CN108281216B - Water-based graphene high-temperature-resistant flame-retardant conductive paste and preparation method and application thereof - Google Patents
Water-based graphene high-temperature-resistant flame-retardant conductive paste and preparation method and application thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 135
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 124
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 239000003063 flame retardant Substances 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title abstract description 19
- 229910001868 water Inorganic materials 0.000 title abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 26
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 8
- 229920005989 resin Polymers 0.000 claims abstract description 8
- 239000011347 resin Substances 0.000 claims abstract description 8
- 239000000243 solution Substances 0.000 claims description 22
- 239000003973 paint Substances 0.000 claims description 15
- 238000000576 coating method Methods 0.000 claims description 10
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 9
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims description 8
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 claims description 6
- 238000009210 therapy by ultrasound Methods 0.000 claims description 6
- 238000005229 chemical vapour deposition Methods 0.000 claims description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 230000033116 oxidation-reduction process Effects 0.000 claims description 4
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 3
- 239000004925 Acrylic resin Substances 0.000 claims description 3
- 229920000178 Acrylic resin Polymers 0.000 claims description 3
- 239000003822 epoxy resin Substances 0.000 claims description 3
- 229910052603 melanterite Inorganic materials 0.000 claims description 3
- 229920001568 phenolic resin Polymers 0.000 claims description 3
- 239000005011 phenolic resin Substances 0.000 claims description 3
- 229920000647 polyepoxide Polymers 0.000 claims description 3
- 229920002635 polyurethane Polymers 0.000 claims description 3
- 239000004814 polyurethane Substances 0.000 claims description 3
- 229920002050 silicone resin Polymers 0.000 claims description 3
- 229910021577 Iron(II) chloride Inorganic materials 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-L Phosphate ion(2-) Chemical compound OP([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-L 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-M dihydrogenphosphate Chemical compound OP(O)([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-M 0.000 claims description 2
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 238000012360 testing method Methods 0.000 description 24
- 239000002002 slurry Substances 0.000 description 15
- 230000000694 effects Effects 0.000 description 13
- 239000011248 coating agent Substances 0.000 description 9
- 239000002270 dispersing agent Substances 0.000 description 7
- 239000002131 composite material Substances 0.000 description 6
- 239000010410 layer Substances 0.000 description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000005485 electric heating Methods 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000004299 exfoliation Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
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- 238000011160 research Methods 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 241000530268 Lycaena heteronea Species 0.000 description 1
- 239000006004 Quartz sand Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000011231 conductive filler Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000001066 destructive effect Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000033444 hydroxylation Effects 0.000 description 1
- 238000005805 hydroxylation reaction Methods 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/24—Conductive material dispersed in non-conductive organic material the conductive material comprising carbon-silicon compounds, carbon or silicon
-
- 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
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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
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B3/00—Ohmic-resistance heating
- H05B3/10—Heating elements characterised by the composition or nature of the materials or by the arrangement of the conductor
- H05B3/12—Heating elements characterised by the composition or nature of the materials or by the arrangement of the conductor characterised by the composition or nature of the conductive material
- H05B3/14—Heating elements characterised by the composition or nature of the materials or by the arrangement of the conductor characterised by the composition or nature of the conductive material the material being non-metallic
- H05B3/145—Carbon only, e.g. carbon black, graphite
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- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Dispersion Chemistry (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Manufacturing & Machinery (AREA)
- Paints Or Removers (AREA)
Abstract
The invention discloses a method for preparing aqueous graphene high-temperature-resistant flame-retardant conductive paste, which comprises the steps of 1) treating graphene to enable the surface to contain hydroxyl; 2) uniformly dispersing the graphene in an aqueous resin. The water-based graphene high-temperature-resistant flame-retardant conductive paste prepared by the method and the application of the water-based graphene high-temperature-resistant flame-retardant conductive paste in preparation of the water-based high-temperature-resistant flame-retardant graphene electrothermal film are also disclosed.
Description
Technical Field
The invention belongs to the field of graphene, and particularly relates to water-based graphene high-temperature-resistant flame-retardant conductive slurry and a preparation method thereof.
Background
Graphene is a two-dimensional material composed of a single layer of carbon atoms, wherein the carbon atoms are arranged in a honeycomb lattice, and the honeycomb structure of graphene is very stable. When external force and graphene are applied, the carbon atom layer can be bent and deformed, so that the carbon atoms do not need to be rearranged to adapt to the external force, and the structural stability is kept. When electrons in the graphene move in an orbit, scattering does not occur due to lattice defects or introduction of foreign atoms. Because the interatomic force is very strong, even if the surrounding carbon atoms are extruded and collided at normal temperature, the interference on electrons in the graphene is very small, the electron mobility exceeds 15000cm 2/V.S at the normal temperature, and the movement speed of the electrons reaches 1/300 of the light speed and is higher than that of the carbon nano tube or the silicon crystal; and the resistivity is only about 10-6 omega cm, lower than copper or silver, and is the material with the minimum resistivity at present. Due to the excellent performance of the graphene, the conductivity of the slurry can be improved to a great extent only by adding a small amount of graphene.
However, graphene is difficult to disperse in an aqueous system, and most of graphene conductive slurry is solvent-based at present, so that a certain degree of pollution is caused to the environment in the using process, and the health of people is harmed. The existing aqueous graphene conductive slurry is prepared by adding a large amount of dispersing agents and stabilizing agents into a system, and the graphene can be stably dispersed by utilizing the dispersing agents. However, the existence of the additives can seriously affect the conductivity of the graphene, and cannot reflect the advantages of the graphene as a conductive filler. The graphene is dispersed in an aqueous system by using the aid, so that the dispersion effect is poor, and the graphene can be agglomerated again after being stored for a long time. For example, patent CN 104464883a discloses graphene conductive paste with a surface adsorbing dispersant, a preparation method and applications thereof. In order to solve the dispersion problem, a surfactant and a dispersant are introduced into the system to help the graphene to be uniformly dispersed. But the surfactant and the dispersant do not participate in the electric conduction, and have certain destructive effect on the electric conduction performance of the product prepared by the slurry. The application and market development of the graphene conductive paste are seriously influenced.
Patent CN 105898906a discloses a method for preparing an electrothermal film by using graphene aqueous slurry, and introduces graphene aqueous slurry and a method for preparing the electrothermal film. Problems still existing with this approach are 1) graphene is dispersed using an auxiliary agent; the dispersion effect is poor; 2) the prepared electrothermal film has no flame retardant effect and has potential safety hazard. The graphene aqueous slurry prepared by the method is difficult to stably store for a long time, and the prepared graphene electrothermal film has great potential safety hazard and is easy to cause casualties caused by fire.
Patent CN 105647549a discloses a graphene flame-retardant film, and a preparation method and application thereof. The method comprises the steps of mixing graphene oxide with a flame retardant to prepare a film. And then reducing the graphene to prepare the graphene flame-retardant film. The graphene flame-retardant film prepared by the method is added with a large amount of flame retardant, so that the electrical property and the mechanical property of the film are seriously influenced, and the advantages of graphene cannot be exerted.
With the continuous and deep research on graphene, the graphene antistatic coating, the graphene electrothermal film, the graphene electromagnetic shielding coating and the like continuously enter the lives of people. The safety of graphene-related products is of increasing concern. Particularly, the graphene electric heating product is applied to winter heating on a large scale, and the safety of the product is more important. At present, graphene electric heating products on the market do not have flame retardant property, and the hidden danger is huge. Therefore, the development of graphene conductive paste having flame retardant effect is urgent.
Disclosure of Invention
Through research, the inventor proposes a functionalized graphene with a flame retardant effect, wherein the surface of the graphene contains hydroxyl. The graphene is chemically or physically treated to include hydroxyl groups on the surface, such as grafted phosphate groups.
Accordingly, in one aspect, the present invention provides a method for preparing an aqueous graphene high temperature resistant flame retardant conductive paste, the method comprising the steps of,
1) treating graphene to enable the surface to contain hydroxyl, so as to obtain hydroxylated graphene;
2) uniformly dispersing the graphene in an aqueous resin.
In one embodiment, the graphene is chemically or physically treated in step 1) to graft phosphate groups on the surface. In a particular embodiment, in step 1):
a) dispersing graphene to FeSO4·7H2O、FeCl2·4H2O、Fe(NO3)2·6H2O or H2O2Etc. in solution;
1, b) carrying out ultrasonic treatment on the prepared solution to ensure that graphene can be uniformly dispersed in the solution;
and c) pouring the dispersed solution into a hydrothermal reaction kettle for reaction.
In one embodiment, the temperature in the hydrothermal reaction vessel in step 1.c) is 180-.
In one embodiment, the graphene used in step 1) is prepared by various methods such as oxidation-reduction, CVD method, mechanical exfoliation, and the like
In one embodiment, the aqueous resin in step 2) is one or more of aqueous epoxy resin, aqueous phenolic resin, aqueous acrylic resin, aqueous polyurethane, aqueous silicone resin, and the like.
In one embodiment, in step 2):
2, a) dispersing the hydroxylated graphene prepared in the step 1) into a solution of phosphorus pentoxide water, phosphoric acid, phosphate, monohydrogen phosphate or dihydrogen phosphate;
2, b) carrying out ultrasonic treatment on the solution prepared in the step 2.a) to uniformly disperse graphene in the solution;
2, c) pouring the solution dispersed in the step 2.b) into a hydrothermal reaction kettle for reaction.
In one embodiment, the temperature in the hydrothermal reaction kettle in step 2.c) is 90-110 ℃.
In a second aspect, the present invention provides the aqueous graphene high temperature resistant flame retardant conductive paste prepared by the method of the first aspect, wherein the surface of the graphene contains hydroxyl groups, and the graphene is uniformly dispersed in the aqueous resin.
In one embodiment, the graphene is chemically or physically treated to graft phosphate groups to the surface.
In one embodiment, the graphene is prepared by various methods such as oxidation-reduction, CVD method, mechanical exfoliation, and the like.
In one embodiment, the aqueous resin is one or more of aqueous epoxy resin, aqueous phenolic resin, aqueous acrylic resin, aqueous polyurethane, aqueous silicone resin, and the like.
In a third aspect, the invention provides application of the aqueous graphene high-temperature-resistant flame-retardant conductive paste of the first aspect of the invention in preparation of an aqueous high-temperature-resistant flame-retardant graphene electrothermal film.
In one embodiment, the use is for antistatic floor paint, electromagnetic shielding paint.
The invention uses the water-based system, and has no VOC emission problem; the graphene used by the invention can be uniformly dispersed in a water system without an auxiliary agent through hydroxylation treatment; the graphene used by the invention contains phosphate groups, and has excellent flame retardant effect without adding a flame retardant; the aqueous graphene high-temperature-resistant flame-retardant conductive paste can work at 200 ℃ for a long time; the flame retardant grade of the water-based graphene high-temperature-resistant flame-retardant conductive paste is V0 grade; the resistivity of the water-based graphene high-temperature-resistant flame-retardant conductive paste is 0.02-10 omega cm.
Detailed Description
The invention provides a high-temperature-resistant flame-retardant aqueous graphene conductive paste, which is prepared from graphene by various methods such as oxidation reduction, a CVD (chemical vapor deposition) method and mechanical stripping, and can be uniformly dispersed in aqueous resin and has a high flame-retardant effect by chemical or physical treatment.
A large amount of dispersing agents or stabilizing agents are added in the existing aqueous graphene conductive slurry in the preparation process to ensure that graphene can be uniformly and stably dispersed in an aqueous system. The dispersant or the stabilizer is coated on the surface of the graphene sheet layer in an action mode, so that the graphene sheet layer is not easy to agglomerate in a water-based system. However, the coating mode can greatly increase the contact resistance between graphene sheets, so that the conductivity of the conductive paste is poor. After the graphene used by the invention is chemically treated, a certain amount of hydroxyl groups are contained on the surface of the graphene. The existence of the hydroxyl enables the graphene to be uniformly and stably dispersed in the slurry system.
The graphene conductive product prepared by the existing aqueous graphene conductive paste technology can only be used for a long time at 80 ℃, so that a plurality of application scenes of the conductive paste are limited. The graphene used in the invention can be treated by a chemical method, so that the temperature resistance of the aqueous graphene conductive product can be remarkably improved, and the aqueous graphene conductive product can stably work for a long time at the maximum temperature of 200 ℃.
The flame retardant effect of the existing graphene flame retardant products is realized by adding a flame retardant. The flame retardant can have a flame retardant effect only when the flame retardant is added by more than 30 wt%, and the electrical property and the mechanical property of a product can be seriously influenced by the flame retardant. Under the national policy of changing coal into electricity, the graphene electric heating product becomes an air port for graphene application. The product prepared by adding the flame retardant into the slurry can seriously influence the conductivity of the slurry, and cannot be applied to electric heating. The flame-retardant functional group is directly grafted on the graphene, so that the graphene has excellent flame-retardant effect while the excellent conductivity of the graphene is ensured. The prepared graphene product can simultaneously ensure excellent electrical property and flame retardant property.
Examples
The process steps and process conditions for preparing the aqueous graphene high-temperature-resistant flame-retardant conductive paste according to one embodiment of the invention may be as follows:
1. preparation of hydroxylated graphene
1.1) dispersing graphene to FeSO4·7H2O, wherein graphene: FeSO4·7H2The proportion of O to deionized water is 1 (15-25) to 1;
1.2) carrying out ultrasonic treatment on the prepared solution for 30min to uniformly disperse graphene in the solution;
1.3) pouring the dispersed solution into a hydrothermal reaction kettle, and reacting for 4-6h at 200 ℃ to obtain the hydroxylated graphene.
2. Preparation of graphene with flame retardant function
2.1) dispersing the hydroxylated graphene prepared in the step 1 into a phosphorus pentoxide aqueous solution, wherein the ratio of graphene to phosphorus pentoxide is (1-10): 1;
2.2) carrying out ultrasonic treatment on the solution prepared in the step 2.1) for 30min to uniformly disperse graphene in the solution;
2.3) pouring the solution dispersed in the step 2.2) into a hydrothermal reaction kettle, and reacting for 1-3h at 100 ℃ to obtain the graphene containing phosphate groups.
3. The flame retardant functional graphene is tested as follows:
3.1) the hydroxylated graphene can be stably dispersed in deionized water for 2 months; the test method is as follows: dispersing hydroxylated graphene in deionized water, standing and storing; and taking the upper solution after 2 months to test the concentration of the graphene. The same as the initial configuration concentration, it is proved that the hydroxylated graphene can be stably dispersed in the deionized water.
3.2) after the functionalized graphene is mixed with the water-based high polymer material, the prepared composite membrane can stably work at 200 ℃; the test method is as follows: the prepared composite membrane is electrified to ensure that the heating temperature reaches 200 ℃. The composite film is electrified for 30 days continuously, the temperature of the composite film is not changed, and the composite film can work stably at 200 ℃ for a long time.
3.3) after the functionalized graphene is mixed with the water-based high polymer material, the prepared composite film still cannot burn after being burnt by open fire for 30s, and the flame retardant effect is far beyond the V0 level.
4. The graphene with the flame retardant function is used as antistatic floor paint and electromagnetic shielding paint
4.1) the steps of using as antistatic floor paint are as follows:
a. cleaning the cement ground, and requiring to be dry and smooth;
b. copper foil or copper wire is laid according to GBJ97 standard, grounding resistance is less than 10 ohm, and the longitudinal and transverse intervals are 2m x 2 m;
c. preparing a proper amount of quartz sand into aqueous graphene high-temperature-resistant flame-retardant slurry, preparing an epoxy floor paint middle layer, and blade-coating to reach a designed thickness;
and d.12h, preparing a proper amount of quartz powder by using the aqueous graphene high-temperature-resistant flame-retardant slurry, preparing an epoxy floor paint surface layer, blade-coating to reach the designed thickness, and drying after 5 days to obtain the flame-retardant anti-static floor paint.
The following tests were carried out on the prepared antistatic floor paint:
and (4) performing an adhesion test according to the standard GB1720-79, wherein the test result is 0 grade. And (3) carrying out an impact resistance test according to the standard GB/T1732-1993, wherein the test result shows that the impact resistance test can bear the impact of a 1KG object falling at a height of 1 m. The abrasion resistance test was carried out according to the standard GB/T1768-1989 with a loss of 0.01g at 500r/min using a 750g weight. The pencil hardness test is carried out according to the standard GB/T6739-1996, and the test result is 2H. Surface resistance test, using a surface resistance meter to test, the test result is 105The flame resistance test, carried out according to standard U L94-2013, was carried out on the samples for two 10 second burn tests, the flame being extinguished within 30 seconds and no combustibles falling.
The performance of the prepared flame-retardant antistatic floor paint is far better than that of common floor paint, and the flame-retardant antistatic floor paint has a very good market prospect.
4.2) the steps for using as electromagnetic shielding coating are as follows:
a. spraying the water-based graphene high-temperature-resistant flame-retardant slurry onto the surface of an object needing electromagnetic shielding by using a spray gun;
b. spraying a layer of protective finish on the surface of the electromagnetic shielding coating
The prepared electromagnetic shielding coating was tested as follows:
and the conductivity test shows that the resistivity is 0.001 omega cm. And (4) testing the electromagnetic shielding performance, namely testing according to the standard GJB6190-2008, wherein the test result shows that the electromagnetic shielding effect of the 10GHz wave band is 80 dB. And (4) performing an adhesion test according to the standard GB1720-79, wherein the test result is 0 grade. The pencil hardness test is carried out according to the standard GB/T6739-1996, and the test result is 2H.
The test result shows that the prepared electromagnetic shielding coating has excellent electromagnetic shielding effect and very good market prospect.
From the results, the flame-retardant functional graphene is suitable for being used as antistatic floor paint and electromagnetic shielding paint.
Claims (8)
1.A method for preparing aqueous graphene high-temperature-resistant flame-retardant conductive paste comprises the following steps,
1) treating graphene to enable the surface to contain hydroxyl, so as to obtain hydroxylated graphene;
2) uniformly dispersing the graphene in an aqueous resin, in step 2):
2, a) dispersing the hydroxylated graphene prepared in the step 1) into aqueous solutions of phosphorus pentoxide, phosphoric acid, phosphate, monohydrogen phosphate and dihydrogen phosphate;
2, b) carrying out ultrasonic treatment on the solution prepared in the step 2.a) to uniformly disperse graphene in the solution;
and 2, c) pouring the solution dispersed in the step 2.b) into a hydrothermal reaction kettle for reaction to obtain the graphene containing phosphate groups.
2. The method for preparing the aqueous graphene high-temperature-resistant flame-retardant conductive paste according to claim 1, in step 1):
a) dispersing graphene to FeSO4·7H2O、FeCl2·4H2O、Fe(NO3)2·6H2O、H2O2In the solution of (1);
1, b) carrying out ultrasonic treatment on the prepared solution to ensure that graphene can be uniformly dispersed in the solution;
and c) pouring the dispersed solution into a hydrothermal reaction kettle for reaction.
3. The method for preparing the aqueous graphene high temperature resistant flame retardant conductive paste according to claim 2, wherein the temperature in the hydrothermal reaction kettle in the step 1.c) is 180-220 ℃.
4. The method for preparing the aqueous graphene high temperature resistant flame retardant conductive paste according to claim 1, wherein the graphene used in the step 1) is prepared by oxidation reduction, CVD method, mechanical stripping and other methods.
5. The method for preparing the aqueous graphene high temperature resistant flame retardant conductive paste according to claim 1, wherein in the step 2), the aqueous resin is one or more of aqueous epoxy resin, aqueous phenolic resin, aqueous acrylic resin, aqueous polyurethane and aqueous silicone resin.
6. The aqueous graphene high-temperature-resistant flame-retardant conductive paste prepared by the method of any one of claims 1 to 5.
7. Use of the aqueous graphene high-temperature-resistant flame-retardant conductive paste prepared by the method of any one of claims 1 to 5 in preparation of an aqueous high-temperature-resistant flame-retardant graphene electrothermal film.
8. The use according to claim 7, in antistatic floor paints, electromagnetic shielding coatings.
Priority Applications (1)
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| CN110303739A (en) * | 2019-05-28 | 2019-10-08 | 宁波捷傲创益新材料有限公司 | A kind of macromolecule heating film, preparation method and applications |
| CN110746853A (en) * | 2019-11-01 | 2020-02-04 | 嘉兴烯成新材料有限公司 | Preparation method of hydroxylated graphene powder coating |
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