CN105778608A - Graphene composite coating and preparation method thereof - Google Patents
Graphene composite coating and preparation method thereof Download PDFInfo
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- CN105778608A CN105778608A CN201410814945.7A CN201410814945A CN105778608A CN 105778608 A CN105778608 A CN 105778608A CN 201410814945 A CN201410814945 A CN 201410814945A CN 105778608 A CN105778608 A CN 105778608A
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Abstract
The invention provides a graphene composite coating, consisting a coating body, a graphene dispersion liquid and a coating additive. The graphene composite coating comprises 40-60 wt% of coating body, 30%-50% of graphene dispersion liquid and 3-10 wt% of coating additive. The graphene dispersion liquid comprises graphene, an aniline oligomer derivative and a disperse medium. The graphene and aniline oligomer derivative form a pi-pi bond, so as to uniformly disperse in the coating body. The invention also provides a preparation method of the graphene composite coating.
Description
Technical field
The present invention relates to a kind of transparent heat insulating dope, particularly relate to a kind of graphite based on Graphene
Alkene composite coating and preparation method thereof.
Background technology
Under the situation that global energy supply is becoming tight and environment goes from bad to worse, energy-saving and emission-reduction become
The target that countries in the world are common.China is energy consumption big country, and annual social total energy consumption is equivalent to 15
Hundred million tons of standard coals, wherein about 30% is architectural energy consumption.In modern building, outside glass accounts for
The ratio of wall is increasing, and the heat transfer carried out by windowpane according to measuring and calculating is divided at winter or summer joint
Do not account for 48% and 71%.In cold winter, it is desirable to obtain more direct solar radiation
Heat energy, it is also desirable to minimizing indoor are thermal-radiating leaks so that indoor can keep higher temperature
Degree；During the broiling summer, people wish again the infra-red radiation heat energy of the sun is blocked in outdoor,
To alleviate the burden of air conditioner refrigerating.
Existing solution glass heat-proof problem mainly has three approach: one is to use Heat insulation type adhering film；
Owing to thermal isolation film is expensive, it is difficult to large-scale popularization, can only use on a small amount of high-grade car.
Two is to use thermal reflecting coating；But existing thermal reflecting coating product is opaque so that it is cannot be extensive
Application.Three are used in the silver-plated double glazing waiting metallics of glass surface；But due to
Production line of hollow glasses equipment and invest huge so that cannot production and application in a large number.
Transparent heat insulating dope is that one can allow glass both keep high light transmittance to meet daylighting requirement,
There is again the material of preferable effect of heat insulation simultaneously.At present, external glass transparent insulating coating uses
Popularity rate is high, and in the U.S., the popularity rate of transparent heat insulating dope is more than 90%；On ground, Europe
District, the popularity rate of transparent heat insulating dope has reached more than 80% the most.In Asia, except in
Outside state Hong Kong, Taiwan and Japan, Korea S, the transparent heat-insulated painting of building glass of other countries
Material popularity rate is averagely less than 20%.The popularity rate of the building glass transparent heat insulating dope of China mainland
Less than 10%.China carries out the policy of energy-saving and emission-reduction the most energetically now, and glass transparent insulating is coated with
Material has the biggest development space.
In recent years, Graphene attracted wide attention in the whole world as a kind of new material.
It is with sp by carbon atom2The monoatomic layer that hydridization connects is constituted, and its theoretic throat is only
0.35nm, is the thinnest two-dimensional material found at present.Graphene has a lot of excellent thing
Physicochemical character, as extremely strong in its electric conductivity: the electronics in Graphene does not has quality, the fortune of electronics
Dynamic speed has exceeded the movement velocity in other metallic monomer or quasiconductor, it is possible to reach light
The 1/300 of speed, just because of this, Graphene has superpower electric conductivity；High transparent: because
Graphene is the thinnest two-dimensional material, and its theoretic throat is only 0.35nm, therefore its light transmittance
High, more than 95% can be reached.It addition, Graphene belongs to a kind of new carbon, carbon exists
Earth resource is the abundantest in laying in, and its content is without limitation on its large-scale application.Therefore, stone
Alkene is potential becomes a kind of transparent heat-insulated material of a new generation substituting ITO for ink.Exploitation is based on graphite
The Graphene composite coating of alkene has huge promotion work for the reducing energy consumption of high energy consumption glass
With.But, current Graphene is prone to due to π-πconjugation and Van der Waals force adsorption
Reunite.Further, since the structure of Graphene uniqueness makes it be difficult to and other medium generation physics
Or chemical action, bond strength is the highest, and application is limited.
Summary of the invention
For the deficiencies in the prior art, present invention is primarily targeted at a kind of Graphene of offer multiple
Closing coating and preparation method thereof, it is saturating that described Graphene composite coating not only has higher visible ray
Light rate, also has higher infrared light rejection rate, is applied to building or vehicles glass
The reducing energy consumption of glass, can play the energy-saving effect of heat-insulation and heat-preservation.
The present invention provides a kind of Graphene composite coating, and it is by coating main body, graphene dispersing solution
And coating additive composition, percent mass shared by coating main body described in Graphene composite coating
Number is 40%～60%, the mass percent shared by described graphene dispersing solution be 30%～50% and
Mass percent shared by described coating additive is 3%～10%, and described graphene dispersing solution includes
Graphene, oligomer of phenylamine derivant and disperse medium, this Graphene by with oligomer of phenylamine
Derivant forms pi-pi bond and is dispersed in described coating main body.
Wherein, described in described graphene dispersing solution, mass percent shared by Graphene is
0.1%～10%, the mass percent shared by described oligomer of phenylamine derivant is 0.1%～10%,
And the mass percent shared by described disperse medium is 80%～90%.
Wherein, described in Graphene composite coating, mass percent shared by coating additive is
3%～5%.
Wherein, described oligomer of phenylamine derivant is the oligomer of phenylamine with functional group, described
Functional group includes carboxyl, alkyl, sulfonic group, phosphate, epoxide group, polyethylene group
And/or polyvinyl alcohol group, described oligomer of phenylamine be aniline trimer, Tetraaniline,
One in aniline pentamer, aniline six aggressiveness, aniline eight aggressiveness or combination.
Wherein, described disperse medium be deionized water, ethanol, acetone, isopropanol, butanol,
In ethyl acetate, toluene, chloroform, dimethylformamide, dimethyl sulfoxide dichloroethanes one
Planting or combination, described coating main body is organic siliconresin, acrylic resin, polyester resin, gathers
One in urethane resin, alkyd resin and epoxy resin or combination.
Wherein, described coating additive includes film former, wetting agent, defoamer and levelling agent, institute
Stating film former is ethylene glycol monobutyl ether, propylene glycol monobutyl ether, dipropylene glycol methyl ether ether ester, second
One in glycol propyl ether, dipropyl ether, propylene glycol phenylate, benzyl alcohol, Lauryl Alcohol ester or group
Closing, described wetting agent is lauryl sulfate, dodecane sulfonate, polyvinyl alcohol, gathers
One in vinylpyrrolidone, organo-silicon compound and organofluorine compound or combination, described
Defoamer be dimethicone, ether ester compound, modified mineral oil, polyoxyethanyl glycerin ether,
One in little molecular metal Organic substance and silicon modified organic polymer or combination, described levelling agent
For butyl glycol ether, cellaburate, polyacrylate, silicone oil, hydroxymethyl cellulose,
One in polydimethylsiloxane, PSI and modified organic silicon compound or group
Close.
The present invention also provides for the preparation method of a kind of Graphene composite coating, and it includes following step
Rapid: oligomer of phenylamine derivant and disperse medium to be mixed, obtains mixture A；To described mixed
In compound A add Graphene, make oligomer of phenylamine derivant mix homogeneously with Graphene and
Form pi-pi bond between oligomer of phenylamine derivant and Graphene and obtain graphene dispersing solution；There is provided
One coating main body, adds described graphene dispersing solution mix homogeneously in described coating main body,
Obtain mixture B；In described mixture B, add coating additive, obtain the compound painting of Graphene
Material, wherein, mass percent shared by coating main body described in described Graphene composite coating
Be 40%～60%, the mass percent shared by described graphene dispersing solution be 30%～50% and
Mass percent shared by described coating additive is 3%～10%.
Wherein, described in described graphene dispersing solution, mass percent shared by Graphene is
0.1%～10%, the mass percent shared by described oligomer of phenylamine derivant is 0.1%～10
%, and the mass percent shared by described disperse medium is 80%～90%.
Wherein, described oligomer of phenylamine derivant is the oligomer of phenylamine with functional group, described
Functional group includes carboxyl, alkyl, sulfonic group, phosphate, epoxide group, polyethylene group
And/or polyvinyl alcohol group, described oligomer of phenylamine be aniline trimer, Tetraaniline,
One in aniline pentamer, aniline six aggressiveness, aniline eight aggressiveness or combination.
Wherein, by the process for dispersing of high-speed stirred, ultrasonic, ball milling and/or sand milling by described
Graphene dispersing solution is mixed homogeneously with described coating main body.
Compared to prior art, in the Graphene composite coating that the present invention provides, by graphite
The surface of alkene powder body, through the modifying and decorating of oligomer of phenylamine derivant, greatly improves Graphene
Dispersibility and chemical stability so that described graphene uniform is scattered in described coating main body
In, therefore described Graphene composite coating is easily attached to automobile front windshield, building glass etc. thoroughly
Bright carrier surface, obtained film is transparent, heat-insulation and heat-preservation, and energy-saving effect is notable.Further,
Described Graphene composite coating, without heavy metal elements such as In, Sn, will not bring heavy metal-polluted
The problem of dye.The preparation method of the Graphene composite coating that the present invention provides, passes through preparation technology
Innovation, can obtain the Graphene composite coating with preferable dispersibility and chemical stability, preparation
Technique is simple, with low cost, the beneficially commercial application of Graphene.
Accompanying drawing explanation
Fig. 1 be the graphene dispersing solution in embodiment of the present invention 1-3 photo (wherein from a left side to
Part not corresponding embodiment 1-3 on the right side).
Fig. 2 is graphene dispersing solution described in embodiment 1 and the Raman of undressed Graphene
(wherein, solid line represents graphene dispersing solution described in embodiment 1 to collection of illustrative plates, and dotted line represents without place
The Graphene of reason).
Detailed description of the invention
Below with reference to Graphene composite coating that the present invention is provided by accompanying drawing and preparation method thereof
It is described further.
The embodiment of the present invention provides the preparation method of a kind of Graphene composite coating, and it includes as follows
Step:
Operation (1): oligomer of phenylamine derivant and disperse medium are mixed, obtains mixture A.
Described oligomer of phenylamine derivant has good dissolubility, dissolves in described disperse medium.
Described oligomer of phenylamine derivant is for Graphene described in modification.Described oligomer of phenylamine spreads out
Biology is the oligomer of phenylamine with functional group, and described functional group includes carboxyl, alkyl, sulfonic acid
Base, phosphate, epoxide group, polyethylene group and/or polyvinyl alcohol group.Preferably,
Described oligomer of phenylamine is that aniline trimer, Tetraaniline, aniline pentamer, aniline six gather
One in body, aniline eight aggressiveness or combination.
Described oligomer of phenylamine or derivatives thereof can have a following structural formula:
(M is mainly sodium ion, potassium ion, quaternary ammonium salt etc.).
Described disperse medium is deionized water, ethanol, acetone, isopropanol, butanol, acetic acid second
One or several in ester, toluene, chloroform, dimethylformamide, dimethyl sulfoxide dichloroethanes
Plant mixed solvent.Described oligomer of phenylamine derivant with the mass ratio of described disperse medium is
(0.1～10): (80～90).In order to avoid when oligomer of phenylamine derivative content too low, then disperse stone
Ink alkene limited in one's ability, and when oligomer of phenylamine derivative content too high, the dispersion of itself
Property also can be affected, it is preferable that described oligomer of phenylamine derivant and described disperse medium
Mass ratio is (0.5～5): (80～90).
Operation (2): add Graphene in described mixture A, makes oligomer of phenylamine derive
Thing is mixed homogeneously with Graphene and forms pi-pi bond between oligomer of phenylamine derivant and Graphene
Obtain graphene dispersing solution.Concrete, due to the phenyl ring in described oligomer of phenylamine derivant and
Graphene-structured is close, thus described oligomer of phenylamine derivant can and Graphene between formed
Pi-pi bond and realize mixing with graphene uniform.It is pointed out that and utilize oligomer of phenylamine to spread out
Forming pi-pi bond between biology and Graphene, this mode is different from grafting modification, and it is also
Do not destroy the structure of Graphene itself, also different from the macromolecule of physical property coated graphite alkene, its
Do not sacrifice the performance of Graphene.It is to say, it is modified by oligomer of phenylamine Derivatives Modified
Graphene, its dispersibility only making Graphene and stability are more preferable, and do not destroy Graphene
Structure, does not the most reduce the original performance of Graphene.
It is appreciated that after described Graphene is added described mixture A, high-speed stirring can be passed through
Mix, the process for dispersing of ultrasonic, ball milling and/or sand milling makes graphene uniform be scattered in mixture A,
Graphene is made to mix homogeneously with oligomer of phenylamine derivant further.
The structure of described Graphene does not limits, it include graphene nanometer sheet, Graphene micron film,
Graphene nanobelt, few layer graphene (2-5 layer), multi-layer graphene (2-9 layer), graphite
Alkene quantum dot and the derivant of these graphite alkenes materials).The definition of described grapheme material
Can be found in document " All in the graphene family A recommended nomenclature
for two-dimensional carbon materials”.Described grapheme material is also selected from thickness
Degree≤20nm, it is highly preferred that the material of thickness≤10nm.In the present embodiment, this graphite
The thickness of alkene material preferably≤3nm, grapheme material is the thinnest, and pliability is the best, the most easily adds
Work.Described grapheme material preparation method do not limit, use well known to those skilled in the art
Prepared by graphene product or the preparation method by routine.Grapheme material can be selected from chemistry
Any one side in oxidizing process such as Brodie method, Hummers method or Staudenmaier method
The grapheme material that graphene oxide prepared by method prepares through thermal expansion.Machinery stripping can also be selected
Peel off from, liquid phase or grapheme material prepared by electrochemical stripping.
Described Graphene is (0.1～10) with the mass ratio of described disperse medium: (80～90).Now,
Described in the graphene dispersing solution obtained, the mass percent shared by Graphene is 0.1%～10%,
Mass percent shared by described oligomer of phenylamine derivant is 0.1%～10%, and described
Mass percent shared by disperse medium is 80%～90%.In order to avoid when Graphene content mistake
Low, its application value is little, and when fruit Graphene too high levels, oligomer of phenylamine derivant
Limited to its dispersion effect, it is preferable that described Graphene with the mass ratio of described disperse medium is
(0.5～5): (80～90).
Operation (3): provide a coating main body, adds described Graphene in described coating main body
Dispersion liquid mix homogeneously, obtain mixture B.Described coating main body be organic siliconresin, third
One in olefin(e) acid resin, polyester resin, polyurethane resin, alkyd resin and epoxy resin or
Combination.Described coating main body is (4～6) with the mass ratio of described graphene dispersing solution: (3～5).Can
To understand, described graphene dispersing solution can pass through high-speed stirred, ultrasonic, ball milling and/or sand milling
Process for dispersing mix homogeneously with described coating main body, so that Graphene is the most dispersed
In described coating main body.
Operation (4): add coating additive in described mixture B, obtains Graphene and is combined
Coating.Described coating additive includes film former, wetting agent, defoamer and levelling agent.Described one-tenth
Membrane is ethylene glycol monobutyl ether, propylene glycol monobutyl ether, dipropylene glycol methyl ether ether ester, ethylene glycol
One in propyl ether, dipropyl ether, propylene glycol phenylate, benzyl alcohol, Lauryl Alcohol ester or combination.
Described wetting agent is lauryl sulfate, dodecane sulfonate, polyvinyl alcohol, polyethylene
One in ketopyrrolidine, organo-silicon compound and organofluorine compound or combination.Described froth breaking
Agent be dimethicone, ether ester compound, modified mineral oil, polyoxyethanyl glycerin ether, little point
One in sub-metallorganic and silicon modified organic polymer or combination.Described levelling agent is second
Glycol butyl ether, cellaburate, polyacrylate, silicone oil, hydroxymethyl cellulose, poly-two
One in methyl-monosilane, PSI and modified organic silicon compound or combination.
Described coating additive is (0.3～1) with the mass ratio of described graphene dispersing solution: (3～5).?
To Graphene composite coating described in mass percent shared by coating main body be 40%～60
%, the mass percent shared by described graphene dispersing solution be 30%～50% and described coating help
Mass percent shared by agent is 3%～10%.In order to avoid when coating additive content too low,
The oligomer of phenylamine derivant of high concentration is disperseed deficiency by it, and when coating additive content mistake
Height, can affect to the performance of Graphene, it is preferable that described coating additive and institute
The mass ratio stating graphene dispersing solution is (0.3～0.5): (3～5).
The present invention also provides for a kind of Graphene composite coating using said method to prepare.Described stone
Ink alkene composite coating is made up of coating main body, graphene dispersing solution and coating additive.At Graphene
Mass percent shared by coating main body described in composite coating is 40%～60%, described graphite
Mass percent shared by alkene dispersion liquid be 30%～50% and described coating additive shared by quality
Percent is 3%～10%.
Described graphene dispersing solution includes Graphene, oligomer of phenylamine derivant and disperse medium,
This Graphene is dispersed in described dispersion by forming pi-pi bond with oligomer of phenylamine derivant
In medium, and then realize described graphene uniform and be scattered in described coating main body.At described stone
Described in ink alkene dispersion liquid, the mass percent shared by Graphene is 0.1%～10%, described aniline
Mass percent shared by oligomer derivative is 0.1%～10%, and described disperse medium institute
The mass percent accounted for is 80%～90%.
In the Graphene composite coating that the present invention provides, by the surface of graphene powder is passed through
The modifying and decorating of oligomer of phenylamine derivant, greatly improve Graphene in composite coating point
Dissipate property and chemical stability so that described Graphene composite coating is easily attached to automotive front baffle glass
The transparent carrier such as glass, building glass surface, obtained film is transparent, and heat-insulation and heat-preservation is energy-conservation
Effect is notable.Further, described Graphene composite coating does not contains the heavy metal elements such as In, Sn,
The problem that will not bring heavy metal pollution.The preparation side of the Graphene composite coating that the present invention provides
Method, is innovated by preparation technology, can obtain the graphite with preferable dispersibility and chemical stability
Alkene composite coating, preparation technology is simple, with low cost, the beneficially commercial application of Graphene.
For further describing the present invention, it is the preparation method of described Graphene composite coating below,
Specific embodiment under different parameters:
Embodiment 1:
The first high-speed stirred under 1500rad/min by 10g aniline trimer and 80g deionized water
Dispersion 10min, obtains mixture A.Again 10g single-layer graphene powder body is added mixture A
In, continue high-speed stirred 20min ultrasonic 10min, i.e. obtain uniform and stable Graphene and divide
Dissipate liquid.
60g organic siliconresin is added in stirring container, then in 1500rad/min high-speed stirring
Add graphene dispersing solution described in 35g under conditions of mixing, stir, obtain mixture B.
In mixture B, addition 2g ethylene glycol monobutyl ether, 2g lauryl sulfate, 0.5g change again
Property mineral oil and 0.5g silicone oil, continue stirring 10min ultrasonic disperse 30min, through 325～400
Eye mesh screen filtration treatment, i.e. obtains Graphene composite coating.
The dispersion effect of described graphene dispersing solution refers to Fig. 1.As seen from Figure 1, described stone
The dispersion effect of ink alkene dispersion liquid is preferable.
The Raman spectrum of described graphene dispersing solution asks for an interview Fig. 2.From Figure 2 it can be seen that 1410
cm-1The absworption peak of position corresponds to pi-pi bond.This explanation is at oligomer of phenylamine derivant and stone
Pi-pi bond is formed between ink alkene.
Obtained Graphene composite coating is carried out performance test.Concrete, by obtained
Graphene composite coating with the bar spreader of 10 μm be respectively coated in
On the flat glass film of 10cm × 10cm × 0.2cm, in 80 DEG C of baking ovens, then it is dried 1h,
To film.
Film is detected according to GB/T 2680 visible by ultraviolet-visible-infrared spectrophotometer
Light transmission rate, infrared light transmittance, ultraviolet light rejection rate.
Detected the adhesive force of film according to GB/T 9286 by cross-hatching.
Detecting the resistance to water of film by room temperature bowssening according to GB/T 1733, the testing time is
96 hours.
Detected the energy of resistance to artificial weathering aging of film according to GB/T 1865 by Weatherometer
Power, the testing time is 1000 hours.
Replace test basis GB/T 1735 by cold-hot and detect the temperature-change resistance of film.
The main performance of the film that obtained Graphene composite coating is made is shown in Table 1.
Embodiment 2:
The first high-speed stirred dispersion under 1500rad/min by 9.9g Tetraaniline and 90g ethanol
10min, obtains mixture A.Again 0.1g multi-layer graphene powder body is added in mixture A,
Continue high-speed stirred 20min ultrasonic 10min, i.e. obtain uniform and stable graphene dispersing solution.
52g acrylic resin is added in stirring container, then in 1500rad/min high-speed stirring
Add graphene dispersing solution described in 45g under conditions of mixing, stir, obtain mixture B.
Again in mixture B add 1g dipropylene glycol methyl ether ether ester, 1g dodecane sulfonate,
0.5g dimethicone and 0.5g hydroxymethyl cellulose, continue stirring 10min ultrasonic disperse
30min, through 325～400 eye mesh screen filtration treatment, i.e. obtains Graphene composite coating.
The dispersion effect of described graphene dispersing solution refers to Fig. 1.As seen from Figure 1, described stone
The dispersion effect of ink alkene dispersion liquid is preferable.
Obtained Graphene composite coating is carried out performance test.Method of testing is with embodiment 1.
The main performance of the film that obtained Graphene composite coating is made is shown in Table 1.
Embodiment 3:
The first high-speed stirred dispersion under 1500rad/min by 0.1g aniline pentamer and 90g acetone
10min, obtains mixture A.Again 9.9g single-layer graphene slurry is added in mixture A,
Continue high-speed stirred 20min ultrasonic 10min, i.e. obtain uniform and stable graphene dispersing solution.
55g polyester resin is added in stirring container, then in 1500rad/min high-speed stirred
Under conditions of add graphene dispersing solution described in 40g, stir, obtain mixture B.Again
In mixture B add 2g glycol propyl ether, 2g polyvinyl alcohol, 0.5g ether ester compound and
0.5g polyacrylate, continues stirring 10min ultrasonic disperse 30min, through 325～400
Eye mesh screen filtration treatment, i.e. obtains Graphene composite coating.
The dispersion effect of described graphene dispersing solution refers to Fig. 1.As seen from Figure 1, described stone
The dispersion effect of ink alkene dispersion liquid is preferable.
Obtained Graphene composite coating is carried out performance test.Method of testing is with embodiment 1.
The main performance of the film that obtained Graphene composite coating is made is shown in Table 1.
Embodiment 4:
The first high-speed stirred under 1500rad/min by 10g aniline six aggressiveness and 85g ethyl acetate
Dispersion 10min, obtain mixture A.Again 5g multi-layer graphene slurry is added mixture A
In, continue high-speed stirred 20min ultrasonic 10min, i.e. obtain uniform and stable Graphene and divide
Dissipate liquid.
40g polyurethane resin is added in stirring container, then in 1500rad/min high-speed stirring
Add graphene dispersing solution described in 50g under conditions of mixing, stir, obtain mixture B.
5g propylene glycol phenylate, 4g polyvinylpyrrolidone, 0.5g polyoxy is added again in mixture B
Ethyl glycerin ether and 0.5g butyl glycol ether, continue stirring 10min ultrasonic disperse 30min,
Through 325～400 eye mesh screen filtration treatment, i.e. obtain Graphene composite coating.
Obtained Graphene composite coating is carried out performance test.Method of testing is with embodiment 1.
The main performance of the film that obtained Graphene composite coating is made is shown in Table 1.
Embodiment 5:
The first high speed under 1500rad/min by 5g Tetraaniline carboxy derivatives and 85g toluene
Dispersed with stirring 10min, obtains mixture A.Again 10g single-layer graphene powder body is added mixing
In thing A, continue high-speed stirred 20min ultrasonic 10min, i.e. obtain uniform and stable graphite
Alkene dispersion liquid.
45g alkyd resin is added in stirring container, then in 1500rad/min high-speed stirred
Under conditions of add graphene dispersing solution described in 45g, stir, obtain mixture B.Again
In mixture B add 4g benzyl alcohol, 4g organosilicon, 1g little molecular metal Organic substance and
1g polydimethylsiloxane, continues stirring 10min ultrasonic disperse 30min, through 325～400
Eye mesh screen filtration treatment, i.e. obtains Graphene composite coating.
Obtained Graphene composite coating is carried out performance test.Method of testing is with embodiment 1.
The main performance of the film that obtained Graphene composite coating is made is shown in Table 1.
Embodiment 6:
The first high speed under 1500rad/min by 5g aniline trimer alkyl derivative and 90g chloroform
Dispersed with stirring 10min, obtains mixture A.Again 5g single-layer graphene slurry is added mixing
In thing A, continue high-speed stirred 20min ultrasonic 10min, i.e. obtain uniform and stable graphite
Alkene dispersion liquid.
60g epoxy resin is added in stirring container, then in 1500rad/min high-speed stirred
Under conditions of add graphene dispersing solution described in 30g, stir, obtain mixture B.Again
5g Lauryl Alcohol ester, 4g organofluorine compound, 0.5g modification is added organic in mixture B
Silicon polymer and 0.5g PSI, continue stirring 10min ultrasonic disperse
30min, through 325～400 eye mesh screen filtration treatment, i.e. obtains Graphene composite coating.
Obtained Graphene composite coating is carried out performance test.Method of testing is with embodiment 1.
The main performance of the film that obtained Graphene composite coating is made is shown in Table 1.
Table 1
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | |
| Visible light transmissivity | 91% | 94% | 93% | 92% | 90% | 95% |
| Infrared light transmittance | 7% | 12% | 10% | 8% | 5% | 15% |
| Ultraviolet light rejection rate | 99% | 98% | 99% | 99% | 99% | 97% |
| Resistance to water | Without exception | Without exception | Without exception | Without exception | Without exception | Without exception |
| Resistance to artificial weathering aging | Without exception | Without exception | Without exception | Without exception | Without exception | Without exception |
| Adhesive force | 0 grade | 0 grade | 0 grade | 0 grade | 0 grade | 0 grade |
| Temperature-change resistance | Without exception | Without exception | Without exception | Without exception | Without exception | Without exception |
From table 1, the film that Graphene composite coating of the present invention is made has higher
Visible light transmissivity, almost can shielding ultraviolet rays completely, can be higher to energy in sunlight
Infrared ray is effectively stopped, and coating is ageing-resistant, waterproof simultaneously, adhesive force, temperature-change resistance are good.
The explanation of above example is only intended to help to understand that the method for the present invention and core thereof are thought
Think.It should be pointed out that, for those skilled in the art, without departing from this
On the premise of bright principle, it is also possible to the present invention is carried out some improvement and modification, these improve and
Modify in the protection domain also falling into the claims in the present invention.Multiple amendment to these embodiments
It is apparent from for those skilled in the art, as defined herein the most former
Reason can realize the most in other embodiments.
Therefore, the present invention is not intended to be limited to the embodiments shown herein, and be to fit to
Principles disclosed herein and the consistent the widest scope of features of novelty.
Claims (10)
1. a Graphene composite coating, it is characterised in that it is by coating main body, graphene dispersion
Liquid and coating additive composition, quality hundred shared by coating main body described in Graphene composite coating
Mark is 40%～60%, and the mass percent shared by described graphene dispersing solution is 30%～50%
And the mass percent shared by described coating additive is 3%～10%, described graphene dispersing solution bag
Including Graphene, oligomer of phenylamine derivant and disperse medium, this Graphene is by oligomeric with aniline
Thing derivant forms pi-pi bond and is dispersed in described coating main body.
Graphene composite coating the most according to claim 1, it is characterised in that at described graphite
Described in alkene dispersion liquid, the mass percent shared by Graphene is 0.1%～10%, and described aniline is low
Mass percent shared by polymers derivant is 0.1%～10%, and shared by described disperse medium
Mass percent be 80%～90%.
Graphene composite coating the most according to claim 1, it is characterised in that multiple at Graphene
Described in conjunction coating, the mass percent shared by coating additive is 3%～5%.
Graphene composite coating the most according to claim 1, it is characterised in that described aniline is low
Polymers derivant is the oligomer of phenylamine with functional group, described functional group include carboxyl, alkyl,
Sulfonic group, phosphate, epoxide group, polyethylene group and/or polyvinyl alcohol group, institute
State oligomer of phenylamine be aniline trimer, Tetraaniline, aniline pentamer, aniline six aggressiveness,
One in aniline eight aggressiveness or combination.
Graphene composite coating the most according to claim 1, it is characterised in that described dispersion is situated between
Matter be deionized water, ethanol, acetone, isopropanol, butanol, ethyl acetate, toluene, chloroform,
One in dimethylformamide, dimethyl sulfoxide dichloroethanes or combination, described coating main body
For organic siliconresin, acrylic resin, polyester resin, polyurethane resin, alkyd resin and ring
One in epoxy resins or combination.
Graphene composite coating the most according to claim 1, it is characterised in that described coating helps
Agent includes that film former, wetting agent, defoamer and levelling agent, described film former are ethylene glycol only son
Ether, propylene glycol monobutyl ether, dipropylene glycol methyl ether ether ester, glycol propyl ether, dipropyl ether, third
One in glycol phenylate, benzyl alcohol, Lauryl Alcohol ester or combination, described wetting agent is 12
Alkyl sulfate, dodecane sulfonate, polyvinyl alcohol, polyvinylpyrrolidone, organosilicon
One in compound and organofluorine compound or combination, described defoamer be dimethicone,
Ether ester compound, modified mineral oil, polyoxyethanyl glycerin ether, little molecular metal Organic substance and change
Property organosilicon polymer in one or combination, described levelling agent is that butyl glycol ether, vinegar fourth are fine
Dimension element, polyacrylate, silicone oil, hydroxymethyl cellulose, polydimethylsiloxane, poly-methyl
One in phenyl siloxane and modified organic silicon compound or combination.
7. a preparation method for Graphene composite coating, it comprises the following steps:
Oligomer of phenylamine derivant and disperse medium are mixed, obtains mixture A；
In described mixture A, add Graphene, make oligomer of phenylamine derivant and Graphene
Mix homogeneously and between oligomer of phenylamine derivant and Graphene formed pi-pi bond obtain Graphene
Dispersion liquid；
One coating main body is provided, in described coating main body, adds described graphene dispersing solution and mix
Close uniformly, obtain mixture B；
In described mixture B, add coating additive, obtain Graphene composite coating,
Wherein, mass percent shared by coating main body described in described Graphene composite coating
Be 40%～60%, the mass percent shared by described graphene dispersing solution be 30%～50% and
Mass percent shared by described coating additive is 3%～10%.
The preparation method of Graphene composite coating the most according to claim 1, it is characterised in that
Described in described graphene dispersing solution, the mass percent shared by Graphene is 0.1%～10%,
Mass percent shared by described oligomer of phenylamine derivant is 0.1%～10%, and described
Mass percent shared by disperse medium is 80%～90%.
The preparation method of Graphene composite coating the most according to claim 8, it is characterised in that
Described oligomer of phenylamine derivant is the oligomer of phenylamine with functional group, and described functional group includes
Carboxyl, alkyl, sulfonic group, phosphate, epoxide group, polyethylene group and/or poly-second
Enol group, described oligomer of phenylamine be aniline trimer, Tetraaniline, aniline pentamer,
One in aniline six aggressiveness, aniline eight aggressiveness or combination.
The preparation method of Graphene composite coating the most according to claim 8, it is characterised in that
By the process for dispersing of high-speed stirred, ultrasonic, ball milling and/or sand milling by described graphene dispersion
Liquid is mixed homogeneously with described coating main body.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201410814945.7A CN105778608B (en) | 2014-12-24 | 2014-12-24 | A kind of graphene composite coating and preparation method thereof |
| EP15865917.7A EP3228592A4 (en) | 2014-12-02 | 2015-11-27 | Graphene dispersant and application thereof |
| PCT/CN2015/095742 WO2016086796A1 (en) | 2014-12-02 | 2015-11-27 | Graphene dispersant and application thereof |
| TW104139658A TWI602611B (en) | 2014-12-02 | 2015-11-27 | Graphene dispersant and its application |
| US15/607,552 US10696790B2 (en) | 2014-12-02 | 2017-05-29 | Graphene dispersant and application thereof |
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| CN201410814945.7A CN105778608B (en) | 2014-12-24 | 2014-12-24 | A kind of graphene composite coating and preparation method thereof |
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| CN107286832A (en) * | 2017-08-01 | 2017-10-24 | 合肥广民建材有限公司 | A kind of waterproof heat-insulating coating and preparation method |
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| CN108219619A (en) * | 2017-12-04 | 2018-06-29 | 佛山杰致信息科技有限公司 | A kind of heat-insulating and sound-proof material and preparation method thereof |
| CN109021633A (en) * | 2018-06-21 | 2018-12-18 | 深圳陶金材料科技有限公司 | A kind of graphene-based high-temperature coatings and preparation method thereof |
| CN110872465A (en) * | 2018-08-29 | 2020-03-10 | 中国石油化工股份有限公司 | Graphene insulating coating and preparation method and application thereof |
| CN110872465B (en) * | 2018-08-29 | 2022-02-01 | 中国石油化工股份有限公司 | Graphene insulating coating and preparation method and application thereof |
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