CN108485501B - Graphene-based water-based paint and preparation method thereof - Google Patents

Graphene-based water-based paint and preparation method thereof Download PDF

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CN108485501B
CN108485501B CN201810412263.1A CN201810412263A CN108485501B CN 108485501 B CN108485501 B CN 108485501B CN 201810412263 A CN201810412263 A CN 201810412263A CN 108485501 B CN108485501 B CN 108485501B
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based paint
curing agent
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CN108485501A (en
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钟家春
钟慧
田雨涵
胡林清
郑晓翼
蒲泽军
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Sichuan Xinghuiteng Group Co ltd
Sichuan University of Science and Engineering
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/44—Polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08—Anti-corrosive paints
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/18—Fireproof paints including high temperature resistant paints
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/24—Electrically-conducting paints
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C08K3/042—Graphene or derivatives, e.g. graphene oxides

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  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
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Abstract

The invention belongs to the field of polymer-based composite coatings, and particularly relates to a graphene-based water-based coating and a preparation method thereof. The invention aims to provide a polyurethane coating which is aqueous, has good ductility, higher toughness and better adhesive force and hardness. According to the invention, through molecular structure design, after hydroxyl functional groups on the surface of GO are isocyanated and acidified through isophorone diisocyanate (IPDI), IPDI is connected to the surface of GO, and then graphene oxide connected with IPDI is reacted with hydroxyl on PCDL through an in-situ polymerization method, so that chemical bonding of GO and PCDL is realized, and the problems of dispersion and interface of GO in a polymer coating are thoroughly solved. The graphene/polycarbonate diol (GO/PCDL) composite coating prepared by the invention has the excellent performance of waterborne polyurethane, also has antistatic property, and can be widely applied to the fields of electronic appliances, functional coatings and the like.

Description

Graphene-based water-based paint and preparation method thereof
Technical Field
The invention belongs to the field of polymer-based composite coatings, and particularly relates to a graphene-based water-based coating and a preparation method thereof.
Background
Polycarbonate diol (PCDL), a macromolecular polymer with terminal hydroxyl groups at both ends of long-chain molecules and a repeating unit of carbonate groups on a main chain, is produced by Japan company at the earliest in 1986, has lower glass transition temperature (Tg), better room temperature flexibility, good hydrolysis resistance in preparing polyurethane coatings, and is widely applied to the coating field.
Graphene is a two-dimensional carbon nanomaterial with a single atom thickness, and since being discovered by scientists in 2004, graphene and carbon nanotubes have rapidly become the leading edge of further research in the field of material science. The macroscopic structure of the graphene material is formed by overlapping micron-sized graphene single sheets with good conductivity, and the structural characteristics also determine that the graphene material has good energy storage capacity. Graphene has good electrical conductivity, a large specific surface area and good thermal conductivity, so that graphene has great research and application prospects in the aspects of dielectric materials and battery materials.
Polyurethanes are an important class of organic polymeric materials, and are prepared by the polyaddition of polyols and polyisocyanates. Wherein, the polyester polyurethane material is not hydrolysis resistant, and the polyether polyurethane material has poor heat resistance, mechanical property and oxidation resistance.
At present, inorganic fillers are often used to improve the performance of polymeric coatings. However, the traditional polymer-based composite coating mostly adopts a physical mode to carry out mechanical blending, and because the interface of the inorganic filler in the polymer is incompatible, the viscosity of the polymer is high, and the filler cannot be uniformly dispersed, the better polymer-based composite coating cannot be obtained.
Chinese patent with application number 201410575831.1 discloses a preparation method of graphene-based conductive flame-retardant waterborne polyurethane coating and adhesive. Adding an amidated graphene intermediate into polycarbonate diol (PCDL), heating, adding isophorone diisocyanate (IPDI) and a catalyst, adding a hydrophilic chain extender to continue reacting when the content of NCO groups reaches 6.4%, adding a cross-linking agent and triethylamine to neutralize and form salt, and adding water to disperse, thereby preparing the graphene-based conductive flame-retardant waterborne polyurethane coating.
The patent document with the application number of 201410036016.8 discloses an in-situ method for preparing a graphene-containing waterborne polyurethane composite conductive coating and a method thereof. The method adopts polymer polyol and polyisocyanate to react to prepare-NCO-terminated waterborne polyurethane prepolymer; and stirring the waterborne polyurethane prepolymer and the aminated modified graphene at a high speed, and adding a neutralizing agent, ice water and a chain extender to obtain the graphene-containing waterborne polyurethane composite conductive coating.
Although the coatings prepared by the two patents have better conductivity, the hardness, tensile strength and corrosion resistance of the coatings are poor. Therefore, it is required to develop an aqueous polyurethane coating material having excellent comprehensive properties.
Disclosure of Invention
The first technical problem to be solved by the invention is to provide a preparation method of a graphene-based water-based paint with excellent comprehensive performance.
The preparation method of the graphene-based water-based paint comprises the following steps:
a. reacting isophorone diisocyanate with hydroxyl on the surface of graphene oxide by an in-situ polymerization method to obtain a GO/IPDI prepolymer;
b. and c, adding the GO/IPDI prepolymer and isophorone diisocyanate prepared in the step a into acetone for dispersion, adding polycarbonate diol, continuing to disperse, heating to evaporate acetone after uniform dispersion, adding a curing agent for curing, and finally adding water for emulsification to prepare the graphene-based water-based coating.
Preferably, in step a, the dispersing aid used in the in-situ polymerization method is N, N-dimethylformamide.
Preferably, in the step a, the mass ratio of the graphene oxide to the isophorone diisocyanate to the N, N-dimethylformamide is 1: 7-15: 50-80; preferably, the mass ratio of the graphene oxide to the isophorone diisocyanate to the N, N-dimethylformamide is 1: 10-12: 65-70; more preferably, the mass ratio of the graphene oxide to the isophorone diisocyanate to the N, N-dimethylformamide is 1:12: 70.
In the step a, the specific preparation method of the GO/IPDI prepolymer comprises the following steps: uniformly mixing graphene oxide, isophorone diisocyanate and N, N-dimethylformamide, heating to 40-70 ℃, reacting for 6-8 hours, and filtering and drying the obtained reaction product to obtain a GO/IPDI prepolymer; preferably, the temperature is raised to 60 ℃ for reaction for 6 h.
Preferably, in step b, the curing agent is triethylamine.
Preferably, in the step b, the molar ratio of the polycarbonate diol to the isophorone diisocyanate to the curing agent is 1: 1.2-1.7: 0.6-1.4; the addition amount of the GO/IPDI prepolymer is 1-5% of the mass of the polycarbonate diol.
Preferably, in the step b, the molar ratio of the polycarbonate diol to the isophorone diisocyanate to the curing agent is 1: 1.5-1.6: 1-1.2; the adding amount of the GO/IPDI prepolymer is 1-4% of the mass of the polycarbonate diol; preferably, the molar ratio of the polycarbonate diol, the isophorone diisocyanate and the curing agent is 1:1.6: 1.2; the GO/IPDI prepolymer was added in an amount of 4% by mass of the polycarbonate diol.
Preferably, in the step b, GO/IPDI, isophorone diisocyanate and acetone are dispersed for 30min, ultrasonic dispersion is adopted for dispersion, and PCDL is added into the solution to continue ultrasonic dispersion for 30 min.
Preferably, in the step b, heating to 40-60 ℃ to evaporate acetone, adding a curing agent, and carrying out curing reaction for 2-5 h at 20-40 ℃.
Preferably, the water is added for emulsification for 5-15 min.
The second technical problem to be solved by the invention is to provide a graphene-based water-based paint, which is prepared by the preparation method of the graphene-based water-based paint.
The third technical problem to be solved by the invention is to provide an application of the graphene-based water-based paint in electronic and electric appliances and functional paints.
The invention has the beneficial effects that:
1. the graphene-based water-based paint prepared by the invention is a polyurethane paint which is water-based, has good ductility, high toughness, good adhesion and hardness, the adhesion is 0 grade, the pencil hardness is more than 4H, the flexibility is less than 1mm, the impact force is more than 50cm, and the corrosion resistance is strong.
2. The graphene-based water-based paint prepared by the invention has excellent antistatic performance.
3. The graphene-based water-based composite coating prepared by the invention has the oxygen index of more than 27.3, longer time for reaching the maximum smoke density, better flame retardant property and capability of being applied to flame retardant coatings.
4. The preparation method is simple.
Drawings
FIG. 1 is an infrared contrast plot of GO/IPDI vs. GO prepared in example 1 of the present invention.
Fig. 2 is a schematic view of the graphene-based water-based paint of the present invention.
Detailed Description
The first technical problem to be solved by the invention is to provide a preparation method of a graphene-based water-based paint with excellent comprehensive performance.
The preparation method of the graphene-based water-based paint comprises the following steps:
a. reacting isophorone diisocyanate with hydroxyl on the surface of graphene oxide by an in-situ polymerization method to obtain a GO/IPDI prepolymer;
b. and c, adding the GO/IPDI prepolymer and isophorone diisocyanate prepared in the step a into acetone for dispersion, adding polycarbonate diol, continuing to disperse, heating to evaporate acetone after uniform dispersion, adding a curing agent for curing, and finally adding water for emulsification to prepare the graphene-based water-based coating.
In the step b, the GO/IPDI prepolymer and the isophorone diisocyanate are added into acetone for dispersion, polycarbonate diol is added for continuous dispersion, and the reason of adopting the step-by-step dispersion is that the problem of GO/IPDI dispersion is solved, the GO/IPDI is agglomerated in the acetone, and the dispersion is uneven if PCDL is added in advance for reaction. Therefore, GO/IPDI is required to be uniformly dispersed in acetone, and PCDL is added for reaction.
According to the method, isophorone diisocyanate (IPDI for short) is subjected to isocyanation on a hydroxyl functional group on the surface of graphene oxide (GO for short) through an in-situ polymerization method, and then IPDI is connected to the surface of GO; and then, reacting the IPDI-grafted graphene oxide with hydroxyl on PCDL through an in-situ polymerization method, so that chemical bonding of GO and PCDL is realized, and the problems of dispersion and interface of GO in the polymer coating are thoroughly solved.
The IPDI is added in the step a to enable IPDI and hydroxyl on GO to perform chemical bonding, and the purpose of adding IPDI in the step b is that as the aqueous polyurethane coating made of PCDL is a two-component coating, IPDI is a curing agent and is also a hard segment component, GO/IPDI only reacts a small part of hydroxyl in PCDL in the curing process, and in addition, PCDL and hard segment IPDI are required to be continuously cured to form a complete aqueous polyurethane coating.
The invention adds proper filler, and adopts polymer-based polyurethane water-based composite paint prepared by polycarbonate diol: on the one hand, suitable fillers enhance the mechanical properties of PCDL, and, on the other hand, aqueous polyurethane coatings made from PCDL have good heat resistance and oxidation resistance.
Preferably, in step a, the dispersing aid used in the in-situ polymerization method is N, N-dimethylformamide.
In order to improve the performance of the graphene-based water-based paint, preferably, in the step a, the mass ratio of graphene oxide to isophorone diisocyanate to N, N-dimethylformamide is 1: 7-15: 50-80; according to the invention, the addition proportion of the graphene oxide is controlled, and local agglomeration can be caused by excessive addition of the graphene oxide, so that the product performance is reduced.
More preferably, the mass ratio of the graphene oxide to the isophorone diisocyanate to the N, N-dimethylformamide is 1: 10-12: 65-70; when the mass ratio of the graphene oxide to the isophorone diisocyanate to the N, N-dimethylformamide is 1:12:70, the performance of the graphene-based water-based paint is optimal.
In the step a, the specific preparation method of the GO/IPDI prepolymer comprises the following steps: uniformly mixing graphene oxide, isophorone diisocyanate and N, N-dimethylformamide, heating to 40-70 ℃, reacting for 6-8 hours, and filtering and drying the obtained reaction product to obtain the GO/IPDI prepolymer. The invention always uses the ultrasonic disperser to disperse the ultrasonic in the temperature-rising reaction process. The obtained GO/IPDI prepolymer is isocyanated graphene oxide.
The invention controls the temperature between 40 and 70 ℃ because: if the reaction temperature is lower than 40 ℃, the reaction speed is too slow, even solidification cannot be achieved, and if the reaction temperature is too high, construction is not changed, and byproducts are easily generated. Preferably, the temperature is raised to 60 ℃ for reaction for 6 h.
Preferably, in step b, the curing agent is triethylamine.
Preferably, in the step b, the molar ratio of the polycarbonate diol to the isophorone diisocyanate to the curing agent is 1: 1.2-1.7: 0.6-1.4; the addition amount of the GO/IPDI prepolymer is 1-5% of the mass of the polycarbonate diol. Too much GO/IPDI prepolymer addition can degrade product performance.
Preferably, in the step b, the molar ratio of the polycarbonate diol to the isophorone diisocyanate to the curing agent is 1: 1.5-1.6: 1-1.2; the adding amount of the GO/IPDI prepolymer is 1-4% of the mass of the polycarbonate diol;
in order to further improve the overall performance of the coating, it is preferred that the molar ratio of polycarbonate diol, isophorone diisocyanate, and curing agent is 1:1.6: 1.2; the GO/IPDI prepolymer was added in an amount of 4% by mass of the polycarbonate diol.
Furthermore, in order to make the dispersion more uniform and the reaction easier to carry out, the invention can firstly carry out ultrasonic stirring and dispersion on the GO/IPDI prepolymer, the IPDI and the acetone for 30min, and then add the PCDL into the solution to continue the ultrasonic dispersion for 30min, so that the dispersion is uniform.
Preferably, in the step b, heating to 40-60 ℃ to evaporate acetone, adding a curing agent, and carrying out curing reaction for 2-5 h at 20-40 ℃.
Wherein the water is added for emulsification for 5-15 min.
The second technical problem to be solved by the invention is to provide a graphene-based water-based paint, which is prepared by the preparation method of the graphene-based water-based paint.
The third technical problem to be solved by the invention is to provide an application of the graphene-based water-based paint in electronic and electric appliances and functional paints.
The following examples are provided to further illustrate the embodiments of the present invention and are not intended to limit the scope of the present invention.
Example 1 preparation of graphene-based waterborne coatings
a. Adding Graphene Oxide (GO) and isophorone diisocyanate (IPDI) into a N, N-Dimethylformamide (DMF) solution according to a certain mass ratio, wherein the ratio is as follows: GO, IPDI: DMF was heated to 40 ℃ at a ratio of 1:7:50, and the reaction was carried out for 6 hours while ultrasonic dispersion was carried out by using an ultrasonic disperser. And filtering and drying the prepared GO/IPDI to obtain a GO/IPDI prepolymer.
b. Weighing raw materials according to the molar ratio of the raw materials, wherein PCDL: IPDI: triethylamine 1:1.2: 0.6; and then weighing GO/IPDI accounting for 1% of the PCDL mass fraction.
Adding the weighed GO/IPDI and IPDI into a 100ml three-necked bottle, adding acetone, ultrasonically stirring and dispersing for 30min, adding PCDL into the solution, continuously ultrasonically dispersing for 30min, pouring the uniformly dispersed solution into the 100ml three-necked bottle with a thermometer and an evaporation device, evaporating acetone at 40-60 ℃, adding triethylamine into the solution, and curing for 2h at 20 ℃. And adding 110g of water into the product to emulsify for 10min to obtain the graphene-based water-based paint S1.
Example 2
On the basis of the embodiment 1, the mixture ratio of GO, IPDI and DMF in the step a, the temperature rise and the reaction time are changed; and c, changing the ratio of PCDL, PDI and ethylamine, the using amount of GO/IPDI prepolymer (represented by the mass fraction of GO/IPDI prepolymer in PCDL), the curing temperature and the curing time in the step b to prepare the graphene-based water-based paint S2-S4, wherein the specific process is shown in Table 1.
TABLE 1
Comparative example 1 the graphene-based conductive flame retardant aqueous polyurethane coating prepared in example 1 of the patent application No. 201410575831.1 was prepared and is designated as D1.
Comparative example 2 the graphene-containing waterborne polyurethane composite conductive coating prepared in example 1 of the patent with application number 201410036016.8 was prepared and is marked as D2.
Test examples
The obtained graphene-based water-based paints S1-S4 and D1-D2 were subjected to performance tests, and the results are shown in Table 2.
TABLE 2
S1 S2 S3 S4 D1 D2
Adhesion/grade 0 0 0 1 1 1
Pencil hardness/H 4H 5H 5H 5H 3H 3H
Flexibility/mm ＜1 ＜1 ＜1 ＜1 ＜1 ＜1
Impact force/cm ＞50 ＞50 ＞50 ＞50 ＞50 ＞50
Salt spray experiment/h 480 492 500 502 282 312
Surface resistivity/omega 1010 109 106 108 109 107
Tensile strength/MPa 60 64 72 70 40 48
Oxygen index 26.8 27.3 27.7 28.5 26.6 27.8
Time to maximum smoke density/S 170 191 210 218 161 211

Claims (16)

1. The preparation method of the graphene-based water-based paint is characterized by comprising the following steps of:
a. reacting isophorone diisocyanate with hydroxyl on the surface of graphene oxide by an in-situ polymerization method to obtain a GO/IPDI prepolymer; wherein, the dispersing auxiliary agent adopted by the in-situ polymerization method is N, N-dimethylformamide; the specific preparation method of the GO/IPDI prepolymer comprises the following steps: uniformly mixing graphene oxide, isophorone diisocyanate and N, N-dimethylformamide according to the mass ratio of 1: 7-15: 50-80, heating to 40-70 ℃, reacting for 6-8 h, and filtering and drying the obtained reaction product to obtain a GO/IPDI prepolymer;
b. b, adding the GO/IPDI prepolymer prepared in the step a and isophorone diisocyanate into acetone for dispersion, adding polycarbonate diol, continuing dispersion, heating to evaporate acetone after uniform dispersion, adding a curing agent for curing, and finally adding water for emulsification to prepare the graphene-based water-based coating; wherein the molar ratio of the polycarbonate diol to the isophorone diisocyanate to the curing agent is 1: 1.2-1.7: 0.6-1.4; the addition amount of the GO/IPDI prepolymer is 1-5% of the mass of the polycarbonate diol.
2. The preparation method of the graphene-based water-based paint according to claim 1, wherein in the step a, the mass ratio of the graphene oxide to the isophorone diisocyanate to the N, N-dimethylformamide is 1: 10-12: 65-70.
3. The preparation method of the graphene-based water-based paint according to claim 2, wherein in the step a, the mass ratio of the graphene oxide to the isophorone diisocyanate to the N, N-dimethylformamide is 1:12: 70.
4. The method for preparing the graphene-based water-based paint according to any one of claims 1 to 3, wherein in the step a, the temperature is raised to 60 ℃ for reaction for 6 hours.
5. The method for preparing the graphene-based water-based paint according to any one of claims 1 to 3, wherein in the step b, the curing agent is triethylamine.
6. The method for preparing the graphene-based water-based paint according to claim 4, wherein in the step b, the curing agent is triethylamine.
7. The preparation method of the graphene-based water-based paint according to claim 1, wherein in the step b, the molar ratio of the polycarbonate diol to the isophorone diisocyanate to the curing agent is 1: 1.5-1.6: 1-1.2; the addition amount of the GO/IPDI prepolymer is 1-4% of the mass of the polycarbonate diol.
8. The method for preparing the graphene-based water-based paint according to claim 7, wherein in the step b, the molar ratio of the polycarbonate diol to the isophorone diisocyanate to the curing agent is 1:1.6: 1.2; the GO/IPDI prepolymer was added in an amount of 4% by mass of the polycarbonate diol.
9. The preparation method of the graphene-based water-based paint according to any one of claims 1 to 3, wherein in the step b, the mixture is heated to 40-60 ℃ to evaporate acetone, and then a curing agent is added to carry out curing reaction for 2-5 hours at 20-40 ℃.
10. The preparation method of the graphene-based water-based paint according to claim 4, wherein in the step b, the acetone is evaporated by heating to 40-60 ℃, and then the curing agent is added for curing reaction for 2-5 hours at 20-40 ℃.
11. The preparation method of the graphene-based water-based paint according to claim 5, wherein in the step b, the acetone is evaporated by heating to 40-60 ℃, and then the curing agent is added for curing reaction for 2-5 hours at 20-40 ℃.
12. The preparation method of the graphene-based water-based paint according to claim 6, wherein in the step b, the acetone is evaporated by heating to 40-60 ℃, and then the curing agent is added for curing reaction for 2-5 hours at 20-40 ℃.
13. The preparation method of the graphene-based water-based paint according to claim 7, wherein in the step b, the acetone is evaporated by heating to 40-60 ℃, and then the curing agent is added for curing reaction for 2-5 hours at 20-40 ℃.
14. The preparation method of the graphene-based water-based paint according to claim 8, wherein in the step b, the acetone is evaporated by heating to 40-60 ℃, and then the curing agent is added for curing reaction for 2-5 hours at 20-40 ℃.
15. The graphene-based water-based paint is prepared by the preparation method of the graphene-based water-based paint as claimed in any one of claims 1 to 14.
16. The use of the graphene-based water-based paint according to claim 15 in electronic and electric appliances and functional paints.
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CN104277198B (en) * 2014-10-25 2016-08-24 朱蕾 A kind of graphene-based conduction flame-retardant aqueous polyurethane coating and the preparation method of adhesive
CN104804169B (en) * 2015-05-22 2017-12-08 烟台大学 A kind of preparation method of graphene modified polyurethane conductive coating paint
US11059015B2 (en) * 2015-06-10 2021-07-13 Council Of Scientific And Industrial Research Microcapsules modified with nanomaterial for controlled release of active agent and process for preparation thereof

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