CN107304378A - A kind of high-temperature chain oil composition and preparation method thereof - Google Patents
A kind of high-temperature chain oil composition and preparation method thereof Download PDFInfo
- Publication number
- CN107304378A CN107304378A CN201610238048.5A CN201610238048A CN107304378A CN 107304378 A CN107304378 A CN 107304378A CN 201610238048 A CN201610238048 A CN 201610238048A CN 107304378 A CN107304378 A CN 107304378A
- Authority
- CN
- China
- Prior art keywords
- weight
- lubricant oil
- consumption
- oil composite
- wear
- 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.)
- Granted
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
- C10M135/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
- C10M135/32—Heterocyclic sulfur, selenium or tellurium compounds
- C10M135/36—Heterocyclic sulfur, selenium or tellurium compounds the ring containing sulfur and carbon with nitrogen or oxygen
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
- C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
- C07D417/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings linked by a chain containing hetero atoms as chain links
-
- 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
-
- 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
- C10N2030/08—Resistance to extreme temperature
-
- 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)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Lubricants (AREA)
Abstract
The invention discloses a kind of high-temperature chain oil composition, on the basis of the weight of lubricant oil composite, the lubricant oil composite contains following components：85 99 weight % lube base oil, the 0.01 10 weight % wear-resistant multipurpose additive of antioxygen, 0.01 5 weight % thiophenols ester type antioxidant, 0.05 5 weight % Zinc oxide nanoparticle, 0.01 5 weight % demulsifier, the wear-resistant multipurpose additive of antioxygen are the compound of structure shown in formula (I).Present invention also offers the preparation method of high-temperature chain oil composition.The high-temperature chain oil composition of the present invention has excellent abrasion resistance and antioxygenic property, can be widely applied to high-temperature chain lubricating area.
Description
Technical field
The present invention relates to lubricating oil field, in particular it relates to a kind of high-temperature chain containing special additive
Fluid composition and preparation method thereof.
Background technology
With developing rapidly for the industries such as petrochemical industry, weaving, printing and dyeing, building materials and traffic, the work(of these equipment
Rate and exploitation speed are improved constantly, transmission system operating temperature more and more higher, the also day of the requirement to chain oils
Become harsh.High-temperature chain transmission is operated in the environment of exposure experience high/low temperature, high-temperature chain oil temperature
Degree is reachable more than 200 DEG C, and lubricating oil is very easy to produce oxidation, therefore chain greasisng oil is with higher
High-temperature oxidation stability and the lubricity good in high temperature are extremely important.The even running of chain and chain link
Small abrasion depend on chain greasisng system good lubrication effect, particularly those bear heavy load and punching
Chain under the conditions of hitting, therefore high-temperature chain oil is also very high for the requirement of extreme pressure and wear resistence.During high temperature
Carbon deposition of oil ageing generation etc. can cause chain wear, may be chain operation irregularity.
Because operating mode becomes harsh and operating temperature rise, hexichol is such as alkylated with existing conventional high-temperature antioxidant
It is wear-resistant to high temperature antioxygen that high-temperature chain oil prepared by amine can not fully meet high-temperature chain oil
With the requirement of reduction high temperature deposition thing generation.Develop with excellent high temperature antioxygen, wear-resistant property, and have
The chain oil composition for having the property of outstanding high temperature resistance coking is always the effort of this area researcher
Direction.
The lube oil additive that can effectively play antioxidation is currently known mainly including phenols and amine
Class compound.Phenolic compound contains one or more phenol functional groups that are obstructed, and aminated compounds then contains one
Individual or multiple nitrogen-atoms, these special functional groups can catch the free radical compounds of oxidizing process generation,
So as to prevent the continuation of oxidizing process from occurring.It is past because the condition of work of Current mechanical equipment tends to be strong
Toward meeting accelerated oxidation speed, shorten the service life of lubricating oil, therefore to the efficiency and economy of antioxidant
Propose higher requirement.
United States Patent (USP) US4824601A reports the alkaline-earth metal of diphenylamine and diisobutylene in acid activation
The lower alkylated amines mixture formed of catalyst (earth catalyst) effect, it is in lubricating oil and other
Oxidation resistance performance is excellent in functional fluid.
United States Patent (USP) US2005230664A1 reports a kind of antioxidant 9 of below general formula, 10- dihydros
The synthetic method of acridine, it is to be contracted using alkylated diphenylamine and aldehydes or ketones under acidic catalyst effect
Close and prepare.
Patent CN1191340C is occurred using the tert-butyl group phenols that is obstructed, aldehyde, carbon disulfide and dialkylamine
Prepare compound is condensed, the compound has the stronger ability for catching free radical and peroxynitrite decomposition compound,
More effective protection can be provided to oil oxidation stability, wear-resistant effect is may also function as.
Patent US4225450 reports a kind of by tert-butyl group phenols and the alkyl aminodithioformic acid of being obstructed
Polysulfide phenolic antioxidant prepared by reactant salt, with preferable antioxidation and wear-resistant effect.
The content of the invention
The invention aims to meet anti-oxidant, abrasion-resistance the high request to high-temperature chain oil,
A kind of high-temperature chain oil composition and preparation method thereof is provided.
The present inventor has found that lubricant oil composite contains structure shown in formula (I) under study for action
Compound：
And the compound is combined with thiophenols ester type antioxidant, can have high-temperature chain oil composition
The excellent performance such as anti-oxidant and wear-resistant.
Therefore, to achieve these goals, on the one hand, the invention provides a kind of combination of high-temperature chain oil
Thing, on the basis of the weight of lubricant oil composite, the lubricant oil composite contains following components：85-99
Weight % lube base oil, the 0.01-10 weight % wear-resistant multipurpose additive of antioxygen, 0.01-5 weight %
Thiophenols ester type antioxidant, 0.05-5 weight % Zinc oxide nanoparticle, 0.01-5 weight % it is broken
Emulsion, the wear-resistant multipurpose additive of antioxygen is the compound of structure shown in formula (I)：
Preferably, on the basis of the weight of lubricant oil composite, the lubricant oil composite contains with the following group
Point：90-99 weight % lube base oil, 0.1-4 weight the % wear-resistant multipurpose additive of antioxygen, 0.05-3
Weight % thiophenols ester type antioxidant, 0.1-3 weight % Zinc oxide nanoparticle, 0.05-3 weight %
Demulsifier.
On the other hand, the invention provides a kind of preparation method of high-temperature chain oil composition, methods described
Including：Will containing lube base oil, the wear-resistant multipurpose additive of antioxygen, thiophenols ester type antioxidant, appoint
The Zinc oxide nanoparticle of choosing, the raw material of optional demulsifier are well mixed and obtain lubricant oil composite, its
In, on the basis of the weight of lubricant oil composite, the consumption of lube base oil is 85-99 weight %,
The consumption of the wear-resistant multipurpose additive of antioxygen is that 0.01-10 weight %, the consumption of thiophenols ester type antioxidant are
0.01-5 weight %, the consumption of Zinc oxide nanoparticle are 0.05-5 weight %, and the consumption of demulsifier is
0.01-5 weight %, the wear-resistant multipurpose additive of antioxygen is the compound of structure shown in formula (I)：
Preferably, on the basis of the weight of lubricant oil composite, the consumption of lube base oil is 90-99
The consumption of the wear-resistant multipurpose additive of weight %, antioxygen is 0.1-4 weight %, the use of thiophenols ester type antioxidant
Amount is that 0.05-3 weight %, the consumption of Zinc oxide nanoparticle are 0.1-3 weight %, the consumption of demulsifier
For 0.05-3 weight %.
The high-temperature chain oil composition of the present invention has excellent abrasion resistance and antioxygenic property, Ke Yiguang
It is general to be applied to chain greasisng field.
Other features and advantages of the present invention will be described in detail in subsequent embodiment part.
Brief description of the drawings
Fig. 1 is the reaction equation of (a) the step of preparing antioxygen wear-resistant multipurpose additive.
Fig. 2 is the reaction equation of (b) the step of preparing antioxygen wear-resistant multipurpose additive.
Fig. 3 is the hydrogen spectrum spectrogram of the wear-resistant multipurpose additive of antioxygen prepared by preparation example.
Fig. 4 is the carbon spectrum spectrogram of the wear-resistant multipurpose additive of antioxygen prepared by preparation example.
Fig. 5 is the mass spectrogram of the wear-resistant multipurpose additive of antioxygen prepared by preparation example.
Embodiment
The embodiment to the present invention is described in detail below.It should be appreciated that this place is retouched
The embodiment stated is merely to illustrate and explain the present invention, and is not intended to limit the invention.
On the one hand, the invention provides a kind of high-temperature chain oil composition, with the weight of lubricant oil composite
On the basis of, lubricant oil composite contains following components：85-99 weight % lube base oil, 0.01-10
The weight % wear-resistant multipurpose additive of antioxygen, 0.01-5 weight % thiophenols ester type antioxidant, 0.05-5
Weight % Zinc oxide nanoparticle, 0.01-5 weight % demulsifier, the wear-resistant multipurpose additive of antioxygen is
The compound of structure shown in formula (I)：
In the present invention, on the basis of the weight of lubricant oil composite, the content of lube base oil is preferably
90-99 weight %；The content of the wear-resistant multipurpose additive of antioxygen is preferably 0.02-5 weight %, more preferably
0.1-4 weight %；The content of thiophenols ester type antioxidant is preferably 0.05-3 weight %；Zinc-oxide nano
The content of grain is preferably 0.1-4 weight %, more preferably 0.1-3 weight %；The content of demulsifier is preferably
0.02-4 weight %, more preferably 0.05-3 weight %.
It is contemplated that the compound by containing structure shown in formula (I) in lubricant oil composite, and
The compound of structure shown in formula (I) is combined with thiophenols ester type antioxidant and realizes goal of the invention, even if
Lubricant oil composite has the excellent performance such as wear-resistant and anti-oxidant.Therefore, in lubricant oil composite
The selection of each conventional constituents, is not limited specifically.
In the present invention, lube base oil can be lube base oil commonly used in the art, for example
Can be mineral lubricating oil and/or synthetic lubricant fluid.
Mineral lubricating oil can be from light fraction mineral oil to heavy distillat mineral oil in viscosity, including liquid stone
Wax oil and hydrofinishing, the alkane that solvent is treated, cycloalkanes and mixing par-affinic-naphthenic types mineral lubricant
Oil, is generally divided into I, II, Group III base oil, and common trade names include I classes 150SN, 600SN,
II classes 100N, 150N, 350N etc..
Synthetic lubricant fluid can include polymerization hydrocarbon ils, alkyl benzene and its derivative, polymerize the specific example of hydrocarbon ils
Son includes but is not limited to polybutene, polypropylene, propylene-isobutylene copolymers, the polybutene of chlorination, poly- (1-
Hexene), poly- (1- octenes), poly- (1- decene), common trade names include PAO4, PAO6, PAO8,
PAO10 etc., alkyl benzene and its derivative specific example includes but is not limited to detergent alkylate, the tetradecane
Base benzene, dinonyl benzene, two (2- ethylhexyls) benzene, alkyl benzene derivate include the diphenyl ether of alkylation
Diphenyl sulfide and its derivative, analog and homologue with alkylation etc..
Another suitable type of synthetic lubricant fluid can be Esters oil, including dicarboxylic acids (such as phthalic acid,
It is butanedioic acid, alkyl succinic acid and alkenyl succinic acid, maleic acid, azelaic acid, suberic acid, decanedioic acid, anti-
Butene dioic acid, adipic acid, linoleic acid dimer, malonic acid, alkyl malonic acid, alkenyl malonic) with
Various alcohol (such as butanol, hexanol, dodecyl alcohol, 2- ethylhexyl alcohols, ethylene glycol, propane diols) hairs
The ester or complex ester of raw condensation reaction generation.The specific example of these esters includes but is not limited to the fourth of adipic acid two
Ester, decanedioic acid two (2- ethylhexyls) ester, the just own ester of fumaric acid acid two, di-n-octyl sebacate, nonyl
Diacid di-isooctyl, two different decayl esters of azelaic acid, dioctyl phthalate, didecyl phthalate,
Decanedioic acid two (larane base) ester, 2- ethylhexyl diester of linoleic acid dimer etc..
Another suitable type of synthetic lubricant fluid can be for fischer tropsch process synthetic hydrocarbon oil and to this synthesis hydrocarbon
Oil by hydroisomerizing, be hydrocracked, the lube base oil that the PROCESS FOR TREATMENT such as dewax is obtained.
In the present invention, lube base oil preferred viscosities index is more than 80, saturated hydrocarbon content and is more than 90 weights
Measure the lube base oil that %, sulfur content are less than 0.03 weight %.
In the present invention, thiophenols ester type antioxidant can be thiophenols ester type antioxidant commonly used in the art,
For example can for the double lauryl alcohol esters (DLTDP) of thio-2 acid, the double octadecyl esters (DSTDP) of thio-2 acid,
2,5- dimercapto -1,3,4- thiadiazoles (DMTD) and 2,2'- thiobis [3- (3,5- di-t-butyl -4- hydroxy benzenes
At least one of base) ethyl propionate], preferably 2,2'- thiobis [3- (3,5- di-tert-butyl-hydroxy phenyl)
Ethyl propionate], such as antioxidant 1035 of Sichuan Yong Ye Chemical Co., Ltd.s production, German BASF is public
Take charge of the IRGANOX L115 of production.
In the present invention, Zinc oxide nanoparticle is the single or composite Nano of the composition containing Zinc oxide nanoparticle
Particle.The high-temperature chain lubricating oil of addition Zinc oxide nanoparticle has preferable high temperature wear resistance, adds
Plus the abrasion resistance of rear oil product is improved.The particle diameter of nano-particle is 3-150nm.
In the present invention, demulsifier can be propylene glycol block polyether, NPE, ethylenediamine
At least one of polyoxypropylene polyoxyethylene ether and propane diamine polyoxypropylene polyoxyethylene ether.
The lubricant oil composite of the present invention can also contain at least one of antirust agent and anti-foaming agent.Antirust
Agent can be selected from imidazoles and/or alkenyl succinic acid esters, preferably 4,5- glyoxalidine, alkenyl imidazoline
At least one of succinate and alkenyl succinic acid ester, for example can be from the safe lubricating oil addition in Jinzhou
T746, T703, T747 of agent Co., Ltd production.Anti-foaming agent can select polysiloxane type anti-foaming agent,
For example can be silicone oil and/or dimethyl silicone polymer.For the content of antirust agent, pour-point depressant and anti-foaming agent
Can be the conventional content in this area, this is known to those skilled in the art, herein without particular/special requirement
Repeat no more.
In the present invention, the preparation method of the compound of structure is preferably included shown in formula (I)：
(a) aniline, sulfur chloride and 4- chloroanilines are reacted, the intermediate shown in generation formula (II)
M,
(b) the intermediate M for obtaining step (a) and dimercapto -1,3,4- thiadiazoles be in the basic conditions
Nucleophilic substitution is carried out, the multipurpose additive shown in formula (I) is generated,
In step (a) of the present invention, the concrete mode that aniline, sulfur chloride and 4- chloroanilines are reacted
Preferably include：
(i) under an inert atmosphere, in the first solvent, by aniline and sulfur chloride at -20-0 DEG C fully
Reacted；
(ii) 4- chloroanilines are added in the reaction system of step (i), 1-3h is reacted at 15-30 DEG C.
In the present invention, inert atmosphere can be the conventional inert atmosphere in this area, for example can by nitrogen,
The gases such as argon gas are provided.
In step (i) of the present invention, the first solvent be preferably selected from dichloromethane, tetrahydrofuran, toluene,
At least one of dimethylbenzene and dioxane, more preferably dichloromethane and/or tetrahydrofuran, more enter one
Step is preferably dichloromethane.
In the present invention in step (i), fully reacted and refer to that reaction is complete, i.e., reaction raw materials are complete
Reacted entirely.Reaction can be monitored using method commonly used in the art, to confirm that reaction is complete,
The method such as can use TLC (TLC) or gas-chromatography is monitored.
In step (ii) of the present invention, 1-3h is reacted at 15-30 DEG C, it is preferably fully anti-in step (i)
Ying Hou, 15-30 DEG C is gradually increased to by the temperature of reaction system, is added 4- chloroanilines and is carried out reaction 1-3h.
Under the preferable case, reaction yield can be further improved.
In step (ii) of the present invention, the feed postitions of 4- chloroanilines is preferably to add by several times, for example can be with
Divide 3-4 addition.Under the preferable case, reaction yield can be further improved.Added for gradation
When, each addition can be with identical, can also be different, for easy to operate, preferably each addition
Amount is identical.
In step (ii) of the present invention, 1-3h is reacted, the mode for stopping reaction can be people in the art
The thinkable various modes of member institute, are quenched, quencher can be this for example, quencher can be added
The conventional quencher in field, for example, can be saturated aqueous common salt.
In the present invention, the consumption of aniline, sulfur chloride and 4- chloroanilines is substantially equimolar amounts, but aniline
Can be suitably excessive with sulfur chloride.The mol ratio of aniline, sulfur chloride and 4- chloroanilines is preferably 0.9-1.5：
0.9-1.5：0.8-1.2.
It will be understood by those skilled in the art that in step (a) of the present invention, it is purer in order to obtain
Intermediate M, in addition it is also necessary to reacted system is post-processed, the mode of post processing can include washing
Wash, dry, removal of solvent under reduced pressure, for example, by the reaction system after being quenched respectively use distilled water and saturation
Brine It, then adds the drier such as anhydrous calcium chloride or anhydrous sodium sulfate at 15-30 DEG C,
Keep 10-60min.It is filtered to remove after drier, solvent is removed at 0.01-0.05MPa, 40-60 DEG C,
To obtain intermediate M.
In step (a) of the present invention, the reaction equation that aniline, sulfur chloride and 4- chloroanilines are reacted
As shown in figure 1, in Fig. 1, the first solvent uses dichloromethane, purpose by way of example only,
The scope of the present invention is not construed as limiting.
In step (b) of the present invention, the condition of nucleophilic substitution is preferably included：Under an inert atmosphere,
In the second solvent, dimercapto-1,3,4-thiadiazole, alkaline reagent and catalyst are mixed at 15-30 DEG C
10-30min, then adds intermediate M, is fully reacted.I.e. alkalescence condition is provided by alkaline reagent.
" inert atmosphere ", " fully being reacted " are as it was previously stated, will not be repeated here.
In the present invention, intermediate M is preferably slowly added to, for example, can add by several times, can typically be divided
3-4 addition.Under the preferable case, reaction yield can be further improved.When being added for gradation,
Each addition can be with identical, can also be different, for easy to operate, preferably each addition phase
Together.
In the present invention, the second solvent is preferably selected from dichloromethane, tetrahydrofuran, toluene, dimethylbenzene, N, N-
At least one of dimethylformamide, more preferably dichloromethane and/or DMF,
Still more preferably it is N,N-dimethylformamide.
In the present invention, alkaline reagent is preferably selected from the inorganic bases such as potassium carbonate, sodium carbonate, sodium methoxide extremely
Few one kind.
In the present invention, catalyst is preferably potassium sulfate.
In step (b) of the present invention, the use of dimercapto-1,3,4-thiadiazole, alkaline reagent and intermediate M
Amount is substantially equimolar amounts, but dimercapto-1,3,4-thiadiazole and alkaline reagent can be suitably excessive.Two
The mol ratio of sulfydryl -1,3,4- thiadiazoles, alkaline reagent and intermediate M is preferably 0.9-3.0：0.9-5.0：
0.8-1.5。
In step (b) of the present invention, the consumption of catalyst can be catalytic amount, with dimercapto -1,3,4- thiophenes two
On the basis of the molal quantity of azoles, the consumption of catalyst is preferably 5-100 moles of %, and more preferably 10-50 rubs
You are %.
In step (b) of the present invention, the reaction that dimercapto-1,3,4-thiadiazole and intermediate M are reacted
Equation is as shown in Fig. 2 in Fig. 2, alkaline reagent uses potassium carbonate, mesh by way of example only
, the scope of the present invention is not construed as limiting.
It will be understood by those skilled in the art that in order to obtain purer final product, i.e., it is of the invention
Multipurpose additive, the present invention, which prepares the method for multipurpose additive, preferably also to be included entering reacted system
Row post processing, the mode of post processing can include washing, dry, removal of solvent under reduced pressure, for example, will fill
Reacted system is divided to pour into the ethyl acetate (or dichloromethane) of 1-10 times of volume, respectively with steaming
Distilled water and saturated common salt water washing, then add anhydrous calcium chloride or anhydrous sodium sulfate at 15-30 DEG C
Deng drier, 10-60min is kept.It is filtered to remove after drier, in 0.01-0.05MPa, 40-60 DEG C
Lower removing solvent, to obtain final product.
Each step of the method for the compound of structure shown in formula (I) is prepared in the present invention preferably under agitation
Carry out, can be the conventional mixing speed in this area, for example, stirring for mixing speed without particular/special requirement
It can be 100-800rpm to mix speed.
In the present invention, for the first solvent and the second solvent amount without particular/special requirement, can for this area it is normal
The solvent load of rule, this is known to those skilled in the art, will not be repeated here.
As described above, it is contemplated that passing through the change containing structure shown in formula (I) in lubricant oil composite
Compound, and the compound of structure shown in formula (I) and thiophenols ester type antioxidant is combined and realizes and invent
Purpose, even if lubricant oil composite has the excellent performance such as wear-resistant and anti-oxidant.Therefore, for lubrication
The preparation method of fluid composition can use method commonly used in the art without particular/special requirement, for example,
Second aspect, present invention also offers a kind of preparation method of high-temperature chain oil composition, this method includes：
Lube base oil, the wear-resistant multipurpose additive of antioxygen, thiophenols ester type antioxidant, optional oxygen will be contained
Change zinc nanoparticles, the raw material of optional demulsifier is well mixed and obtains lubricant oil composite, wherein, with
On the basis of the weight of lubricant oil composite, the consumption of lube base oil is 85-99 weight %, antioxygen resists
The consumption of mill multipurpose additive is that 0.01-10 weight %, the consumption of thiophenols ester type antioxidant are 0.01-5
Weight %, the consumption of Zinc oxide nanoparticle are 0.05-5 weight %, and the consumption of demulsifier is 0.01-5 weights
% is measured, the wear-resistant multipurpose additive of antioxygen is the compound of structure shown in formula (I)：
In the inventive method, on the basis of the weight of lubricant oil composite, the consumption of lube base oil is excellent
It is preferably 0.02-5 weight % to elect 90-99 weight %, the consumption of the wear-resistant multipurpose additive of antioxygen as, more excellent
It is preferably 0.05-3 weight %, zinc oxide to elect 0.1-4 weight %, the consumption of thiophenols ester type antioxidant as
The consumption of nano particle is preferably 0.1-4 weight %, more preferably 0.1-3 weight %, the consumption of demulsifier
Preferably 0.05-4 weight %, more preferably 0.05-3 weight %.
As it was previously stated, in the inventive method, raw material can also contain in antirust agent, pour-point depressant and anti-foaming agent
At least one.
In the inventive method, for mixing mode without particular/special requirement, can will for example remove lube base
Each raw material components of oil are added separately in lube base oil, can also will be each except lube base oil
Component is mixed and made into concentrate and is then added in lube base oil.
In the inventive method, the condition of mixing is preferably included：Temperature is 40-90 DEG C, and the time is 1-6h.
The wear-resistant multipurpose additive of lube base oil, antioxygen, thiophenols ester type antioxidant, zinc-oxide nano
Particle, demulsifier, antirust agent and anti-foaming agent are as it was previously stated, will not be repeated here.
Embodiment
The present invention is further illustrated for following embodiment, but and is not so limited the present invention.
In the following Examples and Comparative Examples：
The complete method of monitoring reaction：Thin-layer chromatography chromatogram (TLC) fluorescence developing method.
Gross production rate=final product mole/aniline moles × 100%
The physico-chemical analysis method of product：Element is determined by inductively coupled plasma ion emission spectroscopy method
Content.
Structure characterization methods：Nuclear magnetic resonance method (1H hydrogen is composed,13C carbon is composed), high resolution mass spectrum.
Preparation example
Nitrogen is filled with the 500ml flasks with electromagnetic agitation sub (mixing speed is 300rpm) to protect
Shield, adds 150ml dichloromethane, then adds 0.2mol sulfur chloride, in ice-water bath fully
After cooling, 0.2mol aniline is added.Monitoring removes ice-water bath to after reacting completely, is placed in 25 DEG C of rooms
Under temperature, question response system is gradually increased to after 25 DEG C, and point 3 addition 4- chloroanilines are reacted, every time
Addition is identical, and 4- chloroanilines 0.15mol is added altogether.Sustained response adds 30ml saturations food after 2 hours
Reaction is quenched in salt solution, and then reaction system is transferred in separatory funnel, respectively with 50ml distilled water and 50ml
Saturated common salt water washing, and add 10g anhydrous sodium sulfates dry 20min at 25 DEG C.Filter after filtering
Solvent is evaporated off under 40 DEG C, 0.05MPa in liquid, obtains intermediate M1.
Nitrogen is filled with the 500ml flasks with electromagnetic agitation sub (mixing speed is 400rpm) to protect
Shield, adds 150ml DMF (DMF), then adds 0.2mol dimercaptos -1,3,4-
Thiadiazoles and 0.2mol potassium carbonate, 0.05mol potassium sulfate, are stirred 20 minutes at 25 DEG C, and points 3
Secondary to add above-mentioned intermediate M1, each addition is identical, and intermediate M1 0.12mol are added altogether.Monitoring
It is complete to reacting, reaction system is then added into 250ml ethyl acetate, and be transferred in separatory funnel, point
Not Yong 100ml distilled water (twice) and 50ml saturated common salt water washings, and add 15g anhydrous slufuric acids
Sodium dries 20min at 25 DEG C.Solvent is evaporated off under 40 DEG C, 0.03MPa in filtrate after filtering, obtains
Final product S1.It is 76% to calculate gross production rate.
The physico-chemical analysis data of product are as follows：Sulfur content, 41.3%；Nitrogen content, 13.9%.
S1 is subjected to structural characterization, hydrogen spectrum, carbon spectrum and high resolution mass spec spectrogram is respectively obtained, respectively
See Fig. 3, Fig. 4 and Fig. 5.
Physico-chemical analysis data from above-mentioned preparation example, Fig. 3, Fig. 4 and Fig. 5 can be seen that S1 has formula
(I) structure shown in.
Embodiment 1
The present embodiment is used to illustrate lubricant oil composite of the present invention and preparation method thereof.
By the S1 of 0.1 parts by weight, the 2,2'- thiobis [3- (3,5- di-t-butyl -4- hydroxy benzenes of 1.2 parts by weight
Base) ethyl propionate], (Turner rice limited material in Shandong is public for the single Zinc oxide nanoparticle of 0.17 parts by weight
Department), ethylenediamine polyoxypropylene polyoxyethylene ether, the polydimethylsiloxanes of 0.1 parts by weight of 0.4 parts by weight
Alkane (being purchased from Hubei xinsihai Chemical Co., Ltd.) is added to the hydrogenation II-10 lubrications of 98 parts by weight
In oil base oil, 3h is stirred at 60 DEG C, it is well mixed to obtain lubricant oil composite A1.
Embodiment 2
The present embodiment is used to illustrate lubricant oil composite of the present invention and preparation method thereof.
By the S1 of 1.1 parts by weight, the 2,2'- thiobis [3- (3,5- di-t-butyl -4- hydroxy benzenes of 0.5 parts by weight
Base) ethyl propionate], (Turner rice limited material in Shandong is public for the single Zinc oxide nanoparticle of 0.21 parts by weight
Department), ethylenediamine polyoxypropylene polyoxyethylene ether, the polydimethylsiloxanes of 0.2 parts by weight of 0.2 parts by weight
Alkane (being purchased from Hubei xinsihai Chemical Co., Ltd.) is added to PAO6 and PAO10 mixing profit
In lubricant base oil (PAO6 is 50 parts by weight, and PAO10 is 47.5 parts by weight), stirred at 40 DEG C
6h is mixed, it is well mixed to obtain lubricant oil composite A2.
Embodiment 3
The present embodiment is used to illustrate lubricant oil composite of the present invention and preparation method thereof.
By the S1 of 1.9 parts by weight, the 2,2'- thiobis [3- (3,5- di-t-butyl -4- hydroxy benzenes of 0.1 parts by weight
Base) ethyl propionate], (Turner rice limited material in Shandong is public for the single Zinc oxide nanoparticle of 0.25 parts by weight
Department), the ethylenediamine polyoxypropylene polyoxyethylene ether of 0.5 parts by weight, the poly dimethyl silicon of 0.01 parts by weight
Oxygen alkane (being purchased from Hubei xinsihai Chemical Co., Ltd.) is added to the adipic acid two of 97.39 parts by weight
In butyl ester, 1h is stirred at 90 DEG C, it is well mixed to obtain lubricant oil composite A3.
Comparative example 1
Method according to embodiment 2 prepares lubricant oil composite, unlike, by S1 replace with wait weigh
2, the 2'- thiobis [3- (3,5- di-tert-butyl-hydroxy phenyl) ethyl propionate] of part is measured, lubricating oil composition is obtained
Thing D1.
Comparative example 2
Method according to embodiment 2 prepares lubricant oil composite, unlike, by 2,2'- thiobis [3- (3,5-
Di-tert-butyl-hydroxy phenyl) ethyl propionate] S1 of parts by weight such as replace with, obtain lubricant oil composite
D2。
Comparative example 3
Method according to embodiment 2 prepares lubricant oil composite, unlike, by S1 and 2,2'- is thio
Double [3- (3,5- di-tert-butyl-hydroxy phenyls) ethyl propionates] dibutyl dithio of parts by weight such as replace with
Carbaminate, obtains lubricant oil composite D3.
Comparative example 4
Method according to embodiment 2 prepares lubricant oil composite, unlike, by S1 and 2,2'- is thio
Double [3- (3,5- di-tert-butyl-hydroxy phenyls) ethyl propionates] the trimethylphenyl phosphorous of parts by weight such as replace with
Sour zinc, obtains lubricant oil composite D4.
Comparative example 5
Method according to embodiment 2 prepares lubricant oil composite, unlike, by S1 and 2,2'- is thio
Double [3- (3,5- di-tert-butyl-hydroxy phenyl) ethyl propionates] the fourth octyl diphenylamine of parts by weight such as replace with,
Obtain lubricant oil composite D5.
Test case
Lubricant oil composite A1-A3, D1-D5 are tested as follows respectively：
The measure of initial oxidation temperature is carried out using TA5000-DSC2910 differential thermal analyzers；
The measure 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 determined by GB/T3142；
Wear scar diameter is determined using SH/T 0189.
The sediment yield that oil product when determining 250 DEG C is produced is tested using swash plate coking analog meter.
It the results are shown in Table 1.
Table 1
| A1 | A2 | A3 | D1 | D2 | D3 | D4 | D5 | |
| Initial oxidation temperature, DEG C | 204 | 211 | 219 | 192 | 190 | 198 | 191 | 192 |
| Oxidation induction period, min | 43.7 | 50.7 | 58.2 | 32.6 | 37.8 | 33.1 | 29.4 | 31.5 |
| PB, kgf | 90 | 100 | 105 | 50 | 65 | 55 | 65 | 50 |
| PD, kgf | 295 | 305 | 310 | 225 | 265 | 220 | 240 | 230 |
| Wear scar diameter d60 40, mm | 0.53 | 0.47 | 0.46 | 0.69 | 0.61 | 0.71 | 0.62 | 0.64 |
| High temperature deposition object amount, mg | 6.9 | 5.5 | 5.1 | 10.2 | 9.6 | 9.2 | 10.3 | 9.7 |
It will be understood by those skilled in the art that initial oxidation temperature is higher, the heat endurance of lubricating oil
Better；Oxidation induction period is longer, and the antioxygenic property of lubricating oil is better；PB, PD value are bigger, lubrication
The wear resistance of oil is better；Wear scar diameter is smaller, and the wear resistance of lubricating oil is better；Coking amount is got over
Height, the high temperature resistance cokeability for representing this test specimen is poorer.
A2 is compared with D1-D5 respectively as can be seen that the lubricant oil composite of the present invention has more
Good inoxidizability and abrasion resistance.
The high-temperature chain oil composition of the present invention has excellent abrasion resistance and antioxygenic property, Ke Yiguang
It is general to be applied to high-temperature chain lubricating area.
The preferred embodiment of the present invention is described in detail above in association with accompanying drawing, still, the present invention is not limited
Detail in above-mentioned embodiment, can be to the present invention in the range of the technology design of the present invention
Technical scheme carry out a variety of simple variants, these simple variants belong to protection scope of the present invention.
It is further to note that each particular technique feature described in above-mentioned embodiment,
In the case of reconcilable, it can be combined by any suitable means, in order to avoid unnecessary
Repeat, the present invention no longer separately illustrates to various possible combinations.
In addition, various embodiments of the present invention can be combined randomly, as long as its
Without prejudice to the thought of the present invention, it should equally be considered as content disclosed in this invention.
Claims (12)
1. a kind of high-temperature chain oil composition, it is characterised in that using the weight of lubricant oil composite as base
Standard, the lubricant oil composite contains following components：85-99 weight % lube base oil, 0.01-10
The weight % wear-resistant multipurpose additive of antioxygen, 0.01-5 weight % thiophenols ester type antioxidant, 0.05-5
Weight % Zinc oxide nanoparticle, 0.01-5 weight % demulsifier, the wear-resistant multiple-effect addition of antioxygen
Agent is the compound of structure shown in formula (I)：
2. lubricant oil composite according to claim 1, wherein, with the weight of lubricant oil composite
On the basis of amount, the lubricant oil composite contains following components：90-99 weight % lube base oil,
The 0.1-4 weight % wear-resistant multipurpose additive of antioxygen, 0.05-3 weight % thiophenols ester type antioxidant, 0.1-3
Weight % Zinc oxide nanoparticle, 0.05-3 weight % demulsifier.
3. lubricant oil composite according to claim 1 or 2, wherein, the lube base
Oil is mineral lubricating oil and/or synthetic lubricant fluid.
4. lubricant oil composite according to claim 1 or 2, wherein, the thiophenols ester type
Antioxidant is the double lauryl alcohol esters of thio-2 acid, thio-2 acid double octadecyl ester, 2,5- dimercaptos -1,3,4-
At least one of thiadiazoles and 2,2'- thiobis [3- (3,5- di-tert-butyl-hydroxy phenyls) ethyl propionate].
5. lubricant oil composite according to claim 1 or 2, wherein, the zinc-oxide nano
Particle is the nano-particle of the composition containing Zinc oxide nanoparticle, and the particle diameter of nano-particle is 3-150nm.
6. lubricant oil composite according to claim 1 or 2, wherein, the demulsifier is third
Diol block polyethers, NPE, ethylenediamine polyoxypropylene polyoxyethylene ether and propane diamine
At least one of polyoxypropylene polyoxyethylene ether.
7. lubricant oil composite according to claim 1 or 2, wherein, the lubricating oil composition
Thing also contains at least one of antirust agent and anti-foaming agent.
8. lubricant oil composite according to claim 7, wherein, the antirust agent is selected from imidazoles
Class and/or alkenyl succinic acid esters, preferably 4,5- glyoxalidine, alkenyl imidazoline succinate and alkenyl
At least one of succinate.
9. lubricant oil composite according to claim 7, wherein, the anti-foaming agent is poly- silica
Alkane type anti-foaming agent, preferably silicone oil and/or dimethyl silicone polymer.
10. a kind of preparation method of high-temperature chain oil composition, it is characterised in that methods described includes：
Lube base oil, the wear-resistant multipurpose additive of antioxygen, thiophenols ester type antioxidant, zinc oxide nano will be contained
Rice grain, the raw material of demulsifier are well mixed and obtain lubricant oil composite, wherein, with lubricant oil composite
Weight on the basis of, the consumption of lube base oil is 85-99 weight %, the wear-resistant multipurpose additive of antioxygen
Consumption be that 0.01-10 weight %, the consumption of thiophenols ester type antioxidant are 0.01-5 weight %, oxidation
The consumption of zinc nanoparticles is 0.05-5 weight %, and the consumption of demulsifier is 0.01-5 weight %, described anti-
The wear-resistant multipurpose additive of oxygen is the compound of structure shown in formula (I)：
11. method according to claim 11, wherein, using the weight of lubricant oil composite as base
Standard, the consumption of lube base oil is that 90-99 weight %, the consumption of the wear-resistant multipurpose additive of antioxygen are 0.1-4
Weight %, the consumption of thiophenols ester type antioxidant are 0.05-3 weight %, the consumption of Zinc oxide nanoparticle
For 0.1-3 weight %, the consumption of demulsifier is 0.05-3 weight %.
12. the method according to claim 11 or 12, wherein, the condition of the mixing includes：
Temperature is 40-90 DEG C, and the time is 1-6h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610238048.5A CN107304378B (en) | 2016-04-18 | 2016-04-18 | A kind of high-temperature chain oil composition and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610238048.5A CN107304378B (en) | 2016-04-18 | 2016-04-18 | A kind of high-temperature chain oil composition and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107304378A true CN107304378A (en) | 2017-10-31 |
| CN107304378B CN107304378B (en) | 2019-08-16 |
Family
ID=60152128
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610238048.5A Active CN107304378B (en) | 2016-04-18 | 2016-04-18 | A kind of high-temperature chain oil composition and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107304378B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111088098A (en) * | 2018-10-23 | 2020-05-01 | 中国石油化工股份有限公司 | High-temperature chain oil composition and preparation method thereof |
| CN114479993A (en) * | 2020-11-12 | 2022-05-13 | 中国石油天然气股份有限公司 | Chain oil composition compatible with water-based paint and preparation method thereof |
| CN117757551A (en) * | 2023-12-12 | 2024-03-26 | 浙江康力博石化有限公司 | High-temperature anti-coking food-grade chain lubricating oil and preparation method thereof |
| CN117757551B (en) * | 2023-12-12 | 2024-05-31 | 浙江康力博石化有限公司 | High-temperature anti-coking food-grade chain lubricating oil and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5177212A (en) * | 1991-07-26 | 1993-01-05 | R.T. Vanderbilt Company, Inc. | Phenolic derivatives of 2,5-dimercapto-1,3,4-thiadiazoles |
| US5336420A (en) * | 1991-05-08 | 1994-08-09 | Mobil Oil Corporation | Antioxidants for functional fluids |
| CN101830865A (en) * | 2010-03-19 | 2010-09-15 | 华东交通大学 | Hydroxyl-containing thiadiazole derivate as well as preparation method and application thereof |
| CN102690703A (en) * | 2011-03-24 | 2012-09-26 | 中国石油化工股份有限公司 | Extreme-pressure long-life industrial lubricant composition |
| CN103320199A (en) * | 2012-03-22 | 2013-09-25 | 中国石油天然气股份有限公司 | Screen phenol-containing thiadiazole type antioxygen antiwear additive and preparation method thereof |
-
2016
- 2016-04-18 CN CN201610238048.5A patent/CN107304378B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5336420A (en) * | 1991-05-08 | 1994-08-09 | Mobil Oil Corporation | Antioxidants for functional fluids |
| US5177212A (en) * | 1991-07-26 | 1993-01-05 | R.T. Vanderbilt Company, Inc. | Phenolic derivatives of 2,5-dimercapto-1,3,4-thiadiazoles |
| CN101830865A (en) * | 2010-03-19 | 2010-09-15 | 华东交通大学 | Hydroxyl-containing thiadiazole derivate as well as preparation method and application thereof |
| CN102690703A (en) * | 2011-03-24 | 2012-09-26 | 中国石油化工股份有限公司 | Extreme-pressure long-life industrial lubricant composition |
| CN103320199A (en) * | 2012-03-22 | 2013-09-25 | 中国石油天然气股份有限公司 | Screen phenol-containing thiadiazole type antioxygen antiwear additive and preparation method thereof |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111088098A (en) * | 2018-10-23 | 2020-05-01 | 中国石油化工股份有限公司 | High-temperature chain oil composition and preparation method thereof |
| CN111088098B (en) * | 2018-10-23 | 2022-10-21 | 中国石油化工股份有限公司 | High-temperature chain oil composition and preparation method thereof |
| CN114479993A (en) * | 2020-11-12 | 2022-05-13 | 中国石油天然气股份有限公司 | Chain oil composition compatible with water-based paint and preparation method thereof |
| CN117757551A (en) * | 2023-12-12 | 2024-03-26 | 浙江康力博石化有限公司 | High-temperature anti-coking food-grade chain lubricating oil and preparation method thereof |
| CN117757551B (en) * | 2023-12-12 | 2024-05-31 | 浙江康力博石化有限公司 | High-temperature anti-coking food-grade chain lubricating oil and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107304378B (en) | 2019-08-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107304380A (en) | A kind of air compressor oil composition and preparation method thereof | |
| CN107304378A (en) | A kind of high-temperature chain oil composition and preparation method thereof | |
| CN106318523A (en) | Motorcycle engine lubricating oil composition and preparation method thereof | |
| CN106318519B (en) | A kind of gasoline engine oil lubricant oil composite and preparation method thereof | |
| CN106318555A (en) | Metal processing lubricating oil composition and preparation method thereof | |
| CN106318554B (en) | A kind of gasoline engine oil lubricant oil composite and preparation method thereof | |
| CN106318557B (en) | A kind of methanol-fueled engine lubricant oil composite and preparation method thereof | |
| CN106318553A (en) | Automatic transmission fluid lubricating oil composition and preparation method thereof | |
| CN106318552A (en) | Hydraulic lubricating oil composition and preparation method thereof | |
| CN106318534A (en) | Metal processing lubricating oil composition and preparation method thereof | |
| CN106318518A (en) | Automatic transmission fluid lubricating oil composition and preparation method thereof | |
| CN107304377A (en) | A kind of high-temperature chain oil composition and preparation method thereof | |
| CN106318536A (en) | Hydraulic lubricating oil composition and preparation method thereof | |
| CN106318546A (en) | Lubricating oil composition for diesel engine and preparation method thereof | |
| CN107304381A (en) | A kind of combustion gas turbine oil composition and preparation method thereof | |
| CN106318535A (en) | Vehicle gear lubricating oil composition and preparation method thereof | |
| CN107304382A (en) | A kind of air compressor oil composition and preparation method thereof | |
| CN106318532A (en) | Lubricating oil composition and preparation method thereof | |
| CN107304379A (en) | A kind of combustion gas turbine oil composition and preparation method thereof | |
| CN106318520A (en) | Lubricating oil composition and preparation method thereof | |
| CN106318558B (en) | A kind of motorcycle engine lubricant oil composite and preparation method thereof | |
| CN106318556A (en) | Vehicle gear lubricating oil composition and preparation method thereof | |
| CN106318559A (en) | Gas engine lubricating oil composition and preparation method thereof | |
| CN106318547B (en) | A kind of methanol-fueled engine lubricant oil composite and preparation method thereof | |
| CN106590852B (en) | A kind of industrial lubrication fluid composition and its manufacturing method |
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 | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20210629 Address after: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen Patentee after: China Petroleum & Chemical Corp. Patentee after: SINOPEC CORP Research Institute OF PETROLEUM PROCESSING Patentee after: Beijing General Fine Chemical Technology Development Co.,Ltd. Address before: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen Patentee before: China Petroleum & Chemical Corp. Patentee before: SINOPEC CORP Research Institute OF PETROLEUM PROCESSING |
|
| TR01 | Transfer of patent right |