CN102898680B - Surface-modified graphene - Google Patents
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- CN102898680B CN102898680B CN201110214959.1A CN201110214959A CN102898680B CN 102898680 B CN102898680 B CN 102898680B CN 201110214959 A CN201110214959 A CN 201110214959A CN 102898680 B CN102898680 B CN 102898680B
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Abstract
The invention provides a surface-modified graphene, comprising a graphene powder and at least one surface-modified layer, wherein the least one surface-modified layer comprises a surface modification agent and at least two functional groups disposed at two ends of the surface modification agent respectively; one functional group of the at least two functional groups can generate a chemical bond with an organic functional group on the surface of the surface-modified graphene powder; and the other functional group of the at least two functional groups forms a surface characteristic of the surface-modified graphene, wherein the surface modification agent comprises at least one of a coupling agent, aliphatic acid and a resin. Therefore, the surface-modified graphene powder can increase the dispersibility of the graphene powder in a solvent, enhance the endophilicity between the graphene powder and an organic polymer, and make the composite material to be more durable and to have wider applications.
Description
Technical field
The invention provides a kind of Graphene of surfaction, espespecially a kind of Graphene that makes the surfaction of graphene powder surface property change through surface modifier.
Background technology
Mono-layer graphite, be called again Graphene (graphene), be a kind of by monolayer carbon atom the crystalline network with the tightly packed one-tenth bi-dimensional cellular of graphite key (sp2) shape, therefore only there is the thickness of a carbon atom, graphite key is the compound keys of covalent linkage and metallic bond, can say the heaven-made match of isolator and electrical conductor.The Andre Geim of Univ Manchester UK in 2004 and Konstantin Novoselov successfully utilize the mode of tape stripping graphite, and confirmation can obtain the Graphene of individual layer, and obtains Nobel prize for physics in 2010.
Graphene be at present the thinnest be in the world also the hardest material, thermal conductivity is higher than CNT (carbon nano-tube) and diamond, under normal temperature, its electronic mobility is also than CNT (carbon nano-tube) or silicon wafer height, resistivity is lower than copper or silver, is the material of resistivity minimum in the world at present.Graphene and CNT (carbon nano-tube) all have in the application of transparency electrode the advantage that pliability is high, reflectivity is low, it is the current first-selection as soft electronic material, but the coating of graphene dispersing solution is many compared with CNT (carbon nano-tube) dispersion liquid difficulty, Graphene is very easy to assemble stack in essence, wish to get the graphene film of high uniformity and individual layer, avoiding graphene platelet to stack unevenly each other, is main technical difficulties but still make the thin slice conducting that contacts with each other.
United States Patent (USP) evenly mixes Graphene with a high polymer binder for No. 20110049437, can coat substrate surface as a coating, changes the surface property of base material, especially improves its electroconductibility.If but Graphene surface and binding agent affinity deficiency make the two be difficult for mixing, and will make this effect unclear.
United States Patent (USP) is coated on epoxy resin hardener surface by Graphene No. 20110017955, in the time of stiffening agent and epoxy resin mixed hardening, can increase the thermal conductivity of epoxy resin.Similar with No. 20110049437th, above-mentioned United States Patent (USP), key is the affinity between Graphene and organic polymer material, when engaging between grapheme material and macromolecular material when good, and the characteristic of competence exertion matrix material.
No. 20100178464th, United States Patent (USP) is by the etching of Graphene edge, on etched edge, connect again organic functional base, as-COOH ,-C=O etc., use the characteristic of improving Graphene surface, but etching method is complicated and with high costs, selected organic functional base and the connectivity on Graphene surface also have doubt.
Summary of the invention
Main purpose of the present invention is to provide a kind of Graphene of surfaction, comprise a graphene powder and at least one surfaction layer, this at least one surfaction layer comprises a surface modifier, this surface modifier comprises at least two functional groups, lay respectively at two ends of this surface modifier, this at least two functional group's a functional group and the organic functional base on graphene powder surface produce chemical bonded refractory, another functional group of this at least two functional group forms the surface property of the Graphene of surfaction, wherein this surface modifier comprises coupler, lipid acid and resin at least one of them.
The structure of above-mentioned coupler is M
x(R)
y(R ')
z, wherein M is metallic element, R is wetting ability functional group, R ' is lipophilicity functional group, M is selected from aluminium, titanium, zirconium or silicon, R is selected from alkoxyl group, carbonyl, carboxyl, acyloxy, amido, stretch alkoxyl group or stretch alcoxyl carboxyl, R ' is selected from vinyl, cycloaliphatic ring oxyalkyl, styryl, methacryloxy, acryloxy, fatty group amido, chloropropane base, fatty group thiohydroxy, fatty group sulfonium ion base, isocyanato, fatty group Urea-based, fatty group carboxyl, fatty group hydroxyl, cyclohexyl, phenyl, fatty group formyl radical, acetyl or benzoyl base, lipid acid is selected from stearic acid or oleic acid, resin is selected from epoxy resin, polyurethane resin, silicone resin, phenol resins or vibrin.
Surface modifier accounts between the weight percent 0.1%-10.0% of Graphene weight of surfaction.
This at least one surfaction layer comprises a first surface upgrading layer and a second surface upgrading layer, and first surface upgrading layer is a coupler layer, and second surface upgrading layer is a resin layer.
This at least one surfaction layer comprises a first surface upgrading layer, a second surface upgrading layer and one the 3rd surfaction layer, and first surface upgrading layer is a coupler layer, and second surface upgrading layer is a resin layer, and the 3rd surfaction layer is a coupler layer.
Therefore, the graphene powder of surfaction of the present invention, can improve the dispersiveness of graphene powder in solvent, also can improve the affinity between graphene powder and organic polymer, in addition, by utilizing the grapheme modified structure of chemical process or character, some " super materials " equally slim, full of elasticity and slim and graceful with Graphene can be become to more solid, make its tool applicability widely, for example, can prepare conducting polymer, or can be for the manufacture of man-made satellite, aircraft and automobile.
Brief description of the drawings
Fig. 1 (A) is pure graphene powder;
Fig. 1 (B) is the schematic diagram according to the Graphene of the surfaction of one embodiment of the invention;
Fig. 2 is the TEM figure of example 1;
Fig. 3 is the XPS figure of example 1;
Fig. 4 is the Graphene TEM figure after example 2 upgradings;
Fig. 5 is the chart that is carried out the result of EDS analysis by the circled of Fig. 4;
Fig. 6 (A), Fig. 6 (B) is the graphene powder XPS figure after example 2 upgradings;
Fig. 7 is the graphene powder XPS figure after example 3 upgradings; And
Fig. 8 is the schematic diagram of the epoxy resin structural that uses of example 4.
Embodiment
Below coordinate and graphic embodiments of the present invention are done to more detailed description, so that those skilled in the art are studying carefully after this specification sheets and can implement according to this.The present invention discloses a kind of Graphene of surfaction, comprises graphene powder and at least one surfaction layer, and this at least one surfaction layer comprises surface modifier.Surface modifier comprises at least two functional groups, lay respectively at two ends of surface modifier, the remaining organic functional base in this at least two functional group's a functional group and graphene powder surface produces chemical bonded refractory, and another functional group of this at least two functional group forms the surface property of the Graphene of this surfaction.
So, the surface property of graphene powder is changed, thereby obtain so that graphene powder is dispersed in solvent, maybe can promote graphene powder and organic macromolecule conjugation, and be beneficial to the follow-up widespread use of Graphene, for example, as transparency conductive electrode, thermally conductive material, ultracapacitor etc.
This surface modifier comprise coupler, lipid acid and resin at least one of them.
Coupler is usually used in plastics mixture, can improve a kind of additive of synthetic resins and inorganic filler or strongthener interface performance, it can reduce the viscosity of entire system in plastic working process, promote the dispersion of inorganic filler in organic resin, improve physical strength and the electrical specification of product, and increase the ability of product opposing environmental factors.Coupler is generally made up of two parts, and a part is close inorganic group, can engage with inorganic filler, and another part is close organic group, can with organic resin effect.Common coupler has silicane, titanate ester, zirconate, aluminium zirconate, aluminate, chromate class, wherein common with silicane.
The structure of coupler of the present invention is M
x(R)
y(R ')
z, wherein M is a metallic element, and R is a wetting ability functional group, and R ' is a lipophilicity functional group, wherein 0≤x≤6,1≤y≤20, and 1≤z≤20.
The M of coupler of the present invention is selected from one of them of aluminium, titanium, zirconium and silicon.
One end of the R of coupler of the present invention and M bond, and R hydrolyzable produces wetting ability functional group corresponding to the other end, make itself and graphene powder surface produce chemical bonded refractory, R is selected from alkoxyl group, carbonyl, carboxyl, acyloxy, amido, stretch alkoxyl group and stretch one of them of alcoxyl carboxyl.
The R ' of coupler of the present invention is selected from one of them of vinyl, cycloaliphatic ring oxyalkyl, styryl, methacryloxy, acryloxy, fatty group amido, chloropropane base, fatty group thiohydroxy, fatty group sulfonium ion base, isocyanato, fatty group Urea-based, fatty group carboxyl, fatty group hydroxyl, cyclohexyl, phenyl, fatty group formyl radical, ethanoyl and benzoyl.One end of R ' and M bond, the other end sees through above-mentioned functional group of different nature, can make the Graphene surface of surfaction produce the characteristic that is different from pure graphene powder, especially be easily scattered in organic carrier or with organic polymer and react, in the time that needs carry out blending from different organic polymers, can select the coupler of tool affinity to carry out the surfaction of pure graphene powder, make to produce between the two chemical bonded refractory.
Fig. 1 (B) is the schematic diagram according to the Graphene of the surfaction of one embodiment of the invention, uses coupler as surface modifier.Fig. 1 (A) represents pure graphene powder, has as seen the organic functional base of a little remnants on it, and Fig. 1 (B) represents the Graphene of surfaction, uses and has M
x(R)
y(R ')
zthe coupler of structure, produce chemical bonded refractory with its wetting ability functional group R and graphene powder surface, and lipophilicity functional group R ' forms the surface property of the Graphene of surfaction.
Surface modifier of the present invention can be selected the lipid acid of high-carbon number, it also possesses two functional groups that have relative two ends, one functional group can react with graphene powder surface, another functional group forms the surface property that is different from pure graphene powder simultaneously, and this high carbon number lipid acid is selected from one of them of stearic acid and oleic acid.
Surface modifier of the present invention can be selected resin, because resin possesses various functional group, therefore the surface property different from pure graphene powder surface can be provided, and this resin is selected from one of them of epoxy resin, polyurethane resin, silicone resin, phenol resins and vibrin.
Surface modifier of the present invention accounts between the weight percent 0.02%-20.0% of Graphene weight of this surfaction, preferably between 0.1%-10.0%.
At least one surfaction layer of the present invention comprises a first surface upgrading layer and a second surface upgrading layer, and wherein this first surface upgrading layer is a coupler layer, and this second surface upgrading layer is a resin layer.
At least one surfaction layer of the present invention comprises a first surface upgrading layer, a second surface upgrading layer and one the 3rd surfaction layer, wherein this first surface upgrading layer is a coupler layer, this second surface upgrading layer is a resin layer, and the 3rd surfaction layer is a coupler layer.
About above-described surface modifier, enumerate several examples of the present invention that can be applicable to below.
First example 1 carries out surface analysis for the pure graphene powder after synthetic, and Fig. 2 is TEM figure, shows that pure Graphene is sheet structure as thin as a wafer, and surface-area is 430m
2/ g, oxygen level is 1.3wt%; Fig. 3 is the carbon test result of XPS, and result shows that graphene powder surface still has small part carbon oxygen or hydrocarbon functional group.
Example 2 adopts coupler aminosiloxane (3-Aminopropyl triethoxysilane) as surface modifier, and its structure is Si (C
3h
6n) (C
2h
5o)
3, embodiment is that surface modifier is added in the mixing solutions of an ethanol and water, then adds graphene powder to carry out mix and blend, last air exhaust filtering take out powder and in baking oven heat drying, can obtain the graphene powder of surfaction.Fig. 4 is the Graphene TEM figure after upgrading, from figure, show that there is another layer film on graphene powder surface, may change for surface the coating of face modification agent, carry out EDS by the circled of Fig. 4 and analyze the Si element signal that can detect as shown in Figure 5, proved that graphene powder surface has surface modifier simultaneously; Fig. 6 (A) and Fig. 6 (B) are the graphene powder XPS figure after upgrading, graphene powder surface has the signal of silicon and nitrogen element as can be seen from FIG., on the collection of illustrative plates of carbon, also show the signal different from pure graphene powder, all prove the definite graphene powder surface that is coated in of surface modifier.
Example 3 adopts coupler tetrabutyl oxygen titanium (Titanium n-butoxide) as surface modifier, and its structure is Ti (C
4h
9o)
4, embodiment is for to add surface modifier in one isopropanol solvent, then adds graphene powder to carry out mix and blend, last air exhaust filtering take out powder and in baking oven heat drying, can obtain the graphene powder of surfaction.Fig. 7 is the graphene powder XPS figure after upgrading, and the signal of titanium elements appears in graphene powder surface as can be seen from FIG., proves the definite graphene powder surface that is coated in of surface modifier.
Example 4 adopts epoxy resin (cresol novolac epoxy resin) as surface modifier, its structure as shown in Figure 8, embodiment is for to be dissolved in surface modifier completely in acetone solvent, add again graphene powder to carry out mix and blend, last air exhaust filtering take out powder and in baking oven heat drying, can obtain the graphene powder of surfaction.
It is initial feed through the graphene powder of coupler aminosiloxane surfaction that example 5 adopts example 2, first epoxy resin is dissolved in acetone solvent completely, add again siloxane surface upgrading mix and blend, last air exhaust filtering take out powder and in baking oven heat drying, can obtain the graphene powder of surfaction.
Therefore, the graphene powder of surfaction of the present invention, its principal feature is, can improve the dispersiveness of graphene powder in solvent, also can improve the affinity between graphene powder and organic polymer, also can make graphene powder stable dispersion in polar aprotic solvent, it can closely be mixed with organic polymer, prepare conducting polymer, for example, need only the Graphene of sneaking into 1% in plastics, it just can become electric conductor, add the Graphene of denier, plastics 30 degree just can be how heat-resisting Celsius, and more durable.
Another feature of the present invention is, by utilizing the grapheme modified structure of chemical process or character, can some are equally slim with Graphene, full of elasticity and slim and graceful " super material " becomes more solid, make its tool applicability widely, for example, Australia has developed a kind of Graphene paper, it is compared with common iron, in weight, want light 6 times, little 5 to 6 times in density, in intensity large 2 times, large 10 times of tensile strength, large 13 times of flexural stiffness, over 10 years, increasing metallic substance is replaced by carbon-based material, at present many aircrafts and automaker have started with carbon fibre material substituted metal material, and the performance of Graphene paper is compared with carbon fibre material, Graphene paper is more outstanding undoubtedly, similar this synthetic " super material " can be for the manufacture of man-made satellite in the future, aircraft and automobile.
The foregoing is only to explain preferred embodiment of the present invention; not attempt is done any pro forma restriction to the present invention according to this; therefore, all have under identical invention spirit, do relevant any modification of the present invention or change, all must be included in the category that the invention is intended to protection.
Claims (1)
1. a Graphene for surfaction, is characterized in that, comprises:
One graphene powder; And
At least one surfaction layer, this at least one surfaction layer comprises a first surface upgrading layer and a second surface upgrading layer, wherein this first surface upgrading layer is a coupler layer, this second surface upgrading layer is a resin layer, the organic functional base on this first surface upgrading layer and this graphene powder surface produces chemical bonded refractory, and this second surface upgrading layer and this first surface upgrading layer produce chemical bonded refractory;
Wherein this surface modifier comprise coupler and lipid acid at least one of them, wherein the structure of this coupler is M
x(R)
y(R ')
z, wherein M is a metallic element, R is a wetting ability functional group, R ' is a lipophilicity functional group, wherein 0≤x≤6, 1≤y≤20, and 1≤z≤20, M is selected from aluminium, one of them of titanium and zirconium, R is selected from alkoxyl group, carbonyl, carboxyl, acyloxy, amido, stretch alkoxyl group and stretch one of them of alcoxyl carboxyl, and R ' is selected from vinyl, cycloaliphatic ring oxyalkyl, styryl, methacryloxy, acryloxy, fatty group amido, chloropropane base, fatty group thiohydroxy, fatty group sulfonium ion base, isocyanato, fatty group Urea-based, fatty group carboxyl, fatty group hydroxyl, cyclohexyl, phenyl, fatty group formyl radical, one of them of ethanoyl and benzoyl,
This resin is epoxy resin;
This lipid acid is selected from one of them of stearic acid and oleic acid;
This surface modifier accounts between the weight percent 0.1%-10.0% of Graphene weight of this surfaction.
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| TW201433635A (en) * | 2013-02-27 | 2014-09-01 | Enerage Inc | Lubricant oil containing graphene |
| CN104031716A (en) * | 2013-03-06 | 2014-09-10 | 安炬科技股份有限公司 | Graphene-containing lubricating oil |
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| TWI546254B (en) * | 2015-01-30 | 2016-08-21 | 安炬科技股份有限公司 | Method of surface modifying graphene |
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| CN108102299A (en) * | 2017-12-29 | 2018-06-01 | 青岛昊鑫新能源科技有限公司 | A kind of high-thermal-conductivity epoxy resin composite material and preparation method thereof |
| CN108410359A (en) * | 2018-04-08 | 2018-08-17 | 赵顺全 | A kind of anti-stone hits automobile antiseptic wax and preparation method thereof |
| CN110776975A (en) * | 2019-09-19 | 2020-02-11 | 西南交通大学 | Titanate modified graphene oxide slurry, lubricating oil composition and preparation method thereof |
| CN113073221B (en) * | 2020-01-03 | 2022-07-22 | 慧隆科技股份有限公司 | Graphene modification method of metal |
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