and preparation method thereof | |
CN107304381B (en) | A kind of combustion gas turbine oil composition and preparation method thereof | |
CN106318545B (en) | A kind of diesel engine lubricating oil composite and preparation method thereof | |
CN106318552B (en) | A kind of hydrodynamic lubrication fluid composition and preparation method thereof | |
CN106318520B (en) | A kind of lubricant oil composite and preparation method thereof | |
CN105586113B (en) | Excellent sodium base grease composition of a kind of antioxygen property and preparation method thereof | |
CN105586132B (en) | Excellent bentonite grease composition of a kind of antioxygenic property and preparation method thereof | |
CN105586112B (en) | Excellent calcium base grease composition of a kind of antioxygen property and preparation method thereof | |
CN106318556B (en) | A kind of vehicle gear lubricating oil composition and preparation method thereof | |
CN105586116B (en) | Excellent bentonite grease composition of a kind of Wear vesistance and preparation method thereof |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |