CN106867625A - Lubricating oil and lube oil additive based on surface modified graphite alkene - Google Patents
Lubricating oil and lube oil additive based on surface modified graphite alkene Download PDFInfo
- Publication number
- CN106867625A CN106867625A CN201510905777.7A CN201510905777A CN106867625A CN 106867625 A CN106867625 A CN 106867625A CN 201510905777 A CN201510905777 A CN 201510905777A CN 106867625 A CN106867625 A CN 106867625A
- Authority
- CN
- China
- Prior art keywords
- graphene
- graphite alkene
- lubricating oil
- surface modified
- modified graphite
- 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.)
- Pending
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
- C10M125/00—Lubricating compositions characterised by the additive being an inorganic material
- C10M125/02—Carbon; Graphite
-
- 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
- C10M177/00—Special methods of preparation of lubricating compositions; Chemical modification by after-treatment of components or of the whole of a lubricating composition, not covered by other classes
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
- C10M2201/04—Elements
- C10M2201/041—Carbon; Graphite; Carbon black
Abstract
A kind of lube oil additive based on surface modified graphite alkene material, comprising the Graphene that bile salt or derivatives thereof is surface-treated, mass percent of the Graphene that described bile salt or derivatives thereof is surface-treated in lubricating oil is
0.01-0.9 %
.And a kind of lubricating oil based on modified graphene.The method of the present invention is simple and easy to apply, and repetitive rate is high, is adapted to large-scale industrialization production.Lube oil additive of the invention has dispersiveness well, and can be effectively increased the abrasion resistance of lubricating oil can simultaneously reduce the loss of engine.
Description
Technical field
The present invention relates to lubricating oil field, especially a kind of lubricating oil and lube oil additive based on surface modified graphite alkene.
Background technology
The performances such as the greasy property of engine and the safe and environment-friendly of automobile and energy-conservation are closely bound up, with the continuous improvement of engine performance, requirement in terms of to lubrication is increasingly sophisticated, harshness, in order to the lube oil additive for improving engine lubrication performance, realize anti-attrition energy-conservation, improve mechanical efficiency also arises at the historic moment.Suitable nano particle how to be selected as additive, and improves its focus of the dispersiveness as lube oil additive area research in recent years.
Graphene as a kind of carbonaceous new material with two-dimensional structure, with specific surface area higher, a series of excellent performances such as thermal conductivity and mechanical property.It is added to Graphene as solid additive in lubricating oil, obvious anti-attrition energy-saving effect can be played.But Graphene additive easily produces layering and deposited phenomenon in use, how to give full play to the efficiency of Graphene, it is the problem that lubricant additive of the exploitation based on grapheme material must be faced to overcome drawbacks described above.
The content of the invention
Regarding to the issue above, the present invention proposes a kind of lubricating oil and lube oil additive based on surface modified graphite alkene, to improve the dispersion stabilization of Graphene, improves the lubricity of engine.
As one aspect of the present invention, the invention provides a kind of lube oil additive based on surface modified graphite alkene, comprising the Graphene that bile salt or derivatives thereof is surface-treated, mass percent of the Graphene that described bile salt or derivatives thereof is surface-treated in lubricating oil is
0.01-0.9 %
。
Wherein, mass percent of the Graphene of described bile salt or derivatives thereof surface treatment in lubricating oil is
0.2-0.6 %
。
Wherein, the bile salt is included but is not limited to selected from cholic acid, deoxycholic acid, chenodesoxycholic acid, lithocholic acid, glycocholic acid, glycochenodeoxycholate, taurocholate, the sodium salt or sylvite of Irish moss (chondrux).
Preferably, the bile salt is NaTDC.
Wherein, the lubricating oil is the automobile oil of commercialization.
Wherein, the Graphene of described bile salt or derivatives thereof surface treatment is added in the aqueous solution containing the bile salt or derivatives thereof by by the aqueous solution of graphite oxide, adds the product obtained after reducing agent reaction.
Wherein, the thickness of the Graphene
0.17-1.4 nm
, piece footpath size is
10-1000nm
。
As another aspect of the present invention, the invention provides a kind of lubricating oil based on surface modified graphite alkene, include the lube oil additive based on surface modified graphite alkene described in as above any one.
As another aspect of the invention, present invention also offers a kind of application of the surface modified graphite alkene described in as above any one in lubricating oil.
The present invention realizes that graphenic surface is processed using two phase process, prepares the Graphene of good dispersion.The method is simple and easy to apply, and repetitive rate is high, is adapted to large-scale industrialization production.Lube oil additive of the invention, with good dispersiveness, it is to avoid the use of traditional dispersant, to be effectively increased the abrasion resistance of lubricating oil can simultaneously reduce the loss of engine.Graphene is surface-treated by NaTDC, the Graphene with dispersiveness very well is prepared, while avoiding the addition of dispersant.
Specific embodiment
To make the object, technical solutions and advantages of the present invention become more apparent, below in conjunction with specific embodiment, the present invention is described in further detail.
Lubricating oil; it is used in all kinds automobile, plant equipment reducing friction; the liquid or semisolid lubricants of protection machinery and workpiece; it is main to play lubrication, cooling, antirust, cleaning, sealing and buffering etc.; divide animal oil, vegetable oil, petroleum oil and the major class of synthetic lubricant fluid four by its source.The lubricating oil used in the present invention is all types of automobile oils of commercialization.
The general name of the acids secreted in bile acid, i.e. bile.Bile acid in normal human bile（
bile acid
）Can be divided into two major classes by structure：One class is sequestered bile acid, including cholic acid（
cholic acid
）, deoxycholic acid（
deoxycholic acid
）, chenodesoxycholic acid（
chenodeoxy cholic acid
）With a small amount of lithocholic acid（
litho chalic acid
）；Another kind of is product, the title conjugated bile acidses that above-mentioned free bile acid is combined with glycine or taurine, mainly including glycocholic acid, glycochenodeoxycholate, taurocholate and Irish moss (chondrux) etc..Bile salt, then be the salt of bile acid, such as sodium salt, sylvite etc..The derivative of bile salt, then be hydrogen atom or atomic group in bile salt by other atoms or atomic group substitution derivative product, such as UDCA,
Na-
Courage acyl
-
（
3-O-
Nitro
-D-
Serine）Deng.
Graphene used in the present invention, can be various known Graphenes, for example it is by mechanically pulling off the Graphene of the methods such as method, chemical oxidization method, crystal epitaxy method, chemical vapour deposition technique, organic synthesis method and CNT stripping method preparation, can also be the Graphene by being processed further treatment, such as single-layer graphene, graphene oxide, reduced graphene, functionalization graphene etc..Big the neglecting of the thickness of the Graphene and piece footpath is actually needed selection, and preferred thickness is
0.17-1.4 nm
, piece footpath size is
10-1000nm
。
The invention discloses a kind of lube oil additive based on surface modified graphite alkene, the Graphene of bile salt or derivatives thereof treatment is wherein with the addition of in lubricating oil, the mass percent that the Graphene of described bile salt or derivatives thereof treatment is shared in lubricating oil is
0.01-0.9%
, preferably
0.2-0.6 %
.Wherein described bile salt or derivatives thereof is preferably NaTDC.
Described lubricating oil can be all types automobile oil of commercialization, and various known lube oil additives, such as antioxidant, dispersant, antiwear additive, viscosity index improver etc. can also be added in the lubricating oil.
The invention also discloses a kind of preparation method of the lube oil additive based on surface modified graphite alkene, comprise the following steps：
Graphite oxide is prepared, is dispersed in being prepared into graphite oxide weak solution in water；
To the aqueous solvent that bile salt or derivatives thereof is added in the graphite oxide weak solution for preparing, reducing agent is added dropwise, target product is obtained after reaction.
Wherein, the reducing agent that the reducing agent can be known in the art, such as hydrazine hydrate.
Wherein, the thickness of the surface modified graphite alkene for obtaining is
0.17-1.4 nm
, piece footpath size is
10-1000nm
。
Lube oil additive based on surface modified graphite alkene obtained above, i.e. mass percent of the modified graphene in lubricating oil be
0.01-0.9 %
, preferably
0.2-0.6 %
。
As a preferred embodiment, the invention also discloses a kind of preparation method of the lube oil additive based on surface modified graphite alkene, comprise the following steps：
Prepare graphite oxide and be configured to graphite oxide weak solution；
Bile salt or derivatives thereof is chosen, such as NaTDC stirring and dissolving is in water；
To deoxycholic acid sodium water solution is added in the graphite oxide weak solution for preparing, two-phase is formed, be warmed up to
60-90
DEG C, preferably
80
DEG C, hydrazine hydrate, reaction is added dropwise
12
-
36
Target product is obtained after hour.
And the lubricating oil based on surface modified graphite alkene is obtained, it is only necessary to the lube oil additive based on surface modified graphite alkene obtained above is directly appended in lubricating oil, stirring mixing obtains final product target product.
In above-mentioned preparation method, the modified Graphene thickness in surface is
0.17-1.4 nm
, piece footpath size is
10-1000nm
.Lube oil additive based on surface modified graphite alkene obtained above, i.e. mass percent of the modified graphene in lubricating oil be
0.01-0.9 %
, preferably
0.2-0.6 %
。
In the preparation process of NaTDC surface treatment Graphene, the addition of graphite oxide powder can be adjusted with visual response degree, for example can be with
1
~
1.5g
Graphite oxide powder adds
250-500g
Deionized water.Add the concentration of the aqueous solution of NaTDC can be
0.25~0.5 mol/L
Between select.
The present invention is illustrated in more detail with reference to specific embodiment.
Embodiment
1
The preparation of graphite oxide：Using
Hummer
Method, at one
250 mL
Beaker in add
2g
Crystalline flake graphite powder, is added thereto under conditions of ice-water bath
1g NaNO3
After add
46mL 98%
's
H2SO4
And it is sufficiently stirred for；It is slowly added to
6g KMnO4
, keep the temperature of solution to exist
20
More than DEG C and keep this condition
5
Minute, then remove ice-water bath and be heated to
35
DEG C, keep this condition
30
Minute；Add
92 mL
Water, be stirred for
15
Minute, temperature will be increased to about
98
℃；Continuously add
80 mL
's
60
℃
3%
Hydrogen peroxide, existed with centrifuge
7200
Turn lower centrifugation
30
Liquid after minute above-mentioned treatment；Residue is cleaned with hot water until upper strata suspension
pH
About
7
；The powder for obtaining is dispersed back into ultrasound in water
45
Minute, obtain a kind of homogeneous suspension after having filtered black residue；Graphite oxide is obtained after suspension is freezed.
NaTDC is surface-treated the preparation of Graphene：Will
1 g
The graphite oxide powder for obtaining is dissolved in deionized water, and microwave irradiation is disperseed, and is added
5.3 g
Concentration is
0.5 mol/L
NaTDC the aqueous solution, be warming up to
80
DEG C, it is added dropwise
2-10 ml
Hydrazine hydrate, and react with this understanding
36 h
After filter, the product that will be obtained rinses multiple with first alcohol and water successively, and vacuum drying obtains the modified Graphene in NaTDC surface.
It is by mass percent
0.15 %
The modified Graphene in NaTDC surface be added in lubricating oil, be uniformly mixed.
Embodiment
2
The preparation of graphite oxide such as embodiment
1
, will
1 g
The graphite oxide powder for obtaining is dissolved in deionized water, ultrasonic disperse, is added
5.3 g
Concentration is
0.25 mol/L
NaTDC organic solution, be warming up to
80
DEG C, it is heated to reflux, the Graphene that NaTDC is surface-treated is obtained by two phase process, the graphene powder of NaTDC surface treatment is filtered and is dried to obtain in cleaning.NaTDC organic solution can be toluene or cyclohexane solution.
It is by mass percent
0.3%
NaTDC surface treatment graphene powder be added in lubricating oil, be uniformly mixed.
Embodiment
3
The preparation such as embodiment of the Graphene of NaTDC surface treatment
2
。
It is by mass percent
0.2%
Lithocholic acid potassium surface treatment graphene powder be added in lubricating oil, stir mixing.
Embodiment 4
The preparation such as embodiment of the Graphene of NaTDC surface treatment
2
。
It is by mass percent
0.01%
NaTDC surface treatment graphene powder be added in lubricating oil, stir mixing.
Embodiment 5
The preparation such as embodiment of the Graphene of NaTDC surface treatment
2
。
It is by mass percent
0.9%
NaTDC surface treatment graphene powder be added in lubricating oil, stir mixing.
Embodiment
6
The preparation such as embodiment of the Graphene of natrium taurocholicum surface treatment
2
。
It is by mass percent
0.6%
Natrium taurocholicum surface treatment graphene powder be added in lubricating oil, stir mixing.
Comparative example
1-2
Prepare the method and embodiment of graphite oxide powder
1
It is identical, differ only in and be added without bile salt, but according to
hummer
Method obtains black graphene powder directly with hydrazine hydrate or sodium borohydride to graphite oxide powder reduction.
It is by mass percent respectively
0.01%
With
0.9%
The modified graphene powder in non-surface is added in lubricating oil, is uniformly mixed.
Storage stability is tested
Obtained target product is stood
15
My god,
30
My god, the situation of object observing product.
By experiment, passing through
15
After it, occur in that obvious reunion is layered in the lubricating oil that with the addition of the Graphene lube oil additive being surface-treated, and with the addition of the lubricating oil of the Graphene lube oil additive of NaTDC surface treatment, even across
30
After it, still can not observe and substantially reunite or be layered with stable dispersion.
Table
1
Embodiment
1-6
And comparative example
1-2
Storage stability list
Anti-attrition energy-conservation performance test
By four-ball tester（
GB/T 308
）With the anti-attrition energy-efficient performance that gear testing machine carrys out test target product.
Found by experiment, when the mass percent of the Graphene of NaTDC surface treatment is
0.2-0.6 %
When, the anti-attrition energy-saving effect of lubricating oil is best.
Table
2
Anti-attrition energy-conservation the performance test results list
By experiment above, after the Graphene by bile salt or derivatives thereof treatment of the invention is added in lubricating oil, can more preferable dispersed graphite alkene so that the dispersion stabilization of lubricating oil, and the lubricity of engine is greatly improved.And the Graphene processed without bile salt or derivatives thereof, although the lubricity of engine can be improved in the case of big addition, but because dispersion inequality also causes the deterioration of other performances.
Although embodiment illustrate only bile salt or derivatives thereof and the surface of graphite oxide is modified, it is appreciated that the inspiration for passing through above-described embodiment, such scheme is equally applicable to the modified of other type graphite alkene for this area.
Particular embodiments described above; the purpose of the present invention, technical scheme and beneficial effect are further described; it should be understood that; the foregoing is only specific embodiment of the invention; it is not intended to limit the invention; all any modification, equivalent substitution and improvements within the spirit and principles in the present invention, done etc., should be included within the scope of the present invention.
Claims (9)
1. a kind of lube oil additive based on surface modified graphite alkene, it is 0.01-0.9 % to include mass percent of the Graphene of the Graphene of bile salt or derivatives thereof surface treatment, described bile salt or derivatives thereof surface treatment in lubricating oil.
2. the lube oil additive based on surface modified graphite alkene according to claim 1, wherein mass percent of the Graphene of described bile salt or derivatives thereof surface treatment in lubricating oil is 0.2-0.6%.
3. the lube oil additive based on surface modified graphite alkene according to claim 1, wherein the bile salt is included but is not limited to selected from cholic acid, deoxycholic acid, chenodesoxycholic acid, lithocholic acid, glycocholic acid, glycochenodeoxycholate, taurocholate, the sodium salt or sylvite of Irish moss (chondrux).
4. the lube oil additive based on surface modified graphite alkene according to claim 1, wherein the bile salt is NaTDC.
5. the lube oil additive based on surface modified graphite alkene according to claim 1, wherein the lubricating oil is the automobile oil of commercialization.
6. the lube oil additive based on surface modified graphite alkene according to claim 1, the Graphene of wherein described bile salt or derivatives thereof surface treatment is added in the aqueous solution containing the bile salt or derivatives thereof by by the aqueous solution of graphite oxide, adds the product obtained after reducing agent reaction.
7. the lube oil additive based on surface modified graphite alkene according to claim 1, wherein the thickness of the Graphene is 0.17-1.4 nm, piece footpath size is 10-1000nm.
8. a kind of lubricating oil based on surface modified graphite alkene, comprising just like the lube oil additive based on surface modified graphite alkene described in any one of claim 1 to 7.
9. application of a kind of surface modified graphite alkene as described in claim 1 to 7 any one in lubricating oil.
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|---|---|---|---|
| CN201510905777.7A CN106867625A (en) | 2015-12-10 | 2015-12-10 | Lubricating oil and lube oil additive based on surface modified graphite alkene |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510905777.7A CN106867625A (en) | 2015-12-10 | 2015-12-10 | Lubricating oil and lube oil additive based on surface modified graphite alkene |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106867625A true CN106867625A (en) | 2017-06-20 |
Family
ID=59238321
Family Applications (1)
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|---|---|---|---|
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| CN106350151A (en) * | 2015-07-14 | 2017-01-25 | 闫立群 | Lubricant additive based on surface modified oxidized graphene, lubricant based on surface modified oxidized graphene, and preparation methods of lubricant additive and lubricant |
-
2015
- 2015-12-10 CN CN201510905777.7A patent/CN106867625A/en active Pending
Patent Citations (6)
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| CN104884198A (en) * | 2012-12-27 | 2015-09-02 | Lg化学株式会社 | Method for manufacturing hollow metal nanoparticle supported by support body |
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