CN106833808A - A kind of lube oil additive, the lubricating oil for adding it, preparation method and purposes - Google Patents
A kind of lube oil additive, the lubricating oil for adding it, preparation method and purposes Download PDFInfo
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- CN106833808A CN106833808A CN201710060623.1A CN201710060623A CN106833808A CN 106833808 A CN106833808 A CN 106833808A CN 201710060623 A CN201710060623 A CN 201710060623A CN 106833808 A CN106833808 A CN 106833808A
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- 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
- C10M125/00—Lubricating compositions characterised by the additive being an inorganic material
- C10M125/02—Carbon; Graphite
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- 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
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Abstract
The present invention relates to a kind of lube oil additive, the additive includes the modified graphite alkenes material aoxidized by TEMPO classes catalyst.The invention provides a kind of lube oil additive, using TEMPO class catalyst graphite oxide alkenes materials, oxy radical (such as hydroxyl is increased in graphite alkenes material, carboxyl etc.) content, increased the hydrophily of graphite alkenes material, then there is the modified graphene with addition substrate oil in the form of dispersion liquid by dispersed, emulsified, realize phase transfer of the modified graphene by microemulsified, it is transferred in substrate oil, obtain the modified lubricating oil of Graphene, method is simple, efficiently, feasibility is good, and while lube base quality is met, also improve its lubricant effect.
Description
Technical field
The invention belongs to technical field of lubricating oil, lubricating oil, the preparation method for be related to a kind of lube oil additive, adding it
And purposes.
Background technology
In industrial production running at full capacity at this stage, the industry such as machine-building, mine metallurgy, chemical industry, medicine, food is direct
It is related to the development of national economy, the fretting wear of machinery equipment part consumes the substantial amounts of energy and resource, it was reported that three points of the whole world
One of energy resource consumption in friction, and the quantity that is failed by fretting wear of various machine components accounts for whole failure parts
More than 80%.It is the world by the way of lubrication in addition to material treatment in itself to extend the service life of part
In the range of general way.How to ensure the normal operation of machinery, reduce the maintenance cost of equipment just into key issue.
Lubricating oil, as a kind of important and extensive petroleum product of use, is indispensable in modern industry.For
Increase the antiwear and friction reduction property of lubricating oil to the full extent, a certain amount of additive, but tradition are often added in lubricating oil
Sulphur, phosphorus and chlorine type antiwear additive would generally corrode friction pair material and produce exhaust emission environment.Therefore, find a kind of
The additive tool of novel environment friendly high-efficiency is of great significance.
In recent years, with the development of nanosecond science and technology, nano material is increasingly extensive as the research of lube oil additive,
CN1632081 discloses a kind of nano carbon lubricating additive, and nano-carbon material as lube oil additive is significantly improved
The abrasion resistance of lubricating oil.
Graphene has the unrivaled advantage of many other materials as a kind of novel nano carbon material, such as has good
Mechanical property, thermal conductivity high etc., special two-dimensional slice structure is conducive to reducing and rubs, therefore Graphene is a kind of preferable
Lube oil additive.Graphene and Nano diamond compounding will be given full play into the advantage of the two, profit is improved to the full extent
The abrasion resistance of lubricating oil.But the nano materials such as Graphene and Nano diamond are due to the potential energy easily group of generation in surface higher
It is poly-, it is not good so as to cause its dispersiveness in lubricating oil, it is also easy to produce layering and precipitates, the performance of final influence lubricating oil.
How to solve the dispersiveness of Graphene and Nano diamond in lubricating oil is a problem demanding prompt solution.
The content of the invention
An object of the present invention is to provide a kind of lube oil additive, and the additive includes being urged by TEMPO classes
The modified graphite alkenes material of agent catalysis oxidation.
For graphite alkenes material, it is directly dispersing in exist in lubricating oil or base oil such as reunites, disperses unequal
Defect, realize it is dispersed relatively difficult, the present invention graphite alkenes material is modified by TEMPO classes catalyst, and general
On the one hand modified graphite alkenes material passes through as lube oil additive, TEMPO class catalyst modification graphite alkenes material
TEMPO class catalyst may be inserted into and bring it about in aggregate swelling, be separated from each other aggregate, be conducive to tending to disperse, if
Again plus external force grinding or concussion are more beneficial for it and scatter；On the other hand it is a certain amount of due to that may contain in graphite alkenes material
Hydroxyl or with other groups exist oxygen element, especially graphene oxide or biomass Graphene, are urged by TEMPO
Change oxidation system by oxygen-containing functional group (especially hydroxyl) oxidation above graphite alkenes material so that between graphite alkenes material
Mutually strut, and further the graphene layer reunited scatter, and then progressively aoxidize, so on the one hand improve graphite
The chemism on olefinic substance surface, on the other hand improves dispersion of the graphite alkenes material in most of solvent (water, alcohol, ketone)
Degree.The lube oil additive that the present invention is provided is added into substrate oil, can reduce the reunion of graphite alkenes material, promotes graphite
Alkenes material is dispersed in substrate oil.
TEMPO classes catalyst includes TEMPO (2,2,6,6- tetramethyl piperidines-nitrogen-oxide) and TEMPO derivatives.
The present invention is not specifically limited to TEMPO class catalyst, as long as the catalyst including N- oxygen radicals is used equally to the present invention.
Preferably, the TEMPO classes catalyst include 2,2,6,6- tetramethyl piperidines-nitrogen-epoxide, 2-aza-adamantane-
N- epoxides, 1- methyl -2-aza-adamantane-N- epoxides, 1,3- dimethyl -2-aza-adamantane-N- epoxides, 4- hydroxyls TEMPO
Any a kind or at least 2 kinds of combination in derivative.
Preferably, the TEMPO classes catalyst is connect in the form of TEMPO class aqueous catalyst solutions with graphite alkenes material
Touch, carry out catalysis oxidation.
It is uniform mixed with graphite alkenes material that the form of TEMPO class aqueous catalyst solutions is more favorable for TEMPO classes catalyst
Close.
Preferably, also it is added with halide salt, and hypohalite in the TEMPO classes catalyst oxidizing process
Any a kind or at least 2 kinds of combination.
Preferably, the hypohalite includes hypochlorite and/or hypoiodite.
Preferably, the halide salt includes Bromide and/or iodized salt.
TEMPO and/or its derivative, halide salt can rapidly in catalysis oxidation graphite alkenes material alcohol group life
Into aldehydes or ketones, and then carboxyl is oxidized in the presence of hypohalite.
Preferably, the hypohalite is added in form of an aqueous solutions, concentration be 5~15wt%, such as 6wt%,
7wt%, 8wt%, 9wt%, 10wt%, 11wt%, 12wt%, 13wt%, 14wt% etc..
Preferably, the hypohalite is dividedly in some parts, and is firstly added the 10~30% of gross mass to be added, one section to be mixed
Remainder is added after time.
Exemplarily, the preparation method of the modified graphene is：It is made into by TEMPO and/or its derivative and with NaBr
The aqueous solution, stirring and dissolving is complete, obtains mixed liquor, is subsequently added graphite alkenes material and continues to stir, and then adds hypohalite
The 10~30% of solution total amount, stirring reaction, remaining 70% is gradually added into.
Preferably, the halide salt includes Bromide and/or iodized salt.
Preferably, the cation in the halide salt and hypohalite include alkali metal ion, preferably include sodium ion and/
Or potassium ion.
Those skilled in the art are it will be clearly understood that TEMPO class catalyst need to rely on TEMPO catalyst system and catalyzings, but this hair
It is bright to be not limited to any specific TEMPO catalyst system and catalyzings, the TEMPO catalyst system and catalyzings that any those skilled in the art be known
It is used equally to the present invention.
Exemplarily, the TEMPO catalyst system and catalyzings be include TEMPO classes catalyst, hypohalite, halide salt it is water-soluble
Liquid, preferably to include the aqueous solution of 2,2,6,6- tetramethyl piperidine nitrogen oxides, sodium hypochlorite, sodium bromide；The TEMPO
Class aqueous catalyst solution pH is preferably 9.5~11.5, more preferably 10-11.
When the TEMPO classes aqueous catalyst solution is TEMPO classes catalyst, hypohalite, the aqueous solution of halide salt, pH
Preferably 9.5~11.5, now the catalysis oxidation efficiency is high.
Used as another example, the TEMPO catalyst system and catalyzings are to include TEMPO classes catalyst, hypohalite, perchloric acid
Salt and/or the chloritic aqueous solution, preferably include 2,2,6,6- tetramethyl piperidine nitrogen oxides, sodium hypochlorite, sub- chlorine
The aqueous solution of sour sodium；The TEMPO classes aqueous catalyst solution pH is preferably 3.5~6, further preferred 4~5.
When the TEMPO classes aqueous catalyst solution is acidity, include TEMPO classes catalyst, hypohalite, perchlorate
And/or during the chloritic aqueous solution, pH is preferably 3.5~6, and now the catalysis oxidation efficiency is high.
The control method of the pH of the TEMPO classes aqueous catalyst solution it is exemplary be：Add sodium hydroxide solution and/or
Glacial acetic acid solution is adjusted, and its content is respectively 0.5~5wt%, can be 1wt%, 2wt%, 4wt% etc..
It is further preferred that in the catalytic oxidation process, the TEMPO classes aqueous catalyst solution is alkalescence, is included
TEMPO classes catalyst, hypohalite, the aqueous solution of halide salt, preferably include 2,2,6,6- tetramethyl piperidine nitrogen oxides,
The aqueous solution of sodium hypochlorite, sodium bromide；The TEMPO classes aqueous catalyst solution pH is preferably 9.5~11.5, more preferably
10-11。
Preferably, in the TEMPO classes aqueous catalyst solution catalytic oxidation process, the addition of TEMPO class catalyst is
The 0.05%~5% of graphite alkenes substance weight, it is exemplary be 0.1%, 0.3%, 0.8%, 1%, 1.2%, 1.5%,
2.5%th, 3.5%, 4%, 4.5% etc.；It is preferred that 0.1%~3%, further preferably 0.3%~2%, more preferably 0.5%-1%.
Preferably, the addition of the hypohalite is the 10%~500% of graphite alkenes substance weight, exemplary to be
50%th, 70%, 100%, 120%, 135%, 160%, 200%, 300%, 400%, 450% etc., preferably 30%~95%, then
It is preferred that 40%-75%.
Preferably, the addition of the halide salt is the 0.5%~50% of graphite alkenes substance weight, it is exemplary be 3%,
8%th, 10%, 12%, 15%, 18%, 25%, 35%, 45% etc., preferably 10%~30, further preferably 3%~20%, more preferably
5%~10%.
Preferably, the additive includes the modified graphite alkenes thing that powder shaped is aoxidized by TEMPO classes catalyst
Matter, the aqueous solution and TEMPO classes that are dispersed with the modified graphite alkenes material that powder shaped is aoxidized by TEMPO classes catalyst
Any a kind or at least 2 kinds of combination in the reaction solution of catalyst graphite oxide alkenes material.
Used as optimal technical scheme, the reaction solution of the TEMPO classes catalyst graphite oxide alkenes material is by such as
It is prepared by lower section method：By graphite alkenes material under the oxidation of TEMPO classes catalyst, catalytic oxidation is carried out, until reaction
The pH of system is constant or adds alcohols material terminating reaction, obtains the anti-of TEMPO class catalyst graphite oxide alkenes materials
Answer liquid；
Preferably, in the reaction solution of the TEMPO classes catalyst graphite oxide alkenes material, in terms of Graphene, instead
The concentration of graphite alkenes material in liquid is answered for below 20mg/g, such as 1.5mg/g, 1.8mg/g, 2.3mg/g, 2.7mg/g,
3.5mg/g、4.3mg/g、4.8mg/g、5.5mg/g、6.4mg/g、7.7mg/g、8.5mg/g、9.6mg/g、10.5mg/g、
12mg/g, 13mg/g, 14mg/g, 15mg/g, 18mg/g etc., preferably 1~10mg/g, further preferred 3~5mg/g.
As the modified graphite alkenes thing that optimal technical scheme, the powder shaped are aoxidized by TEMPO classes catalyst
Matter is prepared via a method which：By the reaction solution washing of TEMPO class catalyst graphite oxide alkenes materials, dry, obtain
The modified graphite alkenes material that powder shaped is aoxidized by TEMPO classes catalyst.
Exemplarily, the dry method is preferably：Freezing processing 10 under conditions of product is placed in into -20~-25 DEG C
~20h, is then placed on carrying out pre-freeze in the cold-trap of freeze drier, and the condenser temperature of freeze drier is -50~-80
℃；Pre-freeze terminate after under 1~10Pa of vacuum 24~48h of freeze-drying.
It is described to be dispersed with the modified graphite that powder shaped is aoxidized by TEMPO classes catalyst as optimal technical scheme
The aqueous solution of alkenes material is prepared via a method which：The modified graphite that powder shaped is aoxidized by TEMPO classes catalyst
Alkenes material is dispersed in water, and obtains being dispersed with the modified graphite alkenes thing that powder shaped is aoxidized by TEMPO classes catalyst
The aqueous solution of matter.
Preferably, it is described to be dispersed with modified graphite alkenes material that powder shaped is aoxidized by TEMPO classes catalyst
In the aqueous solution, in terms of Graphene, the concentration of graphite alkenes material is below 20mg/g, such as 1.5mg/g, 1.8mg/ in reaction solution
g、2.3mg/g、2.7mg/g、3.5mg/g、4.3mg/g、4.8mg/g、5.5mg/g、6.4mg/g、7.7mg/g、8.5mg/g、
9.6mg/g, 10.5mg/g, 12mg/g, 13mg/g, 14mg/g, 15mg/g, 18mg/g etc., preferably 1~10mg/g, it is further excellent
Select 3~5mg/g.
The material with graphene film Rotating fields is can be understood as graphite alkenes material of the present invention, for institute
Graphite alkenes material is stated, the present invention is not specifically limited, the material with SP2 hydridization carbon plate Rotating fields that can be dispersed in water
It is used equally to the present invention.
Preferably, the graphite alkenes material includes that Graphene, biomass Graphene, graphene oxide, Graphene derive
Any a kind of thing or at least 2 kinds of mixing, preferably biomass Graphene and/or graphene oxide.
Preferably, the Graphene derivative includes any 1 in element doping Graphene or functional group's graphite alkene thing
Kind or at least 2 kinds of combination.
Wherein, biomass Graphene is to contain single-layer graphene, few layer graphene, graphite with biomass as prepared by raw material
Alkene nano-lamellar structure, and carried metal/nonmetallic compound, the number of plies are not more than 10 layers of two-dimensional nano Carbon Materials, or even can
Be more than on the basis of the carbon composite comprising graphitized charcoal, metal/non-metal compound；The biomass Graphene is also
Including the Graphene by being prepared to biomass resource hydrothermal carbonization method.
Preferably, the biomass Graphene uses the biomass Graphene of Jinan holy well company, i.e., with agriculture and forestry organic waste material
It is primary raw material, the carbon nanomaterial compound containing Graphene obtained by steps such as hydrolysis, catalytic treatment, heat treatments,
It is mainly characterized by containing Graphene, agraphitic carbon and non-carbon nonoxygen element, and the non-carbon nonoxygen element includes Fe, Si and Al unit
Element, the non-carbon nonoxygen element content is the 0.5wt%~6wt% of compound.If number of patent application is 201510819312.X
The product of preparation.The leading indicator of the biomass Graphene it is exemplary can be：Electrical conductivity ＞ 3000S/m, preferably ＞
5000S/m；Specific surface area ＞ 150m2/ g, preferably ＞ 300m2/g；Raman spectrum IG/ID ＞ 2, preferably ＞ 3；C/O ＞ 35.0.
Preferably, the Graphene derivative includes any 1 in element doping Graphene or functional group's graphite alkene thing
Kind or at least 2 kinds of combination.
Preferably, the element doping Graphene is including in metal-doped Graphene or nonmetal doping Graphene
Any a kind or at least 2 kinds of combination.
The metal-doped metallic element it is typical but non-limiting including potassium, sodium, gold, silver, iron, copper, nickel, chromium, titanium,
Any a kind or at least 2 kinds of combination in vanadium or cobalt.
The nonmetal doping Graphene it is typical but non-limiting including nitrogen, phosphorus, silicon, boron or oxygen in any 1
Kind or at least 2 kinds of combination.
Doped chemical in the element doping Graphene it is exemplary can be potassium and nitrogen combination, iron, titanium and silicon
Combination, the combination of vanadium, cobalt and phosphorus, gold, the combination of nickel and oxygen, the combination of nickel, chromium and vanadium, the combination of potassium, nitrogen and phosphorus, iron, potassium,
Combination of nitrogen, phosphorus and oxygen etc..
Preferably, the nonmetal doping Graphene includes nitrogen-doped graphene, phosphorus doping Graphene or sulfur doping
Any a kind or at least 2 kinds of combination in Graphene.
Preferably, functional group's graphite alkene includes being grafted with the Graphene of functional group.
Preferably, functional group's graphite alkene includes any a kind or at least 2 be grafted with hydroxyl, carboxyl or amino
The Graphene of the combination planted.
Those skilled in the art are it will be clearly understood that in the Graphene of the function dough, can also be grafted people in the art
It is any to the helpful functional group of dispersed graphite alkenes material that member is obtained in that.
Preferably, the hydroxyl includes-R1- OH, the R1Including alkyl, preferably include methyl, ethyl, propyl group, butyl,
Any a kind or at least 2 kinds of combination in amyl group, hexyl, vinyl, acrylic.
Preferably, the carboxyl includes-R2- COOH, the R2Including alkyl, methyl, ethyl, propyl group, fourth are preferably included
Any a kind or at least 2 kinds of combination in base, amyl group, hexyl.
Preferably, the carboxyl includes R3-NH3, the R3Including alkyl, methyl, ethyl, propyl group, fourth are preferably included
Any a kind or at least 2 kinds of combination in base, amyl group, hexyl.
The two of the object of the invention are to provide a kind of modification of lubricating oils, are added with described in the first purpose in the modification of lubricating oils
Lube oil additive.
Preferably, the amount of graphite alkenes material is 0.005~3wt% of substrate oil in the modification of lubricating oils, for example
0.006wt%, 0.008wt%, 0.014wt%, 0.022wt%, 0.035wt%, 0.065wt%, 0.078wt%,
0.089wt%, 0.093wt%, 0.121wt%, 0.126wt%, 0.128wt%, 0.131wt%, 0.136wt%,
0.138wt%, 0.141wt%, 0.146wt%, 0.148wt%, 0.151wt%, 0.156wt%, 0.158wt%,
0.161wt%, 0.166wt%, 0.168wt%, 0.171wt%, 0.176wt%, 0.178wt%, 0.181wt%,
0.186wt%, 0.188wt%, 0.191wt%, 0.196wt%, 0.198wt%, 0.202wt%, 0.206wt%,
0.209wt%, 0.222wt%, 0.236wt%, 0.249wt%, 0.252wt%, 0.266wt%, 0.279wt%,
0.282wt%, 0.296wt% etc., preferably 0.01~0.1wt%, further preferred 0.01~0.05wt%.
Graphite alkenes material in substrate oil of the present invention is introduced by lube oil additive.
Preferably, described is to be added dropwise from dropwise addition by the feed postition that modified graphene dispersion liquid is added into substrate oil
Mode adds into substrate oil graphite alkenes material dispersion liquid, advantageously in graphite alkenes material dispersion liquid in substrate oil
Dispersion.
The rate of addition is preferably 0.5~20mL/min, such as 0.6mL/min, 0.7mL/min, 1.5mL/min,
1.8mL/min, 3mL/min, 5mL/min, 8mL/min, 12mL/min, 15mL/min, 18mL/min etc..
Preferably, any a kind or at least 2 including finished lube, semi-finished product lubricating oil and base oil of the substrate oil
The combination planted.
Substrate oil of the present invention can be understood as not containing graphite alkenes material and Nano diamond finished lube,
Do not contain the semi-finished product lubricating oil of graphite alkenes material and Nano diamond or do not contain graphite alkenes material and nanometer Buddha's warrior attendant
The base oil for making lubricating oil of stone.
The finished lube can be market any profit for not containing graphite alkenes material and Nano diamond on sale
Lubricating oil, wherein contain base oil, and lube oil additive, the lube oil additive include it is well known in the art it is any can
Be added to the functional additive in lubricating oil, such as antioxidant, antiwear additive, friction modifier, EP agent, detersive,
Dispersant, foam in hibitors, corrosion prevention rust preventer, flow point improver, viscosity index improver etc..
The base oil, alternatively referred to as lube base oil, are the oil bases for being not added with any additive, including mineral base
Any a kind or at least 2 kinds of combination in oil, synthetic base oil or biological basis oil.
The semi-finished product lubricating oil be from base oil to finished lube during, the oil of any processing time section
Product, it is only necessary to which satisfaction does not contain graphite alkenes material and Nano diamond and can be used as substrate oil of the invention.
Those skilled in the art are it will be clearly understood that what the present invention was modified is not add graphite alkenes material (including biology
The graphite alkenes such as matter Graphene, Graphene derivative material) and Nano diamond base oil or product oil or semi-finished product oil, it is right
It is modified by step of the present invention in base oil or semi-finished product oil, correlation can also be continuously added according to prior art
Functional additive, such as antioxidant, antiwear additive, friction modifier, EP agent, detersive, dispersant, foam suppress
Agent, corrosion prevention rust preventer, flow point improver, viscosity index improver etc., addition are referred to feature in the prior art and add
Plus the addition of agent.
Preferably, the base oil include mineral base oil, synthetic base oil or biological basis oil in any a kind or extremely
Few 2 kinds combination.
Preferably, Nano diamond is also added with the modification of lubricating oils, the modified nm of gold of oleophylic is preferably added with
Hard rock.
Nano diamond can be dispersed between the lamellar structure of graphite alkenes material, and graphite alkenes material is by with molten
The form of liquid is dispersed in lubricating oil, while realizing the dispersed of Nano diamond, can farthest be played
The greasy property of both materials, plays synergy, reduces friction.
Preferably, the Nano diamond account for substrate oil 0.01~0.1wt%, such as 0.02wt%, 0.03wt%,
0.04wt%, 0.05wt%, 0.06wt%, 0.07wt%, 0.08wt%, 0.09wt% etc..
Preferably, the particle diameter of the Nano diamond is in below 20nm, such as 19nm, 18nm, 17nm, 16nm, 15nm,
14nm, 13nm, 12nm, 11nm, 10nm, 9nm, 8nm, 7nm, 6nm, 5nm, 4nm, 3nm, 2nm, 1nm, 0.5nm etc., preferably 10nm
Hereinafter, preferably 4~8nm.
Preferably, the modified Nano diamond of the oleophylic is prepared via a method which to obtain：
A be distributed to unmodified Nano diamond in dispersion liquid by ()；
(b) and then mix with modifying agent；
C () stirring reaction obtains the modified Nano diamond solution of oleophylic.
Preferably, the dispersion liquid includes the combination of any a kind or at least 2 kinds in petroleum ether, oleic acid, atoleine.
Preferably, the modifying agent includes the combination of coupling agent and ashless dispersant.
The addition of ashless dispersant can make during oil product use due to oxidation or other chemical actions formed it is insoluble
Material keeps suspending, and prevents greasy filth from condensing and insoluble matter precipitation；And prevent soot particles from condensing, and reduce and glue during use
The growth of degree.
Preferably, the coupling agent include titanium class coupling agent, tin class coupling agent, silicon class coupling agent in any a kind or extremely
Few 2 kinds combination, preferably titanate coupling agent.
Preferably, the ashless dispersant includes that succimide, succinate, boronation succimide, succinyl are sub-
Any a kind or at least 2 kinds of combination in amino acid and its derivative.
Preferably, ashless dispersant includes T151 dispersants (mono alkenyl succimide), T152 dispersants (double focusing isobutyl
Imidodicarbonic diamide), the combination of any a kind of T154 dispersants (polyisobutene succinimide) or at least 2 kinds, further preferably
T154 dispersants (polyisobutene succinimide).
Those skilled in the art it will be clearly understood that the unmodified Nano diamond can be obtained by prior art, this
Invention is not specifically limited, and exemplary described unmodified Nano diamond passes through trinitrotoluene and/or ring trimethylene
Generated after the blast of trintriamine composite explosives.
Preferably, the purity of the Nano diamond be more than 50wt%, preferably more than 75wt%, further preferably
More than 90wt%, particularly preferred more than 95wt%.
Preferably, in the preparation method of the modified Nano diamond of the oleophylic, mixing time preferred more than 10min is excellent
Select 0.5~10h, further preferred 2~8h, particularly preferred 4~6h.
The present invention is not specifically limited to whipping temp, can realize that the temperature of back flow reaction is capable of achieving the present invention, shows
Example property ground, the whipping temp be 70~120 DEG C, such as 72 DEG C, 76 DEG C, 78 DEG C, 83 DEG C, 88 DEG C, 92 DEG C, 95 DEG C, 99 DEG C,
103 DEG C, 108 DEG C, 115 DEG C, 118 DEG C etc..
Preferably, the solvent of the modifier solution includes any a kind or at least 2 in petroleum ether, oleic acid, atoleine
The combination planted.
Preferably, the concentration of Nano diamond is in the Nano diamond solution that the oleophylic that the step (c) obtains is modified
Below 3wt%, such as 0.5wt%, 0.7wt%, 0.9wt%, 1.1wt%, 1.3wt%, 1.5wt%, 1.7wt%,
1.9wt%, 2.1wt%, 2.3wt%, 2.5wt%, 2.7wt%, 2.9wt% etc., preferably below 2wt%, further preferred 0.5
~1.5wt%, particularly preferred 0.8~1.2wt%.
Nano diamond addition is excessive, is not it is obvious that and being susceptible to reunite to properties of product lifting.
Preferably, coupling agent concentrations for dispersion liquid quality 5~20wt%, such as 6wt%, 9wt%, 1.1wt%,
13wt%, 15wt%, 17wt%, 19wt% etc., preferably 8~13wt%；
Preferably, ashless dispersants agent concentration for dispersion liquid quality 5~20wt%, such as 6wt%, 9wt%, 1.1wt%,
13wt%, 15wt%, 17wt%, 19wt% etc., preferably 8~13wt%.
The three of the object of the invention are to provide a kind of preparation method of the modification of lubricating oils as described in the second purpose, methods described bag
Include following steps：
Lube oil additive is added into substrate oil, after emulsification, the water phase in removal emulsion obtains modified lubrication
Oil.
Preferably, the lube oil additive is added into substrate oil in liquid form.
It is further preferred that the lube oil additive is aoxidized with being dispersed with powder shaped by TEMPO classes catalyst
Modified graphite alkenes material the aqueous solution form add to substrate oil in.
The present invention will disperse the aqueous solution of graphite alkenes material to add during into substrate oil, and water phase and oil phase occur breast
Change, graphite alkenes material can realize the transfer from the opposite oil phase of water, complete uniform point of graphite alkenes material in substrate oil
Dissipate.
Preferably, the preparation method of the modification of lubricating oils adds Nano diamond after the water phase in removing emulsion,
It is uniformly dispersed；
Preferably, the Nano diamond is the Nano diamond solution that oleophylic is modified.
The mode of emulsification of the present invention is not particularly limited, emulsifying manner that any those skilled in the art can be known
It is used equally to the present invention.
The mode of the emulsification includes concussion emulsion process, stirring and emulsifying method, syringe emulsion process, ultrasonic emulsification, grinds
Any a kind or at least 2 kinds of combination in alms bowl emulsion process, preferably stirring and emulsifying method and/or concussion emulsion process.
When stirring and emulsifying method is selected, graphite alkenes material dispersion liquid can be selected with the speed of 0.5~2mL/min, one
While in dropping to substrate oil, while being stirred, realizing emulsification.
Preferably, the mixing speed of the stirring and emulsifying method is 3000~5000r/min, such as 3200r/min, 3500r/
Min, 3700r/min, 4300r/min, 4500r/min, 4700r/min, 4900r/min etc., 70~80 DEG C of whipping temp, for example
71 DEG C, 72 DEG C, 73 DEG C, 74 DEG C, 75 DEG C, 76 DEG C, 77 DEG C, 78 DEG C, 79 DEG C etc..
In lubricating oil, the presence of water can influence the lubricant effect of lubricating oil, it is possible to cause the corrosion to lubricating component
Problem, therefore moisture therein is needed away in lubricating oil.The present invention is not specifically limited for removing the method for water phase.
Preferably, the method for the water phase in the removal emulsion includes layering except water law, distillation are except water law, heating volatilization
Except water law, dry except the combination of any a kind or at least 2 kinds in water law.
Preferably, the layering removes water law, ultrasonic emulsion breaking layering except water law or centrifugation are broken except water law includes that demulsifier is layered
Breast layering is except the combination of any a kind or at least 2 kinds in water law.
Being meant that for the combination can be the combination of any water removal phase method and/or any group being layered except water law
Close, exemplary can first carry out demulsifier layering except water law, remove most water phase, add drier to be done afterwards
Dry water removal；Or can first carry out ultrasonic emulsion breaking layering except water law, most of water phase is removed, heating volatilization is carried out afterwards to be removed
Water phase etc..
After removing water phase step, the moisture in lubricating oil disclosure satisfy that the relevant regulations of country, such as meets and contains
Water is less than 0.1%, under normal circumstances less than 0.03%, such as requirement of GB GB/T 260-1977.
Preferably, the demulsifier is layered except water law comprises the following steps：To demulsifier is added in the product after emulsification, make
Water phase and oil phase are layered, and remove water phase；It is preferred that continuously adding drier in the oil phase that layering is obtained except water law, remove remaining
Water phase.
The present invention is not particularly limited to demulsifier, and typical but non-limiting demulsifier of the present invention can be selected from amine
With the block copolymer of epoxide condensation product T1001, polyether type high polymer demulsifier DL32, oxirane and expoxy propane
T1002, LZ5957 etc..
Preferably, the distillation removes water law includes atmospheric distillation and/or distillation under vacuum, and the purpose of vacuum distillation is
Accelerate evaporation rate, reduce heating-up temperature.
Preferably, the boiling point of the vapo(u)rizing temperature less than the base oil of the distillation water removal.
Preferably, the vacuum distillation includes rotary evaporation.
Preferably, the heating volatilization is except the boiling point of the heating-up temperature less than the base oil of water law.
Preferably, the drying is except water law is including adding drier water removal.
But if containing the Graphene after function dough or element doping in modified graphite alkenes material, its function for containing
The element of group or doping there is no baneful influence to lubricating oil quality or also there is benefit may reside in the stone for preparing
In black alkene modification of lubricating oils, if there is significantly influence inferior for the quality of lubricating oil, it is necessary to be removed, to meet
Relevant regulations.Minimizing technology can be the element of the functional group or doping that whole is removed by reduction step, or remove part
Functional group or doping element, the species of specific removal is not specifically limited, it is only necessary to meets the lubricating oil after removal and meets
Relevant regulations, and the mode for removing also is not specifically limited.
Preferably, after the water phase in emulsion process and/or in removal emulsion, reduction treatment is carried out.
The mode of the oxygen-containing matrix removal in modified graphene can be included into following three kinds of modes：
Mode one：Alternatively, reduction step is carried out in emulsion process, for removing the part in the modified graphene
Or whole oxygen-containing functional groups.
Mode two：Alternatively, reduction step is carried out after the water phase in removal emulsion, for removing the modified graphene
In part or all of oxygen-containing functional group.
Mode three：Alternatively, reduction step is carried out in emulsion process, and is carried out after the water phase in removing emulsion
Reduction step, for removing the part or all of oxygen-containing functional group in the modified graphene.
Preferably, the method for the reduction treatment includes reducing agent reducing process and/or heating reducing process.
Preferably, the reducing agent reducing process includes adding reducing agent to be reduced.
Preferably, the addition of the reducing agent is 10~200wt%, the preferably 50~100wt% of graphite alkenes material,
Such as 15wt%, 18wt%, 23wt%, 27wt%, 50wt%, 70wt%, 90wt%, 105wt%, 120wt%, 150wt%,
165wt%, 170wt%, 190wt% etc., preferably 50~100wt%.
Preferably, the reducing agent includes ascorbic acid, hydrazine hydrate, ethylenediamine, sodium citrate, Cys, hydrogen iodine
Any a kind or at least 2 kinds of combination in acid or sodium borohydride.
Preferably, the heating reducing process is included in non-oxidizing atmosphere, and heating is reduced.
Preferably, the heating reducing process step includes：In autoclave, protective atmosphere and/or reduction are passed through
Property atmosphere, heating reduction；Temperature≤200 DEG C of the heating reduction, pressure≤1.6MPa.
Reduction temperature too high destroys the greasy property of lubricating oil, and too low reduction temperature does not reach reduction effect.
As optional technical scheme, Nano diamond is added after the water phase in the removal emulsion, be uniformly dispersed.
The four of the object of the invention are to provide a kind of purposes of the modification of lubricating oils as described in the second purpose, the modified lubrication
Lubrication of the oil for mechanical structure.
Compared with prior art, the invention has the advantages that：
(1) the invention provides a kind of lube oil additive, using TEMPO class catalyst graphite oxide alkenes things
Matter, increases the content of oxy radical (such as hydroxyl, carboxyl) in graphite alkenes material, increased the parent of graphite alkenes material
It is aqueous, then there is the modified graphene in addition substrate oil in the form of dispersion liquid, to be emulsified by dispersed, realize changing
Property the Graphene phase transfer that passes through microemulsified, be transferred in substrate oil, obtain the modified lubricating oil of Graphene, method is simple, high
Effect, feasibility is good, and while lube base quality is met, also improves its lubricant effect；
(2) in optimal technical scheme, present invention cooperation addition Nano diamond, the Nano diamond can be dispersed in
Between the lamellar structure of graphite alkenes material, and graphite alkenes material passes through to be dispersed in as a solution in lubricating oil,
The dispersed of Nano diamond is realized simultaneously, lubricant effect can be further improved, reduces friction.
Specific embodiment
Technical scheme is further illustrated below by specific embodiment.
Those skilled in the art it will be clearly understood that the embodiment be only to aid in understand the present invention, be not construed as to this hair
Bright concrete restriction.
C/O hereinafter refers both to weight ratio.
The selection of graphite alkenes material：
Biomass Graphene A：Preparation method is that China Patent Publication No. is CN105502330A embodiments 4, and C/O is 36.
Biomass Graphene B：Preparation method is that China Patent Publication No. is CN104016341A embodiments 7, and C/O is 40.
Biomass Graphene C：Preparation method is that China Patent Publication No. is CN104724699A embodiments 1, and C/O is 500.
Graphene D：" the model of Changzhou No.6 Element Material Technology Co., Ltd.'s production：SE1231 ", C/O are 60.
Graphene E：" the model of Changzhou No.6 Element Material Technology Co., Ltd.'s production：SE1132 ", C/O are 30.
Graphene F：" the model of Changzhou No.6 Element Material Technology Co., Ltd.'s production：SE1430 ", C/O are 6.5.
Graphene oxide G：" the model of Changzhou No.6 Element Material Technology Co., Ltd.'s production：SE2430W ", C/O
It is 1.
Preparation example 1
(1) 1g biomass Graphene A are taken, adds 200g water to stir to form uniform slurries, then add TEMPO catalysis
Oxidising composition (0.01gTEMPO, 1g sodium hypochlorite, 0.05g sodium bromides) stirring reaction, the NaOH by 0.5wt% is molten
The glacial acetic acid solution regulation of liquid and 1wt% makes the pH of reaction system be maintained in the range of 10.5-11, stops after pH no longer changes
Reaction obtains suspension, and the reaction time is 2.5h, obtains 1# modified graphene dispersion liquids.
Preparation example 2
Step (2) is carried out after preparation example 1：The 1# modified graphenes dispersion liquid filtering that preparation example 1 is obtained, and use water
Repeatedly washed, be centrifuged, each centrifugal speed is 1000rpm, each centrifugation time is 5min, final washing to suspension
PH is neutrality, and modified graphene powder is obtained after drying；The modified graphene powder is dispersed in water afterwards, obtains graphite
Alkene concentration is the 2# modified graphene dispersion liquids of 20mg/g.
Preparation example 3
It is that TEMPO catalysis oxidation composition each component contents are different from the difference of preparation example 2, specially：
0.005gTEMPO, 0.75g sodium hypochlorite, 0.1g sodium bromides, obtain the 3# modified graphenes that Graphene concentration is 10mg/g and disperse
Liquid.
Preparation example 4
It is that TEMPO catalysis oxidation composition each component contents are different from the difference of preparation example 2, specially：
0.02gTEMPO, 0.5g sodium hypochlorite, 0.05g sodium bromides, obtain the 4# modified graphenes that Graphene concentration is 3mg/g and disperse
Liquid.
Preparation example 5
It is that TEMPO catalysis oxidation composition each component contents are different from the difference of preparation example 2, specially：
0.05gTEMPO, 5g sodium hypochlorite, 0.2g sodium bromides, obtain 5# modified graphene dispersion liquids.
Preparation example 6-7
It is that TEMPO catalysis oxidation composition components are different from the difference of preparation example 2, respectively (0.01g 2- azepines are golden
Firm alkane-N- epoxides, 1g sodium hypochlorite, 0.05g KIs) and (0.01g 4- hydroxyl TEMPO, 1g sodium hypochlorite, 0.05g iodate
Sodium), obtain 6# modified graphenes dispersion liquid (preparation example 6) and 7# modified graphenes dispersion liquid (preparation example 7).
Preparation example 8-13
It is that biomass Graphene A is replaced with into biomass Graphene B, biomass graphite respectively with the difference of preparation example 2
Alkene C, Graphene D, Graphene E, Graphene F and graphene oxide G, obtain 8# modified graphenes dispersion liquid (preparation example 8), 9# and change
Property graphene dispersing solution (preparation example 9), 10# modified graphenes dispersion liquid (preparation example 10), 11# modified graphenes dispersion liquid (system
Standby example 11), 12# modified graphenes dispersion liquid (preparation example 12), 13# modified graphenes dispersion liquid (preparation example 13).
Preparation example 14
From the difference of preparation example 2 be step (1) reaction system pH it is different, its pH is existed by acid adding or alkali condition
In the range of 7.5-8.5,14# modified graphenes dispersion liquid (preparation example 14) are obtained.
Preparation example 15
It is to increase grinding steps before step (2) is dried with the difference of preparation example 2, it is specific as follows：
By product and distilled water with 1：10 quality uses ultrasonic homogeneous point that power is 400W than wiring solution-forming under normal temperature
Dissipate machine carries out decentralized processing 30min with the mixing speed of 10000rpm, obtains 15# modified graphenes dispersion liquid (preparation example 15).
Preparation example 16
It is to increase grinding steps before step (2) is dried with the difference of preparation example 2, it is specific as follows：
By product and distilled water with 1：1000 quality uses mechanical agitator than wiring solution-forming, under normal temperature with 500rpm's
Speed continuously stirs 72h, obtains 16# modified graphenes dispersion liquid (preparation example 16).
Preparation example 17
It is step (1) the catalysis oxidation time to add ethanol terminating reaction after 1.5h with the difference of preparation example 2, obtains
17# modified graphenes dispersion liquid (preparation example 17).
Embodiment 1~17：
(1) 1#~17# modified graphites aqueous solution that 20g such as preparation examples obtain is taken and with the rate uniform of 30 drop/minutes
Ground is to dropwise addition in the 1000g substrates oil in stirring (content that graphene oxide accounts for substrate oil is 0.01wt%)；
(2) after completion of dropping, the oil product of step (2) is stirred at 80 DEG C, treats that the moisture in substrate oil is waved completely
Hair, lubricating oil returns to oily, and now graphene oxide is evenly dispersed in substrate oil, obtains modification of lubricating oils.
Embodiment 18~23：
Distinctive points with embodiment 1 are that carry out step (2 ') before step (2) is specially respectively：Add 0.1g anti-bad
Hematic acid (embodiment 18), addition 0.01g ascorbic acid (embodiment 19), addition 0.05g ascorbic acid (embodiment 20), addition
0.2g ascorbic acid (embodiment 21), addition 0.1g hydrazine hydrates (embodiment 22), addition 0.1g hydroiodic acids (embodiment 23).
Embodiment 24~26
Distinctive points with embodiment 2 are that the addition of modified graphite aqueous solution is respectively 25g, 50g in step (1),
150g。
Embodiment 27
Distinctive points with embodiment 2 are that 20g modified graphite aqueous solutions in step (1) are replaced with into the modified stones of 0.4g
Black alkene powder (the modified graphene powder that i.e. step 2 of preparation example 2 is obtained after drying).
Embodiment 28
Distinctive points with embodiment 1 are to carry out step (3)~(5) after step (2)：
(3) a certain amount of Nano diamond powder is taken, is placed in petroleum ether, be uniformly dispersed after cell pulverization ultrasound
Particle diameter below 20nm nanodiamond liquid dispersion, dispersion liquid concentration is 1wt%；
(4) to adding a certain amount of dispersant T154 (double succinyl of polyisobutene in step (3) nanodiamond liquid dispersion
Imines) and titanate coupling agent TM91 (the two quality be respectively dispersion liquid 10%) back flow reaction 6h is carried out at 80 DEG C,
Obtain the nanodiamond liquid dispersion that the oleophylic that concentration is 1wt% is modified；
(5) the modified nanodiamond liquid dispersion of oleophylic for taking 50g 1wt% is added drop-wise in step (2) product, and stirring is super
Modification of lubricating oils is obtained after sound.
Embodiment 29~31
Distinctive points with embodiment 29 are that the particle diameter and dispersion liquid concentration of Nano diamond are respectively in step (3)：
Below 15nm, concentration is 2% (embodiment 29)；Below 10nm, concentration is 1.5% (embodiment 30)；Below 5nm, concentration is
0.5% (embodiment 31).
Embodiment 32
Distinctive points with embodiment 28 are that the addition of the modified nanodiamond liquid dispersion of oleophylic is in step (5)
10g。
Embodiment 33
It is that step (4) is different from the distinctive points of embodiment 28, specially：To in step (3) nanodiamond liquid dispersion
(the two quality is each to add a certain amount of dispersant T151 dispersants (mono alkenyl succimide) and titanate coupling agent TM91
From for dispersion liquid 5%)
Embodiment 34
It is that step (4) is different from the distinctive points of embodiment 28, specially：To in step (3) nanodiamond liquid dispersion
(the two quality is each to add a certain amount of dispersant T152 dispersants (double focusing isobutyl imidodicarbonic diamide) and titanate coupling agent TM91
From for dispersion liquid 20%)
Embodiment 35
Distinctive points with embodiment 28 are, Shandong zero kilometer petrochemical industry Co., Ltd in step (1)-alloy is armoring
The CAS that model lubricating oil is replaced by the magnificent mutually beneficial biochemical industry offer in Beijing is the base oil of 8002-05-9.
Comparative example 1
Using Shandong zero kilometer petrochemical industry Co., Ltd-alloy plate armour model lubricating oil.
Comparative example 2
Distinctive points with embodiment 2 are, directly by 20g concentration for the biomass Graphene A of 20mg/g is added to 1000g
In substrate oil.
Performance test：
The modification of lubricating oils of embodiment and comparative example is carried out into abrasion resistance test based on four-ball test, test condition is
40kg/1200rpm/75 DEG C/1h, 60kg/1200rpm/75 DEG C/1h and 80kg/1200rpm/75 DEG C/1h, test result is shown in Table
1。
Table 1
By table 1, it can be seen that after with the addition of the modified graphite alkenes materials of TEMPO, friction resistant performance is obviously improved, then add
The cooperation of upper Nano diamond, friction resistant performance makes moderate progress again.
Applicant states that the present invention illustrates process of the invention by above-described embodiment, but the present invention not office
It is limited to above-mentioned processing step, that is, does not mean that the present invention has to rely on above-mentioned processing step and could implement.Art
Technical staff it will be clearly understood that any improvement in the present invention, equivalence replacement and auxiliary element to raw material selected by the present invention
Addition, selection of concrete mode etc., within the scope of all falling within protection scope of the present invention and disclosing.
Claims (10)
1. a kind of lube oil additive, it is characterised in that the additive is included by changing that TEMPO classes catalyst is aoxidized
Property graphite alkenes material.
2. lube oil additive as claimed in claim 1, it is characterised in that the TEMPO classes catalyst includes 2,2,6,6-
Tetramethyl piperidine-nitrogen-epoxide, 2-aza-adamantane-N- epoxides, 1- methyl -2-aza-adamantane-N- epoxides, 1,3- dimethyl -
Any a kind or at least 2 kinds in 2-aza-adamantane-N- epoxides, 4- hydroxyl TEMPO derivatives of combination；
Preferably, the TEMPO classes catalyst is contacted in the form of TEMPO class aqueous catalyst solutions with graphite alkenes material, is entered
Row catalysis oxidation；
Preferably, also it is added with the TEMPO classes catalyst oxidizing process any in halide salt, and hypohalite
1 kind or at least 2 kinds of combination；
Preferably, the hypohalite includes hypochlorite and/or hypoiodite；
Preferably, the halide salt includes Bromide and/or iodized salt；
Preferably, the cation in the halide salt and hypohalite includes alkali metal ion, preferably includes sodium ion and/or potassium
Ion；
It is further preferred that in the catalytic oxidation process, the TEMPO classes aqueous catalyst solution is alkalescence, includes TEMPO
Class catalyst, hypohalite, the aqueous solution of halide salt, preferably include 2,2,6,6- tetramethyl piperidine nitrogen oxides, secondary chlorine
The aqueous solution of sour sodium, sodium bromide；The TEMPO classes aqueous catalyst solution pH is preferably 9.5~11.5, more preferably 10-
11；
Preferably, in the TEMPO classes aqueous catalyst solution catalytic oxidation process, the addition of TEMPO class catalyst is graphite
The 0.05%~5% of alkenes substance weight, preferably 0.1%~3%, further preferably 0.3%~2%, more preferably 0.5%-1%；
Preferably, the addition of the hypohalite is the 10%~500% of graphite alkenes substance weight, preferably 30%~
95%, further preferably 40%-75%；
Preferably, the addition of the halide salt is the 0.5%~50% of graphite alkenes substance weight, preferably 10%~30, then
It is preferred that 3%~20%, more preferably 5%~10%.
3. lube oil additive as claimed in claim 1 or 2, it is characterised in that the additive includes that powder shaped is passed through
TEMPO classes catalyst oxidation modified graphite alkenes material, be dispersed with powder shaped by TEMPO classes catalyst aoxidize
The aqueous solution of modified graphite alkenes material and the reaction solution of TEMPO class catalyst graphite oxide alkenes materials in appoint
The combination of a kind or at least 2 kinds of meaning；
Preferably, the reaction solution of the TEMPO classes catalyst graphite oxide alkenes material is prepared via a method which：By stone
Black alkenes material carries out catalytic oxidation under the oxidation of TEMPO classes catalyst, until the pH of reaction system is constant or adds
Enter alcohols material terminating reaction, obtain the reaction solution of TEMPO class catalyst graphite oxide alkenes materials；
Preferably, in the reaction solution of the TEMPO classes catalyst graphite oxide alkenes material, in terms of Graphene, reaction solution
The concentration of middle graphite alkenes material is below 20mg/g, preferably 1~10mg/g, further preferred 3~5mg/g；
Preferably, the modified graphite alkenes material that the powder shaped is aoxidized by TEMPO classes catalyst is by the following method
Prepare：By the reaction solution washing of TEMPO class catalyst graphite oxide alkenes materials, dry, obtain powder shaped by TEMPO
The modified graphite alkenes material of class catalyst oxidation；
Preferably, it is described to be dispersed with the water-soluble of the modified graphite alkenes material that powder shaped is aoxidized by TEMPO classes catalyst
Liquid is prepared via a method which：Powder shaped is scattered in by the modified graphite alkenes material that TEMPO classes catalyst is aoxidized
In water, obtain being dispersed with the aqueous solution of the modified graphite alkenes material that powder shaped is aoxidized by TEMPO classes catalyst；
Preferably, it is described to be dispersed with the water-soluble of the modified graphite alkenes material that powder shaped is aoxidized by TEMPO classes catalyst
In liquid, in terms of Graphene, in reaction solution the concentration of graphite alkenes material be below 20mg/g, preferably 1~10mg/g, further it is excellent
Select 3~5mg/g；
Preferably, the graphite alkenes material includes Graphene, biomass Graphene, graphene oxide, Graphene derivative
Any a kind or at least 2 kinds of mixing, preferably biomass Graphene and/or graphene oxide；
Preferably, the Graphene derivative include any a kind in element doping Graphene or functional group's graphite alkene thing or
At least 2 kinds of combination.
4. a kind of modification of lubricating oils, it is characterised in that be added with one of claims 1 to 3 in the modification of lubricating oils described
Lube oil additive；
Preferably, the amount of graphite alkenes material is 0.005~0.3wt% of substrate oil, preferably 0.01 in the modification of lubricating oils
~0.1wt%, further preferred 0.01~0.05wt%；
Preferably, it is described that lube oil additive is added into the feed postition into substrate oil to be added dropwise in liquid form, the drop
Acceleration is preferably 0.5~20mL/min；
Preferably, the substrate oil includes any a kind or at least 2 kinds of finished lube, semi-finished product lubricating oil and base oil
Combination；
Preferably, the base oil includes any a kind or at least 2 in mineral base oil, synthetic base oil or biological basis oil
The combination planted.
5. modification of lubricating oils as claimed in claim 4, it is characterised in that a nanometer Buddha's warrior attendant is also added with the modification of lubricating oils
Stone, is preferably added with the modified Nano diamond of oleophylic；
Preferably, the Nano diamond accounts for 0.01~0.1wt% of substrate oil；
Preferably, the particle diameter of the Nano diamond is in below 20nm, preferably preferably below 10nm, 4~8nm；
Preferably, the modified Nano diamond of the oleophylic is prepared via a method which to obtain：
A be distributed to unmodified Nano diamond in dispersion liquid by ()；
(b) and then mix with modifying agent；
C () stirring reaction obtains the modified Nano diamond solution of oleophylic；
Preferably, the dispersion liquid includes the combination of any a kind or at least 2 kinds in petroleum ether, oleic acid, atoleine；
Preferably, the modifying agent includes the combination of coupling agent and ashless dispersant；
Preferably, the coupling agent includes any a kind or at least 2 kinds in titanium class coupling agent, tin class coupling agent, silicon class coupling agent
Combination, preferred titanate coupling agent；
Preferably, the ashless dispersant includes succimide, succinate, boronation succimide, succimide acid
And its any a kind or at least 2 kinds of combination in derivative；
Preferably, ashless dispersant includes mono alkenyl succimide, double focusing isobutyl imidodicarbonic diamide, polyisobutene succinimide
Any a kind or at least 2 kinds of combination, further preferred polyisobutene succinimide；
Preferably, in the preparation method of the modified Nano diamond of the oleophylic, stirring reaction is more than back flow reaction 10min,
It is preferred that 0.5~10h, further preferred 2~8h, particularly preferred 4~6h；
Preferably, the concentration of Nano diamond is 3wt% in the Nano diamond solution that the oleophylic that the step (c) obtains is modified
Hereinafter, preferably below 2wt%, further preferred 0.5~1.5wt%, particularly preferred 0.8~1.2wt%；
Preferably, coupling agent concentrations are the 5~20wt%, preferably 8~13wt% of dispersion liquid quality；
Preferably, ashless dispersants agent concentration is the 5~20wt%, preferably 8~13wt% of dispersion liquid quality.
6. a kind of preparation method of the modification of lubricating oils as described in claim 4 or 5, it is characterised in that methods described includes as follows
Step：
Lube oil additive is added into substrate oil, after emulsification, the water phase in removal emulsion obtains modification of lubricating oils；
Preferably, the lube oil additive is added into substrate oil in liquid form；
It is further preferred that the lube oil additive is being dispersed with powder shaped by changing that TEMPO classes catalyst is aoxidized
Property graphite alkenes material the aqueous solution form add to substrate oil in.
7. method as claimed in claim 6, it is characterised in that methods described after the water phase in removing emulsion, receive by addition
Rice diamond, is uniformly dispersed；
Preferably, the Nano diamond is the Nano diamond solution that oleophylic is modified.
8. method as claimed in claims 6 or 7, it is characterised in that the mode of the emulsification includes concussion emulsion process, stirring breast
Any a kind or at least 2 kinds of combination in change method, syringe emulsion process, ultrasonic emulsification, mortar emulsion process, preferably stir
Emulsion process and/or concussion emulsion process；
Preferably, the mixing speed of the stirring and emulsifying method is 3000~5000r/min, 70~80 DEG C of whipping temp；
Preferably, the method for the water phase in the removal emulsion includes layering except water law, distillation are except water law, heating volatilization water removal
Method, the combination for drying any a kind or at least 2 kinds removed in water law；
Preferably, the layering removes water law includes that demulsifier layering removes water law or centrifugation demulsification point except water law, ultrasonic emulsion breaking layering
Layer is except the combination of any a kind or at least 2 kinds in water law；
Preferably, the demulsifier is layered except water law comprises the following steps：To demulsifier is added in the product after emulsification, make water phase
With oil phase layering, water phase is removed；It is preferred that continuously adding drier in the oil phase that layering is obtained except water law, remaining water is removed
Phase；
Preferably, the distillation removes water law includes atmospheric distillation and/or distillation under vacuum；
Preferably, the boiling point of the vapo(u)rizing temperature less than the base oil of the distillation water removal；
Preferably, the vacuum distillation includes rotary evaporation；
Preferably, the heating volatilization is except the boiling point of the heating-up temperature less than the base oil of water law；
Preferably, the drying is except water law is including adding drier water removal.
9. the method as described in one of claim 6~8, it is characterised in that in emulsion process and/or in removal emulsion
After water phase, reduction treatment is carried out；
Preferably, the method for the reduction treatment includes reducing agent reducing process and/or heating reducing process；
Preferably, the reducing agent reducing process includes adding reducing agent to be reduced；
Preferably, the addition of the reducing agent is the 10~200wt%, preferably 50~100wt% of graphite alkenes material；
Preferably, the reducing agent include ascorbic acid, hydrazine hydrate, ethylenediamine, sodium citrate, Cys, hydroiodic acid or
Any a kind or at least 2 kinds of combination in sodium borohydride；
Preferably, the heating reducing process is included in non-oxidizing atmosphere, and heating is reduced；
Preferably, the heating reducing process step includes：In autoclave, protective atmosphere and/or reproducibility gas are passed through
Atmosphere, heating reduction；Temperature≤200 DEG C of the heating reduction, pressure≤1.6MPa.
10. the purposes of a kind of modification of lubricating oils as described in claim 4 or 5, it is characterised in that the modification of lubricating oils is used for
The lubrication of mechanical structure.
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| CN113926488A (en) * | 2021-11-14 | 2022-01-14 | 福州大学 | Preparation method of Fe-Si suspension bed hydrocracking catalyst |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112522013A (en) * | 2020-12-01 | 2021-03-19 | 辽宁汽众润滑油生产有限公司 | Additive for repairing wear scratches in automobile engine and preparation method thereof |
| CN113926488A (en) * | 2021-11-14 | 2022-01-14 | 福州大学 | Preparation method of Fe-Si suspension bed hydrocracking catalyst |
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