CN105778608B - A kind of graphene composite coating and preparation method thereof - Google Patents
A kind of graphene composite coating and preparation method thereof Download PDFInfo
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- CN105778608B CN105778608B CN201410814945.7A CN201410814945A CN105778608B CN 105778608 B CN105778608 B CN 105778608B CN 201410814945 A CN201410814945 A CN 201410814945A CN 105778608 B CN105778608 B CN 105778608B
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Abstract
The present invention provides a kind of graphene composite coatings, it is made of coating main body, graphene dispersing solution and coating additive, mass percent shared by the coating main body described in graphene composite coating is 40%~60%, mass percent shared by the graphene dispersing solution be 30%~50% and the coating additive shared by mass percent be 3%~10%, the graphene dispersing solution includes graphene, oligomer of phenylamine derivative and decentralized medium, which is dispersed in the coating main body and forming pi-pi bond with oligomer of phenylamine derivative.The present invention also provides a kind of preparation methods of graphene composite coating.
Description
Technical field
The present invention relates to a kind of transparent heat insulating dope more particularly to a kind of graphene composite coating based on graphene and its
Preparation method.
Background technique
Global energy supply be becoming tight under the situation of environment worsening, energy-saving and emission-reduction have become countries in the world jointly
Target.China is energy consumption big country, and annual social total energy consumption is equivalent to 1,500,000,000 tons of standard coals, wherein 30% or so is building consumption
Energy.In modern building, the ratio that glass accounts for exterior wall is increasing, according to measuring and calculating by the heat that windowpane carries out be delivered in the winter,
Summer accounts for 48% and 71% respectively.In cold winter, it is desirable to more obtain direct solar radiation thermal energy, while again
It is expected that leaking for indoor heat radiation is reduced, so that interior is able to maintain higher temperature；During the broiling summer, wish again will too by people
The infra-red radiation thermal energy of sun is blocked in outdoor, to mitigate the burden of air conditioner refrigerating.
It is existing to solve the problems, such as glass heat-proof mainly and have three approach: first is that using Heat insulation type adhering film；Due to thermal isolation film price
It is expensive, it is difficult to which that large-scale popularization can only use on a small amount of high-grade car.Second is that using thermal reflecting coating；But existing heat reflection
Film product is opaque, it is widely applied can not.Three are used in hollow glass made of the silver-plated equal metallicses of glass surface；
But since production line of hollow glasses equipment and investment are huge, so that can not mass production use.
Transparent heat insulating dope is that one kind can allow glass that high light transmittance had not only been kept to meet daylighting requirement, but also have preferable
The material of heat insulation.Currently, external glass transparent insulating coating is high using popularity rate, in the U.S., transparent heat insulating dope
Popularity rate is more than 90%；80% or more is also had reached in the popularity rate of European Region, transparent heat insulating dope.In Asia,
Other than Hong-Kong, Taiwan and Japan, South Korea, the building glass transparent heat insulating dope popularity rate of other countries is average not
To 20%.The popularity rate of the building glass transparent heat insulating dope of China mainland is less than 10%.Carry out section energetically in present China
The policy of energy emission reduction, glass transparent insulating coating have very big development space.
In recent years, graphene was attracted wide attention as a kind of new material in the whole world.It is by carbon atom with
sp2What the monoatomic layer of hydridization connection was constituted, theoretic throat is only 0.35nm, is the most thin two-dimentional material found at present
Material.Graphene has many excellent physicochemical properties, and as its electric conductivity is extremely strong: the electronics in graphene does not have quality, electricity
The movement velocity of son has been more than the movement velocity in other metallic monomers or semiconductor, can reach the 1/300 of the light velocity, just
Because in this way, graphene possesses superpower electric conductivity；High transparency: because graphene is most thin two-dimensional material, theoretic throat
It is only 0.35nm, therefore its light transmittance is high, can achieve 95% or more.In addition, graphene belongs to a kind of new carbon,
Carbon very abundant in earth resource deposit, content is without limitation on its large-scale application.Therefore, graphene is potential becomes one
The transparent heat-insulated material of a new generation of kind substitution ITO.The graphene composite coating based on graphene is developed for high energy consumption glass
Reducing energy consumption has huge impetus.However, at present graphene due to π-πconjugation and Van der Waals force suction-operated and
It is easy to reunite.In addition, since the unique structure of graphene makes it be difficult to occur physically or chemically to act on other media, in conjunction with
Intensity is not high, and application field is limited.
Summary of the invention
In view of the deficiencies of the prior art, the main purpose of the present invention is to provide a kind of graphene composite coating and its preparations
Method, the graphene composite coating not only incite somebody to action by visible light transmittance rate with higher, infrared light rejection rate also with higher
Its reducing energy consumption for being applied to building or vehicles glass, can play the energy-saving effect of heat-insulation and heat-preservation.
The present invention provides a kind of graphene composite coating, is made of coating main body, graphene dispersing solution and coating additive,
Mass percent shared by the coating main body described in graphene composite coating is 40%~60%, the graphene dispersing solution institute
The mass percent accounted for be 30%~50% and the coating additive shared by mass percent be 3%~10%, the graphite
Alkene dispersion liquid includes graphene, oligomer of phenylamine derivative and decentralized medium, the graphene by with oligomer of phenylamine derivative
It forms pi-pi bond and is dispersed in the coating main body.
Wherein, mass percent shared by the graphene described in the graphene dispersing solution is 0.1%~10%, described
Mass percent shared by oligomer of phenylamine derivative is quality percentage shared by 0.1%~10% and the decentralized medium
Number is 80%~90%.
Wherein, mass percent shared by the coating additive described in graphene composite coating is 3%~5%.
Wherein, the oligomer of phenylamine derivative be the oligomer of phenylamine with functional group, the functional group include carboxyl,
Alkyl, sulfonic group, phosphate, epoxy group, polyethylene group and/or polyvinyl alcohol group, the oligomer of phenylamine are benzene
One of amine tripolymer, Tetraaniline, aniline pentamer, six aggressiveness of aniline, eight aggressiveness of aniline or combination.
Wherein, the decentralized medium be deionized water, ethyl alcohol, acetone, isopropanol, butanol, ethyl acetate, toluene, chloroform,
One of dimethylformamide, dimethyl sulfoxide dichloroethanes or combination, the coating main body are organic siliconresin, acrylic acid
One of resin, polyester resin, polyurethane resin, alkyd resin and epoxy resin or combination.
Wherein, the coating additive includes film forming agent, wetting agent, defoaming agent and levelling agent, and the film forming agent is ethylene glycol
Monobutyl ether, propylene glycol monobutyl ether, dipropylene glycol methyl ether ether ester, glycol propyl ether, dipropyl ether, propylene glycol phenylate, benzyl alcohol, ten
One of two carbon alcohol esters or combination, the wetting agent are lauryl sulfate, dodecane sulfonate, polyvinyl alcohol, gather
One of vinylpyrrolidone, organo-silicon compound and organofluorine compound or combination, the defoaming agent be dimethicone,
One in ether ester compound, modified mineral oil, polyoxyethanyl glycerin ether, small molecule metallorganic and silicon modified organic polymer
Kind or combination, the levelling agent are butyl glycol ether, cellaburate, polyacrylate, silicone oil, hydroxymethyl cellulose, gather
One of dimethylsilane, polymethylphenylsiloxane and modified organic silicon compound or combination.
The present invention also provides a kind of preparation methods of graphene composite coating comprising following steps: by oligomer of phenylamine
Derivative and decentralized medium mixing, obtain mixture A；Graphene is added into the mixture A, makes oligomer of phenylamine derivative
It is uniformly mixed with graphene and forms pi-pi bond between oligomer of phenylamine derivative and graphene and obtain graphene dispersing solution；It mentions
For a coating main body, the graphene dispersing solution is added in Xiang Suoshu coating main body and is uniformly mixed, obtains mixture B；To institute
It states in mixture B and coating additive is added, obtain graphene composite coating, wherein applied described in the graphene composite coating
Expect that mass percent shared by main body is 40%~60%, mass percent shared by the graphene dispersing solution is 30%~
50% and the coating additive shared by mass percent be 3%~10%.
Wherein, mass percent shared by the graphene described in the graphene dispersing solution is 0.1%~10%, described
Mass percent shared by oligomer of phenylamine derivative is quality percentage shared by 0.1%~10% and the decentralized medium
Number is 80%~90%.
Wherein, the oligomer of phenylamine derivative be the oligomer of phenylamine with functional group, the functional group include carboxyl,
Alkyl, sulfonic group, phosphate, epoxy group, polyethylene group and/or polyvinyl alcohol group, the oligomer of phenylamine are benzene
One of amine tripolymer, Tetraaniline, aniline pentamer, six aggressiveness of aniline, eight aggressiveness of aniline or combination.
Wherein, by the dispersing method of high-speed stirred, ultrasound, ball milling and/or sand milling by the graphene dispersing solution and institute
Coating main body is stated to be uniformly mixed.
Compared to the prior art, it in graphene composite coating provided by the invention, is passed through by the surface to graphene powder
The modifying and decorating for crossing oligomer of phenylamine derivative greatly improves the dispersibility and chemical stability of graphene, so that the stone
Black alkene is dispersed in the coating main body, therefore the graphene composite coating is easily attached to automobile front windshield, building
The transparent carriers such as glass surface, obtained film is transparent, heat-insulation and heat-preservation, and energy-saving effect is significant.Also, the graphene is compound
The problem of coating is free of the heavy metal elements such as In, Sn, will not bring heavy metal pollution.Graphene composite coating provided by the invention
Preparation method, innovated by preparation process, can obtain with preferably dispersibility and chemical stability graphene composite coating,
Preparation process is simple, low in cost, conducive to the industrial application of graphene.
Detailed description of the invention
Fig. 1 is that the photo of the graphene dispersing solution in 1-3 of the embodiment of the present invention (wherein respectively corresponds embodiment from left to right
1-3)。
Fig. 2 is Raman map (wherein, the solid line generation of graphene dispersing solution and untreated graphene described in embodiment 1
Graphene dispersing solution described in table embodiment 1, dotted line represent untreated graphene).
Specific embodiment
Graphene composite coating provided by the invention and preparation method thereof is described further below with reference to attached drawing.
The embodiment of the present invention provides a kind of preparation method of graphene composite coating comprising following steps:
Process (1): oligomer of phenylamine derivative and decentralized medium are mixed, mixture A is obtained.The oligomer of phenylamine spreads out
Biology has good dissolubility, dissolves in the decentralized medium.The oligomer of phenylamine derivative is used for modification institute
State graphene.The oligomer of phenylamine derivative is the oligomer of phenylamine with functional group, and the functional group includes carboxyl, alkane
Base, sulfonic group, phosphate, epoxy group, polyethylene group and/or polyvinyl alcohol group.Preferably, the oligomer of phenylamine
For one of aniline tripolymer, Tetraaniline, aniline pentamer, six aggressiveness of aniline, eight aggressiveness of aniline or combination.
Described oligomer of phenylamine or derivatives thereof can have the following structure formula:
(M is mainly sodium ion, potassium ion, quaternary ammonium salt etc.).
The decentralized medium is deionized water, ethyl alcohol, acetone, isopropanol, butanol, ethyl acetate, toluene, chloroform, diformazan
One or more of base formamide, dimethyl sulfoxide dichloroethanes mixed solvent.The oligomer of phenylamine derivative with it is described
The mass ratio of decentralized medium is (0.1~10): (80~90).It is too low in order to avoid working as oligomer of phenylamine derivative content, then divide
The ability for dissipating graphene is limited, and when oligomer of phenylamine derivative content is excessively high, the dispersibility of itself also will receive influence,
Preferably, the mass ratio of the oligomer of phenylamine derivative and the decentralized medium is (0.5~5): (80~90).
Process (2): graphene is added in the mixture A, is uniformly mixed oligomer of phenylamine derivative with graphene
And pi-pi bond is formed between oligomer of phenylamine derivative and graphene and obtains graphene dispersing solution.Specifically, due to the aniline
Phenyl ring and graphene-structured in oligomer derivative is close, thus the oligomer of phenylamine derivative can between graphene shape
It realizes at pi-pi bond and is mixed with graphene uniform.It should be pointed out that utilizing shape between oligomer of phenylamine derivative and graphene
At pi-pi bond, this mode is different from grafting modification, the structure of graphene itself is not destroyed, also different from physical
The macromolecule of coated graphite alkene does not sacrifice the performance of graphene.That is, being changed by oligomer of phenylamine Derivatives Modified
Property graphene, only make the dispersibility of graphene and stability more preferable, and do not destroy the structure of graphene, also do not reduce graphite
The original performance of alkene.
It is appreciated that after the mixture A is added in the graphene, can by high-speed stirred, ultrasound, ball milling and/or
The dispersing method of sand milling makes graphene uniform be scattered in mixture A, mixes graphene with oligomer of phenylamine derivative
Uniformly.
The structure of the graphene is unlimited comprising graphene nanometer sheet, graphene nanobelt, lacks graphene micron film
Layer graphene (2-5 layers), multi-layer graphene (2-9 layers), graphene quantum dot and these graphite alkenes materials derivative).
The definition of the grapheme material can be found in document " All in the graphene family-A recommended
nomenclature for two-dimensional carbon materials".The grapheme material is also selected from thickness
Degree≤20nm, it is highly preferred that thickness≤10nm material.In the present embodiment, the grapheme material thickness preferably≤3nm,
Grapheme material is thinner, and flexibility is better, is more easily worked.The preparation method of the grapheme material is unlimited, using ability
Graphene product known to field technique personnel is prepared with conventional preparation method.Grapheme material can be selected from chemical oxygen
The graphene oxide of any one method preparation in change method such as Brodie method, Hummers method or Staudenmaier method is through warm
Expand grapheme material obtained.The grapheme material of mechanical stripping, liquid phase removing or electrochemical stripping preparation can also be selected.
The mass ratio of the graphene and the decentralized medium is (0.1~10): (80~90).At this point, obtained graphite
Mass percent shared by graphene described in alkene dispersion liquid is 0.1%~10%, shared by the oligomer of phenylamine derivative
Mass percent is that mass percent shared by 0.1%~10% and the decentralized medium is 80%~90%.In order to avoid
When graphene content is too low, application value is little, and works as fruit graphene too high levels, and oligomer of phenylamine derivative is to its point
It is limited to dissipate effect, it is preferable that the mass ratio of the graphene and the decentralized medium is (0.5~5): (80~90).
Process (3): providing a coating main body, and the graphene dispersing solution is added in Xiang Suoshu coating main body and mixes equal
It is even, obtain mixture B.The coating main body is organic siliconresin, acrylic resin, polyester resin, polyurethane resin, alkyd tree
One of rouge and epoxy resin or combination.The mass ratio of the coating main body and the graphene dispersing solution is (4~6): (3
~5).It is appreciated that the graphene dispersing solution can dispersing method by high-speed stirred, ultrasound, ball milling and/or sand milling and institute
It states coating main body to be uniformly mixed, so that graphene be made further to be dispersed in the coating main body.
Process (4): coating additive is added in Xiang Suoshu mixture B, obtains graphene composite coating.The coating additive packet
Include film forming agent, wetting agent, defoaming agent and levelling agent.The film forming agent is ethylene glycol monobutyl ether, propylene glycol monobutyl ether, dipropylene glycol
One of methyl ether ether ester, glycol propyl ether, dipropyl ether, propylene glycol phenylate, benzyl alcohol, Lauryl Alcohol ester or combination.It is described
Wetting agent be lauryl sulfate, dodecane sulfonate, polyvinyl alcohol, polyvinylpyrrolidone, organo-silicon compound and
One of organofluorine compound or combination.The defoaming agent is dimethicone, ether ester compound, modified mineral oil, polyoxy
One of ethyl glycerin ether, small molecule metallorganic and silicon modified organic polymer or combination.The levelling agent is second two
Alcohol butyl ether, cellaburate, polyacrylate, silicone oil, hydroxymethyl cellulose, polydimethylsiloxane, polymethyl-benzene base silicon oxygen
One of alkane and modified organic silicon compound or combination.
The mass ratio of the coating additive and the graphene dispersing solution is (0.3~1): (3~5).Obtained graphene
Mass percent shared by coating main body described in composite coating is 40%~60%, quality shared by the graphene dispersing solution
Percentage be 30%~50% and the coating additive shared by mass percent be 3%~10%.In order to avoid being helped when coating
Agent content is too low, disperses deficiency to the oligomer of phenylamine derivative of high concentration, and work as coating additive too high levels, can be to stone
The performance of black alkene affects, it is preferable that the mass ratio of the coating additive and the graphene dispersing solution is (0.3
~0.5): (3~5).
The present invention also provides a kind of graphene composite coatings prepared using the above method.The graphene composite coating by
Coating main body, graphene dispersing solution and coating additive composition.Quality shared by the coating main body described in graphene composite coating
Percentage is 40%~60%, and mass percent shared by the graphene dispersing solution is 30%~50% and the coating additive
Shared mass percent is 3%~10%.
The graphene dispersing solution includes graphene, oligomer of phenylamine derivative and decentralized medium, the graphene by with
Oligomer of phenylamine derivative forms pi-pi bond and is dispersed in the decentralized medium, and then realizes the graphene uniform point
It dissipates in the coating main body.Mass percent shared by the graphene described in the graphene dispersing solution be 0.1%~
10%, mass percent shared by the oligomer of phenylamine derivative is shared by 0.1%~10% and the decentralized medium
Mass percent is 80%~90%.
It is derivative by oligomer of phenylamine by the surface to graphene powder in graphene composite coating provided by the invention
The modifying and decorating of object greatly improves dispersibility and chemical stability of the graphene in composite coating, so that the graphene
Composite coating is easily attached to the transparent carriers such as automobile front windshield, building glass surface, and obtained film is transparent, heat-insulated guarantor
Temperature, energy-saving effect are significant.Also, the graphene composite coating will not be brought heavy metal-polluted without heavy metal elements such as In, Sn
The problem of dye.The preparation method of graphene composite coating provided by the invention, is innovated by preparation process, can obtain having preferable
The graphene composite coating of dispersibility and chemical stability, preparation process is simple, low in cost, answers conducive to the industrialization of graphene
With.
To further describe the present invention, here is the preparation method of the graphene composite coating, under different parameters
Specific embodiment:
Embodiment 1:
First by 10g aniline tripolymer and 80g deionized water, high-speed stirred disperses 10min at 1500rad/min, is mixed
Close object A.10g single-layer graphene powder is added in mixture A again, continues high-speed stirred 20min and ultrasound 10min to get arriving
Uniform and stable graphene dispersing solution.
60g organic siliconresin is added in stirring container, is then added under conditions of 1500rad/min high-speed stirred
Graphene dispersing solution described in 35g, stirs evenly, and obtains mixture B.2g ethylene glycol monobutyl ether, 2g ten is added into mixture B again
Dialkyl sulfate, 0.5g modified mineral oil and 0.5g silicone oil, continue to stir 10min and ultrasonic disperse 30min, through 325~400
Mesh screen filtration treatment to get arrive graphene composite coating.
The dispersion effect of the graphene dispersing solution is referring to Figure 1.As seen from Figure 1, the dispersion of the graphene dispersing solution
Effect is preferable.
The Raman spectrum of the graphene dispersing solution is see Fig. 2.From Figure 2 it can be seen that in 1410cm-1The absorption peak pair of position
It should be in pi-pi bond.This explanation forms pi-pi bond between oligomer of phenylamine derivative and graphene.
Obtained graphene composite coating is tested for the property.Specifically, by obtained graphene composite coating
It is respectively coated on 10cm × 10cm × 0.2cm plate glass on piece with 10 μm of bar spreader, then in 80 DEG C of baking ovens
Dry 1h, obtains film.
The visible light transmittance, infrared of film is detected according to GB/T 2680 by ultraviolet-visible-infrared spectrophotometer
Light transmission rate, ultraviolet light rejection rate.
The adhesive force of film is detected according to GB/T 9286 by cross-hatching.
The water resistance of film is detected according to GB/T 1733 by room temperature bowssening, the testing time is 96 hours.
By the resistance to artificial weathering aging ability of the Weatherometer foundation detection film of GB/T 1865, the testing time is
1000 hours.
The temperature-change resistance of film is detected according to GB/T 1735 by cold-hot alternating test.
The main performance of film made of obtained graphene composite coating is shown in Table 1.
Embodiment 2:
First by 9.9g Tetraaniline and 90g ethyl alcohol, high-speed stirred disperses 10min at 1500rad/min, is mixed
Object A.0.1g multi-layer graphene powder is added in mixture A again, continues high-speed stirred 20min and ultrasound 10min to get to
Even stable graphene dispersing solution.
52g acrylic resin is added in stirring container, is then added under conditions of 1500rad/min high-speed stirred
Graphene dispersing solution described in 45g, stirs evenly, and obtains mixture B.1g dipropylene glycol methyl ether ether is added into mixture B again
Ester, 1g dodecane sulfonate, 0.5g dimethicone and 0.5g hydroxymethyl cellulose continue to stir 10min and ultrasonic disperse
30min arrives graphene composite coating through 325~400 mesh screen filtration treatments.
The dispersion effect of the graphene dispersing solution is referring to Figure 1.As seen from Figure 1, the dispersion of the graphene dispersing solution
Effect is preferable.
Obtained graphene composite coating is tested for the property.Test method is the same as embodiment 1.Obtained graphene
The main performance of film made of composite coating is shown in Table 1.
Embodiment 3:
First by 0.1g aniline pentamer and 90g acetone, high-speed stirred disperses 10min at 1500rad/min, is mixed
Object A.9.9g single-layer graphene slurry is added in mixture A again, continues high-speed stirred 20min and ultrasound 10min to get to
Even stable graphene dispersing solution.
55g polyester resin is added in stirring container, 40g then is added under conditions of 1500rad/min high-speed stirred
The graphene dispersing solution, stirs evenly, and obtains mixture B.2g glycol propyl ether, 2g polyethylene is added into mixture B again
Alcohol, 0.5g ether ester compound and 0.5g polyacrylate continue to stir 10min and ultrasonic disperse 30min, through 325~400 mesh
The screen to filtrate handles to arrive graphene composite coating.
The dispersion effect of the graphene dispersing solution is referring to Figure 1.As seen from Figure 1, the dispersion of the graphene dispersing solution
Effect is preferable.
Obtained graphene composite coating is tested for the property.Test method is the same as embodiment 1.Obtained graphene
The main performance of film made of composite coating is shown in Table 1.
Embodiment 4:
First by six aggressiveness of 10g aniline and 85g ethyl acetate, high-speed stirred disperses 10min at 1500rad/min, it obtains
Mixture A.5g multi-layer graphene slurry is added in mixture A again, continues high-speed stirred 20min and ultrasound 10min to get arriving
Uniform and stable graphene dispersing solution.
40g polyurethane resin is added in stirring container, is then added under conditions of 1500rad/min high-speed stirred
Graphene dispersing solution described in 50g, stirs evenly, and obtains mixture B.5g propylene glycol phenylate, the poly- second of 4g is added into mixture B again
Alkene pyrrolidone, 0.5g polyoxyethanyl glycerin ether and 0.5g butyl glycol ether continue to stir 10min and ultrasonic disperse 30min, warp
325~400 mesh screen filtration treatments to get arrive graphene composite coating.
Obtained graphene composite coating is tested for the property.Test method is the same as embodiment 1.Obtained graphene
The main performance of film made of composite coating is shown in Table 1.
Embodiment 5:
First by 5g Tetraaniline carboxy derivatives and 85g toluene, high-speed stirred disperses 10min at 1500rad/min,
Obtain mixture A.10g single-layer graphene powder is added in mixture A again, continues high-speed stirred 20min and ultrasound 10min,
Obtain uniform and stable graphene dispersing solution.
45g alkyd resin is added in stirring container, 45g then is added under conditions of 1500rad/min high-speed stirred
The graphene dispersing solution, stirs evenly, and obtains mixture B.It is small that 4g benzyl alcohol, 4g organosilicon, 1g is added into mixture B again
Molecular metal organic matter and 1g polydimethylsiloxane continue to stir 10min and ultrasonic disperse 30min, through 325~400 mesh screens
Filtration treatment to get arrive graphene composite coating.
Obtained graphene composite coating is tested for the property.Test method is the same as embodiment 1.Obtained graphene
The main performance of film made of composite coating is shown in Table 1.
Embodiment 6:
First by 5g aniline tripolymer alkyl derivative and 90g chloroform, high-speed stirred disperses 10min at 1500rad/min,
Obtain mixture A.5g single-layer graphene slurry is added in mixture A again, continues high-speed stirred 20min and ultrasound 10min, i.e.,
Obtain uniform and stable graphene dispersing solution.
60g epoxy resin is added in stirring container, 30g then is added under conditions of 1500rad/min high-speed stirred
The graphene dispersing solution, stirs evenly, and obtains mixture B.5g Lauryl Alcohol ester, 4g Organic fluoride is added into mixture B again
Compound, 0.5g silicon modified organic polymer and 0.5g polymethylphenylsiloxane continue to stir 10min and ultrasonic disperse
30min arrives graphene composite coating through 325~400 mesh screen filtration treatments.
Obtained graphene composite coating is tested for the property.Test method is the same as embodiment 1.Obtained graphene
The main performance of film made of composite coating is shown in Table 1.
Table 1
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | |
| Visible light transmittance | 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% |
| Water resistance | It is without exception | It is without exception | It is without exception | It is without exception | It is without exception | It is without exception |
| Resistance to artificial weathering aging | It is without exception | It is without exception | It is without exception | It is without exception | It is without exception | It is without exception |
| Adhesive force | 0 grade | 0 grade | 0 grade | 0 grade | 0 grade | 0 grade |
| Temperature-change resistance | It is without exception | It is without exception | It is without exception | It is without exception | It is without exception | It is without exception |
Seen from table 1, film visible light transmittance with higher made of graphene composite coating of the present invention, it is several
Can complete shielding ultraviolet rays, the higher infrared ray of energy in sunlight can effectively be stopped, at the same coating it is ageing-resistant,
Waterproof, adhesive force, temperature-change resistance are good.
The above description of the embodiment is only used to help understand the method for the present invention and its core ideas.It should be pointed out that pair
For those skilled in the art, without departing from the principle of the present invention, the present invention can also be carried out
Some improvements and modifications, these improvements and modifications also fall within the scope of protection of the claims of the present invention.To these embodiments
A variety of modifications are it will be apparent that the general principles defined herein can be not for those skilled in the art
It is realized in other embodiments in the case where being detached from the spirit or scope of the present invention.Therefore, the present invention is not intended to be limited to this
These embodiments shown in text, and it is to fit to the widest scope consistent with the principles and novel features disclosed herein.
Claims (7)
1. a kind of graphene composite coating, which is characterized in that it is made of coating main body, graphene dispersing solution and coating additive,
Mass percent shared by the coating main body described in graphene composite coating is 40%~60%, the graphene dispersing solution institute
The mass percent accounted for be 30%~50% and the coating additive shared by mass percent be 3%~10%, the graphite
Alkene dispersion liquid includes graphene, oligomer of phenylamine derivative and decentralized medium, the graphene by with oligomer of phenylamine derivative
It forms pi-pi bond and is dispersed in the coating main body；
The graphene composite coating is made by following steps:
Oligomer of phenylamine derivative and decentralized medium are mixed, mixture A is obtained；
Graphene is added into the mixture A, is uniformly mixed oligomer of phenylamine derivative with graphene and oligomeric in aniline
Pi-pi bond is formed between object derivative and graphene obtains graphene dispersing solution；
One coating main body is provided, the graphene dispersing solution is added in Xiang Suoshu coating main body and is uniformly mixed, mixture is obtained
B；
Coating additive is added into the mixture B, obtains graphene composite coating.
2. graphene composite coating according to claim 1, which is characterized in that the graphite described in the graphene dispersing solution
Mass percent shared by alkene is 0.1%~10%, mass percent shared by the oligomer of phenylamine derivative is 0.1%~
10% and the decentralized medium shared by mass percent be 80%~90%.
3. graphene composite coating according to claim 1, which is characterized in that the coating described in graphene composite coating helps
Mass percent shared by agent is 3%~5%.
4. graphene composite coating according to claim 1, which is characterized in that the oligomer of phenylamine derivative is with active
The oligomer of phenylamine that can be rolled into a ball, the functional group includes carboxyl, alkyl, sulfonic group, phosphate, epoxy group, polyethylene group
And/or polyvinyl alcohol group, the oligomer of phenylamine is aniline tripolymer, Tetraaniline, aniline pentamer, aniline six are poly-
One of body, eight aggressiveness of aniline or combination.
5. graphene composite coating according to claim 1, which is characterized in that the decentralized medium be deionized water, ethyl alcohol,
One of acetone, isopropanol, butanol, ethyl acetate, toluene, chloroform, dimethylformamide, dimethyl sulfoxide, dichloroethanes
Or combination, the coating main body are organic siliconresin, acrylic resin, polyester resin, polyurethane resin, alkyd resin and epoxy
One of resin or combination.
6. graphene composite coating according to claim 1, which is characterized in that the coating additive includes film forming agent, wetting
Agent, defoaming agent and levelling agent, the film forming agent are ethylene glycol monobutyl ether, propylene glycol monobutyl ether, glycol propyl ether, dipropyl ether, third
One of glycol phenylate, benzyl alcohol, Lauryl Alcohol ester or combination, the wetting agent are lauryl sulfate, dodecyl
One of sulfonate, polyvinyl alcohol, polyvinylpyrrolidone, organo-silicon compound and organofluorine compound or combination, it is described
Defoaming agent is dimethicone, ether ester compound, modified mineral oil, polyoxyethanyl glycerin ether, small molecule metallorganic and changes
Property one of organosilicon polymer or combination, the levelling agent be butyl glycol ether, cellaburate, polyacrylate,
One of silicone oil, hydroxymethyl cellulose and modified organic silicon compound or combination.
7. graphene composite coating according to claim 1, which is characterized in that by high-speed stirred, ultrasound, ball milling and/or
The graphene dispersing solution is uniformly mixed by the dispersing method of sand milling with the coating main body.
Priority Applications (5)
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| CN201410814945.7A CN105778608B (en) | 2014-12-24 | 2014-12-24 | A kind of graphene composite coating and preparation method 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 |
| EP15865917.7A EP3228592A4 (en) | 2014-12-02 | 2015-11-27 | Graphene dispersant and application thereof |
| US15/607,552 US10696790B2 (en) | 2014-12-02 | 2017-05-29 | Graphene dispersant and application thereof |
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| CN106189713A (en) * | 2016-08-25 | 2016-12-07 | 北京尚德安耐新材料科技有限公司 | The preparation and application of watersoluble plumbago alkene anticorrosive paint |
| JP6615411B1 (en) * | 2016-11-17 | 2019-12-04 | 中国科学院▲寧▼波材料技▲術▼▲与▼工程研究所Ｎｉｎｇｂｏ Ｉｎｓｔｉｔｕｔｅ Ｏｆ Ｍａｔｅｒｉａｌｓ Ｔｅｃｈｎｏｌｏｇｙ ＆ Ｅｎｇｉｎｅｅｒｉｎｇ，Ｃｈｉｎｅｓｅ Ａｃａｄｅｍｙ Ｏｆ Ｓｃｉｅｎｃｅｓ | Hexagonal boron nitride epoxy composite anticorrosion paint, its production method and application |
| CN106896260A (en) * | 2017-02-09 | 2017-06-27 | 广东电网有限责任公司云浮供电局 | A kind of electrical verification coating and electricity-testing method |
| 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 |
| CN109666332A (en) * | 2017-10-16 | 2019-04-23 | 山东欧铂新材料有限公司 | A kind of preparation method of anticorrosive paint graphene epoxy resin dispersion liquid, annular-oxygen and rich zinc antiseptic dope and preparation method thereof |
| 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 |
| 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 |
| CN109553095A (en) * | 2019-01-12 | 2019-04-02 | 福建师范大学 | A kind of preparation method of high concentration aqueous's graphene dispersing solution |
| CN110373084A (en) * | 2019-02-22 | 2019-10-25 | 福建科华中盈新材料有限公司 | It is a kind of to apply the graphene coating and preparation method thereof heat-insulated in glass antiultraviolet |
| CN110156000B (en) * | 2019-06-04 | 2022-07-12 | 四川恒力盛泰石墨烯科技有限公司 | Multistage dispersion method of graphene |
| CN110615894A (en) * | 2019-06-15 | 2019-12-27 | 威海晨源分子新材料有限公司 | Hyperbranched polyesteramine and application thereof in water-based paint |
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