CN102898680A - Surface-modified graphene - Google Patents
Surface-modified graphene Download PDFInfo
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- CN102898680A CN102898680A CN2011102149591A CN201110214959A CN102898680A CN 102898680 A CN102898680 A CN 102898680A CN 2011102149591 A CN2011102149591 A CN 2011102149591A CN 201110214959 A CN201110214959 A CN 201110214959A CN 102898680 A CN102898680 A CN 102898680A
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Images
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), a kind of by the crystalline network of monolayer carbon atom with the tightly packed one-tenth bi-dimensional cellular of graphite key (sp2) shape, the thickness that therefore a carbon atom is only arranged, the 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 in the world also be the hardest material, thermal conductivity is higher than CNT (carbon nano-tube) and diamond, also ratio nano carbon pipe or silicon wafer height of its electronic mobility under the normal temperature, resistivity is lower than copper or silver, is the present material of resistivity minimum in the world.Graphene and CNT (carbon nano-tube) all have the advantage that pliability is high, reflectivity is low in the application of transparency electrode, it is present first-selection as the soft electronic material, yet the coating of graphene dispersing solution is many than 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.
No. the 20110049437th, United States Patent (USP) evenly mixes Graphene with a high polymer binder, can coat substrate surface as a coating, changes the surface property of base material, especially improves its electroconductibility.If yet the Graphene surface is not enough with the binding agent affinity, so that the two is difficult for mixing, will be so that this effect be clear.
United States Patent (USP) is coated on the epoxy resin hardener surface with Graphene No. 20110017955, when stiffening agent and Resins, epoxy mixed hardening, can increase the thermal conductivity of Resins, epoxy.Similar with No. the 20110049437th, above-mentioned United States Patent (USP), key is the affinity between Graphene and the organic polymer material, when engaging when good the characteristic of competence exertion matrix material between grapheme material and the macromolecular material.
No. the 20100178464th, United States Patent (USP) is with the etching of Graphene edge, connect the organic functional base at etched edge again, as-COOH ,-C=O etc., use the characteristic of improving the Graphene surface, yet etching method is complicated and with high costs, and 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, and 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 ')
zWherein M is metallic element; R is the wetting ability functional group; R ' is the 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 the alcoxyl carboxyl; R ' is selected from vinyl; the cycloaliphatic ring oxyalkyl; styryl; methacryloxy; acryloxy; the fatty group amido; the chloropropane base; the fatty group thiohydroxy; fatty group sulfonium ion base; isocyanato; the fatty group Urea-based; the fatty group carboxyl; the fatty group hydroxyl; cyclohexyl; phenyl; the fatty group formyl radical; the acetyl or benzoyl base; lipid acid is selected from stearic acid or oleic acid, and resin is selected from Resins, epoxy; 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 the organic polymer, in addition, by utilizing the grapheme modified structure of chemical process or character, can become more solid to some the same with Graphene slim, full of elasticity and slim and graceful " super material ", make widely applicability of its tool, for example can prepare conducting polymer, or can be for the manufacture of man-made satellite, aircraft and automobile.
Description of 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 behind 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) are the graphene powder XPS figure behind example 2 upgradings;
Fig. 7 is the graphene powder XPS figure behind example 3 upgradings; And
Fig. 8 is the schematic diagram of example 4 employed epoxy resin structurals.
Embodiment
Below cooperation is graphic does more detailed description to embodiments of the present invention, so that those skilled in the art can implement after studying this specification sheets carefully 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 namely is changed, thereby get so that graphene powder Uniform Dispersion in solvent, maybe can promote graphene powder and organic macromolecule conjugation, and be beneficial to the follow-up widespread use of Graphene, such 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 during plastics are mixed, 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 the 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 generally is comprised of two parts, and a part is close inorganic group, can engage with inorganic filler, and another part is close organic group, can with the organic resin effect.Common coupler has silicane, titanate ester, zirconate, aluminium zirconate, aluminate, chromate class, and is 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.
The end of the R of coupler of the present invention and M bond, and the 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.The 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 easily be scattered in the organic carrier or with organic polymer and react, when 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 and produce chemical bonded refractory between the two.
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, as seen has the organic functional base of a little remnants on it, and Fig. 1 (B) represents the Graphene of surfaction, uses to have 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 relative two ends are arranged, one functional group can react with the 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 Resins, epoxy, 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, the below enumerates several and can be applicable to example of the present invention.
Example 1 at first 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 then is 1.3wt%; Fig. 3 is the carbon test result of XPS, and the result shows that the 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 adds graphene powder again and carries out mix and blend for surface modifier is added in the mixing solutions of an ethanol and water, 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 behind the upgrading, show that from figure there is another layer film on the graphene powder surface, namely may change for the surface coating of face modification agent, carry out EDS by the circled of Fig. 4 and analyze the Si element signal that to detect as shown in Figure 5, proved that simultaneously the graphene powder surface has surface modifier; Fig. 6 (A) and Fig. 6 (B) are the graphene powder XPS figure behind the upgrading, the 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, prove that all surface modifier determines to be coated in the graphene powder surface.
Example 3 adopts coupler tetrabutyl oxygen titanium (Titanium n-butoxide) as surface modifier, and its structure is Ti (C
4H
9O)
4, embodiment adds graphene powder again and carries out mix and blend for surface modifier is added in the isopropanol solvent, 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 behind the upgrading, and the signal of titanium elements appears in the graphene powder surface as can be seen from FIG., proves that surface modifier determines to be coated in the graphene powder surface.
Example 4 adopts Resins, epoxy (cresol novolac epoxy resin) as surface modifier, its structure as shown in Figure 8, embodiment is for to be dissolved in surface modifier in the acetone solvent fully, add again graphene powder and 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, be dissolved in Resins, epoxy in the acetone solvent fully first, 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 the organic polymer, also can make the graphene powder stable dispersion in polar aprotic solvent, it can closely be mixed with organic polymer, the preparation conducting polymer, for example, as long as in plastics, sneak into 1% Graphene, it just can become electric conductor, the Graphene that adds denier, plastics just can how heat-resisting 30 degree Celsius, and more durable.
Another characteristics of the present invention are, by utilizing the grapheme modified structure of chemical process or character, can be the same with Graphene slim some, full of elasticity and slim and graceful " super material " becomes more solid, make widely applicability of its tool, for example, Australia has developed a kind of Graphene paper, it is compared with common iron, want light 6 times in weight, little 5 to 6 times on the density, on the intensity large 2 times, large 10 times of tensile strength, large 13 times of flexural stiffness, increasing metallic substance is replaced by carbon-based material over 10 years, and at present many aircrafts and automaker have begun 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, and similar this synthetic " super material " can be for the manufacture of man-made satellite in the future, aircraft and automobile.
The above only is in order to explain preferred embodiment of the present invention; be not that attempt is done any pro forma restriction to the present invention according to this; therefore, all have identical invention spirit is lower do relevant any modification of the present invention or change, all must be included in the category that the invention is intended to protect.
Claims (10)
1. the Graphene of a surfaction is characterized in that, comprises:
One graphene powder; And
At least one surfaction layer, this at least one surfaction layer comprises a surface modifier, comprise 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 this 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 this surfaction
Wherein this surface modifier comprise coupler, lipid acid and resin at least one of them.
2. the Graphene of surfaction as claimed in claim 1 is characterized in that, the structure of this coupler 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.
3. the Graphene of surfaction as claimed in claim 2 is characterized in that, M is selected from one of them of aluminium, titanium, zirconium and silicon.
4. the Graphene of surfaction as claimed in claim 2 is characterized in that, R is selected from alkoxyl group, carbonyl, carboxyl, acyloxy, amido, stretch alkoxyl group and stretch the alcoxyl carboxyl wherein it
5. the Graphene of surfaction as claimed in claim 2; it is characterized in that, R ' 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.
6. the Graphene of surfaction as claimed in claim 1 is characterized in that, this lipid acid is selected from one of them of stearic acid and oleic acid.
7. the Graphene of surfaction as claimed in claim 1 is characterized in that, this resin is selected from one of them of Resins, epoxy, polyurethane resin, silicone resin, phenol resins and vibrin.
8. the Graphene of surfaction as claimed in claim 1 is characterized in that, this surface modifier accounts between the weight percent 0.1%-10.0% of Graphene weight of this surfaction.
9. the Graphene of surfaction as claimed in claim 1, it is characterized in that, this at least one surfaction layer 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.
10. the Graphene of surfaction as claimed in claim 1, it is characterized in that, this at least one surfaction layer 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.
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