CN113444420A - Epoxy resin-graphene/graphene oxide composite coating and preparation method thereof - Google Patents
Epoxy resin-graphene/graphene oxide composite coating and preparation method thereof Download PDFInfo
- Publication number
- CN113444420A CN113444420A CN202110530313.8A CN202110530313A CN113444420A CN 113444420 A CN113444420 A CN 113444420A CN 202110530313 A CN202110530313 A CN 202110530313A CN 113444420 A CN113444420 A CN 113444420A
- Authority
- CN
- China
- Prior art keywords
- graphene
- graphene oxide
- epoxy resin
- powder
- composite coating
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 99
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 88
- 238000000576 coating method Methods 0.000 title claims abstract description 48
- 239000011248 coating agent Substances 0.000 title claims abstract description 45
- 239000002131 composite material Substances 0.000 title claims abstract description 33
- 239000004593 Epoxy Substances 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- -1 silicon modified graphene Chemical class 0.000 claims abstract description 52
- 239000007788 liquid Substances 0.000 claims abstract description 40
- 239000006185 dispersion Substances 0.000 claims abstract description 31
- 239000003822 epoxy resin Substances 0.000 claims abstract description 31
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 31
- 239000000843 powder Substances 0.000 claims abstract description 28
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 22
- 239000010703 silicon Substances 0.000 claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims abstract description 7
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 claims abstract description 7
- 150000001263 acyl chlorides Chemical class 0.000 claims abstract description 5
- 150000001412 amines Chemical class 0.000 claims abstract description 4
- 125000003700 epoxy group Chemical group 0.000 claims abstract description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 28
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 26
- 238000003756 stirring Methods 0.000 claims description 25
- 238000005406 washing Methods 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 18
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims description 16
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 15
- 229910052757 nitrogen Inorganic materials 0.000 claims description 13
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 12
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 10
- 229960001701 chloroform Drugs 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 9
- 230000004048 modification Effects 0.000 claims description 8
- 238000012986 modification Methods 0.000 claims description 8
- 238000001291 vacuum drying Methods 0.000 claims description 7
- 125000003277 amino group Chemical group 0.000 claims description 5
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- 239000002518 antifoaming agent Substances 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 238000005286 illumination Methods 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 238000007789 sealing Methods 0.000 claims description 4
- 238000003760 magnetic stirring Methods 0.000 claims description 3
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 239000012046 mixed solvent Substances 0.000 claims description 2
- 229920000570 polyether Polymers 0.000 claims description 2
- 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 abstract description 15
- 239000003063 flame retardant Substances 0.000 abstract description 14
- WGMVWLFIGVCPPV-UHFFFAOYSA-N 4-diazobutanoic acid Chemical compound OC(=O)CCC=[N+]=[N-] WGMVWLFIGVCPPV-UHFFFAOYSA-N 0.000 abstract description 7
- 239000000463 material Substances 0.000 abstract description 6
- 230000007797 corrosion Effects 0.000 abstract description 4
- 238000005260 corrosion Methods 0.000 abstract description 4
- 238000012360 testing method Methods 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 14
- 239000003973 paint Substances 0.000 description 8
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000007921 spray Substances 0.000 description 6
- 238000011160 research Methods 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000005507 spraying Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000002114 nanocomposite Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- AHDSRXYHVZECER-UHFFFAOYSA-N 2,4,6-tris[(dimethylamino)methyl]phenol Chemical compound CN(C)CC1=CC(CN(C)C)=C(O)C(CN(C)C)=C1 AHDSRXYHVZECER-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 244000137852 Petrea volubilis Species 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 150000004074 biphenyls Chemical class 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000013530 defoamer Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical class C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 238000001757 thermogravimetry curve Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000004634 thermosetting polymer Substances 0.000 description 1
- 239000005028 tinplate Substances 0.000 description 1
- 230000001960 triggered effect Effects 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
Images
Classifications
-
- 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
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Carbon And Carbon Compounds (AREA)
- Paints Or Removers (AREA)
Abstract
The invention relates to an epoxy resin-graphene/graphene oxide composite coating and a preparation method thereof, and the preparation method comprises the following steps: s11: adding graphene and dicyclohexylcarbodiimide into 3-aminopropyltriethoxysilane to obtain organosilicon modified graphene powder; s12: preparing organic silicon modified graphene powder into organic silicon modified graphene dispersion liquid; s21: carrying out a photo-grafting reaction on graphene oxide and 4, 4-diazobutyric acid to prepare carboxyl modified graphene oxide powder; s22: preparing amine modified graphene oxide powder from the carboxyl modified graphite oxide through the reaction of acyl chloride, epoxy group and amine; s3: and (3) preparation of the epoxy resin-graphene/graphene oxide composite coating. According to the invention, the modified graphene and graphene oxide are added into the epoxy resin system, so that the dispersity of the graphene and the graphene oxide in the epoxy resin system is improved, the flame retardant property of the epoxy resin coating is improved, and the strength, toughness, heat resistance and corrosion resistance of the material are also improved.
Description
Technical Field
The invention belongs to the technical field of coatings, and particularly relates to an epoxy resin-graphene/graphene oxide composite coating and a preparation method thereof.
Background
Epoxy resin is taken as a typical thermosetting polymer, has the advantages of excellent adhesiveness, mechanical property, electrical insulation property, chemical stability, low shrinkage rate, easiness in processing and forming, low cost and the like, so that the epoxy resin is widely applied to the high and new technical fields of integrated circuits, transportation, aerospace and the like, and the epoxy resin for the integrated circuits is used in high-frequency and high-voltage occasions and faces the test of continuously emitted heat; the epoxy resin composite material for the airplane and the high-speed train is in a relatively closed environment, and once a fire disaster happens, serious loss which is difficult to recover is easily caused. Therefore, the epoxy resin material must be subjected to flame retardant treatment. Traditionally, the flame-retardant epoxy resin is halogen-containing epoxy resin synthesized by using tetrabromobisphenol A as a raw material, and a cured product has good mechanical property, electrical property and flame retardance. However, with the increasing environmental awareness of countries around the world, the european union has issued two instructions, ralls and WEEE, which stipulate that 6 substances in total, namely lead, mercury, cadmium, hexavalent chromium, polybrominated biphenyls and polybrominated diphenyl ethers, must not be contained in the electronic and electrical products sold in the european union. These instructions have hidden the application prospect of brominated flame-retardant epoxy resin and have become largely and civilian without halogen. Halogen-free flame-retardant epoxy resin is one of the hot directions of research in the field of flame retardance for decades, and although many research works can achieve satisfactory flame-retardant effects, the mechanical properties and the thermal stability of the material are deteriorated. In recent years, the rapid development of the nano composite technology provides a new idea for the research and development of the halogen-free flame-retardant epoxy resin, and can effectively solve the contradiction between the flame retardant property and other properties of the material. In 2004, the discovery of graphene triggered a huge research heat and quickly became a new member of the polymer nanocomposite family. The research of graphene on the flame-retardant polymer nanocomposite just starts, the application research of graphene and derivatives thereof on the flame-retardant epoxy resin composite is systematically developed, and the flame-retardant epoxy resin system is enriched and perfected, so that the method has very important significance.
Disclosure of Invention
In order to achieve the purpose, the invention provides an epoxy resin-graphene/graphene oxide composite coating and a preparation method thereof, wherein the graphene/graphene oxide is used for improving the flame retardant property of epoxy resin and improving the mechanical strength and the corrosion resistance of an epoxy resin system coating.
The technical scheme of the invention is a preparation method of an epoxy resin-graphene/graphene oxide composite coating, which comprises the following steps:
s1: preparation of graphene modification liquid
S11: adding graphene and dicyclohexylcarbodiimide into 3-aminopropyltriethoxysilane, ultrasonically dispersing for 1h, then reacting for 12h at 75 ℃, cooling, centrifuging, washing, and vacuum drying to obtain organosilicon modified graphene powder;
s12: adding the organic silicon modified graphene powder obtained in the step S11 into acetone for ultrasonic dispersion for 30min to obtain organic silicon modified graphene dispersion liquid;
s2: preparation of graphene oxide modification liquid
S21: carrying out a photo-grafting reaction on graphene oxide and 4, 4-diazobutyric acid to prepare carboxyl modified graphene oxide powder;
s22: converting carboxyl on the surface of the carboxyl modified graphene oxide prepared by the step S21 into acyl chloride, and then preparing amino modified graphene oxide powder by reacting the acyl chloride with epoxy groups and amino groups;
s3: preparation of epoxy resin-graphene/graphene oxide composite coating
S31: adding the organic silicon modified graphene dispersion liquid obtained in the step S12 into epoxy resin and a mixed solvent, and performing ultrasonic dispersion for 30min to obtain a component A;
s32: adding the amino modified graphene oxide powder obtained in the step S22 into a curing agent and a defoaming agent, and ultrasonically stirring for 2 hours to obtain a component B;
s33: and adding the component B obtained in the step S32 into the component A in the step S31, stirring for 10min, and vacuumizing for 10min to obtain the epoxy resin-graphene/graphene oxide composite coating.
Preferably, the specific steps of preparing the carboxyl-modified graphene oxide in step S21 are as follows:
s211: adding graphene oxide into trichloromethane, ultrasonically dispersing for 15min, adding 4, 4-diazobutyric acid, and magnetically stirring for 15min to obtain a dispersion liquid A;
s212: and (3) placing the dispersion liquid A under UV illumination, magnetically stirring to react for 2h, filtering, washing and drying in vacuum to obtain carboxyl modified graphene oxide powder.
Preferably, the specific steps of preparing the amine-modified graphene oxide in step S22 are as follows:
s221: adding thionyl chloride into the carboxyl modified graphene oxide powder obtained in the step S212, sealing and ultrasonically dispersing for 10min, introducing nitrogen to remove air in a reaction system, adding acetone, magnetically stirring for reaction for 10min at room temperature, heating to 30 ℃, magnetically stirring for reaction for 2h under the protection of nitrogen, filtering, washing and vacuum drying to obtain powder B;
s222: adding the powder B obtained in the step S221 into trichloromethane, and performing ultrasonic dispersion for 15min to obtain a dispersion liquid C;
s223: adding triethylamine and an accelerator into the polyetheramine, introducing nitrogen to remove air in a reaction system, and stirring at a low temperature for 30min to obtain a mixed solution D;
s224: and dropwise adding the dispersion liquid C of the S222 into the mixed liquid D in the S223, reacting for 1-2h at 0-50 ℃, filtering, washing and drying in vacuum to obtain the amino modified graphene oxide powder.
Preferably, the usage amount of the organosilicon modified graphene powder is 0.02-0.2% of the weight of the component A, the usage amount of the amine group modified graphene oxide powder is 0.02-0.08% of the weight of the component B, and the weight ratio of the component A to the component B is (10-13): (6-9).
Preferably, the mass ratio of the graphene, the dicyclohexylcarbodiimide and the 3-aminopropyltriethoxysilane in step S11 is 2: 1: 1.
preferably, the mass ratio of the silicone-modified graphene powder to acetone in step S12 is 1: 100.
Preferably, the mass ratio of the graphene oxide to the chloroform-neutralized 4, 4' -diazobutyric acid in step S211 is 0.1: 25: 4.
preferably, the mass ratio of the carboxyl-modified graphene oxide powder, the thionyl chloride, the acetone and the polyether amine in the step S21 is 0.08:80:8: 30.
In addition, the invention also provides an epoxy resin-graphene/graphene oxide composite coating which is prepared according to any one of claims 1 to 8.
The invention has the advantages of
(1) According to the invention, the modified graphene and graphene oxide are added into the epoxy resin system, so that the dispersion degree of the graphene and graphene oxide in the epoxy resin system is improved, the flame retardant property of the epoxy resin coating is improved, and the strength, toughness, heat resistance and corrosion resistance of the material are improved;
(2) according to the invention, the amount of amine participating in epoxy curing reaction is increased to the maximum extent by utilizing the graphene oxide with rich amine groups on the surface, so that the epoxy resin coating and the cross section of a coating generate stronger adhesive action, and the service life of the coating is prolonged;
(3) the organic silicon modified graphene can improve the dispersibility of the organic silicon modified graphene, improve the interaction force between the graphene and epoxy resin, enable organic silane and the graphene to generate a chemical bond table, and enable the organic silicon modified graphene and the epoxy resin to generate a chemical reaction through an oxygen radical ring opening reaction, so that the graphene and the epoxy resin are connected through a chemical bond, the problem of agglomeration caused by physical dispersion is avoided, meanwhile, the organic silicon modified graphene with a good dispersion state can form a more effective barrier effect, and the coating shows excellent flame retardant performance.
Drawings
FIG. 1 shows that the heat radiation remote is 35kW/m in examples and comparative examples of the present invention2HRR curve of time;
FIG. 2 is an optical photograph of a 48h salt spray test of coatings prepared according to examples of the present invention and comparative examples; FIG. 3 TGA curves under nitrogen for coatings prepared according to the examples of the invention and comparative examples.
Detailed Description
The present invention will be further described with reference to specific examples, but the present invention is not limited to these examples.
Example 1
The preparation method of the epoxy resin-graphene/graphene oxide composite coating comprises the following steps:
s1: preparation of graphene modification liquid
S11: adding 1g of graphene and 5g of dicyclohexylcarbodiimide into 500ml of 3-aminopropyltriethoxysilane, ultrasonically dispersing for 1h, then reacting for 12h at 75 ℃, cooling, centrifuging, washing, and vacuum drying to obtain organic silicon modified graphene powder;
s12: adding 0.2g of the organic silicon modified graphene powder obtained in the step S11 into 20ml of acetone, and performing ultrasonic dispersion for 30min to obtain an organic silicon modified graphene dispersion liquid;
s2: preparation of graphene oxide modification liquid
S211: adding 1g of graphene oxide into 250ml of trichloromethane, ultrasonically dispersing for 15min, adding 40ml of 4, 4-diazobutyric acid, and magnetically stirring for 15min to obtain a dispersion liquid A;
s212: and (2) placing the dispersion liquid A under UV illumination, carrying out magnetic stirring reaction for 2h, filtering the dispersion liquid A by using a 0.2um polytetrafluoroethylene filter membrane, ultrasonically washing the filtered product by using a large amount of ethyl acetate for multiple times until the filtrate is colorless and transparent to remove the residual 4, 4-diazobutyric acid, and drying the powder in a vacuum oven at 80 ℃ after washing to obtain the carboxyl modified graphene oxide powder.
S221: adding 800ml of thionyl chloride into 0.8g of carboxyl modified graphene oxide powder obtained in the step S212, sealing and ultrasonically dispersing for 10min, introducing nitrogen to remove air in a reaction system, adding 80ml of acetone, magnetically stirring and reacting for 10min at room temperature, heating to 30 ℃, magnetically stirring and reacting for 2h under the protection of nitrogen, and then performing suction filtration treatment by using a 0.2um polytetrafluoroethylene filter membrane. Then, continuously washing the powder by using dry trichloromethane to remove the residual thionyl chloride, and washing to obtain powder B;
s222: adding the powder B obtained in the step S221 into trichloromethane, and performing ultrasonic dispersion for 15min to obtain a dispersion liquid C;
s223: adding 2g of triethylamine and 1.5g of DMP-30 accelerator into 300g of polyetheramine D230, introducing nitrogen to remove air in a reaction system, and stirring at low temperature for 30min to obtain a mixed solution D;
s224: and dropwise adding the dispersion liquid C of the S222 into the mixed liquid D in the S223, reacting for 1-2h at 0-50 ℃, filtering, washing and drying in vacuum to obtain the amino modified graphene oxide powder.
S3: preparation of epoxy resin-graphene/graphene oxide composite coating
S31: adding the organic silicon modified graphene dispersion liquid obtained in the step S12 into 740g of epoxy resin E21, 60g of n-butanol and 180g of xylene, and performing ultrasonic dispersion for 30min to obtain a component A;
s32: adding 0.12g of the amino modified graphene oxide powder obtained in the step S224 into 597g of polyetheramine D230 and 3g of defoaming agent, and ultrasonically stirring for 2 hours to obtain a component B;
s33: and adding the component B obtained in the step S32 into the component A in the step S31, stirring for 10min, and vacuumizing for 10min to obtain the epoxy resin-graphene/graphene oxide composite coating.
Example 2
The preparation method of the epoxy resin-graphene/graphene oxide composite coating comprises the following steps:
s1: preparation of graphene modification liquid
S11: adding 1g of graphene and 5g of dicyclohexylcarbodiimide into 500ml of 3-aminopropyltriethoxysilane, ultrasonically dispersing for 1h, then reacting for 12h at 75 ℃, cooling, centrifuging, washing, and vacuum drying to obtain organic silicon modified graphene powder;
s12: adding 0.2g of the organic silicon modified graphene powder obtained in the step S11 into 20ml of acetone, and performing ultrasonic dispersion for 30min to obtain an organic silicon modified graphene dispersion liquid;
s2: preparation of graphene oxide modification liquid
S211: adding 1g of graphene oxide into 250ml of trichloromethane, ultrasonically dispersing for 15min, adding 40ml of 4, 4-diazobutyric acid, and magnetically stirring for 15min to obtain a dispersion liquid A;
s212: and (2) placing the dispersion liquid A under UV illumination, carrying out magnetic stirring reaction for 2h, filtering the dispersion liquid A by using a 0.2um polytetrafluoroethylene filter membrane, ultrasonically washing the filtered product by using a large amount of ethyl acetate for multiple times until the filtrate is colorless and transparent to remove the residual 4, 4-diazobutyric acid, and drying the powder in a vacuum oven at 80 ℃ after washing to obtain the carboxyl modified graphene oxide powder.
S221: adding 800ml of thionyl chloride into 0.8g of carboxyl modified graphene oxide powder obtained in the step S212, sealing and ultrasonically dispersing for 10min, introducing nitrogen to remove air in a reaction system, adding 80ml of acetone, magnetically stirring and reacting for 10min at room temperature, heating to 30 ℃, magnetically stirring and reacting for 2h under the protection of nitrogen, and then performing suction filtration treatment by using a 0.2um polytetrafluoroethylene filter membrane. Then, continuously washing the powder by using dry trichloromethane to remove the residual thionyl chloride, and washing to obtain powder B;
s222: adding the powder B obtained in the step S221 into trichloromethane, and performing ultrasonic dispersion for 15min to obtain a dispersion liquid C;
s223: adding 2g of triethylamine and 1.5g of DMP-30 accelerator into 300g of polyetheramine D230, introducing nitrogen to remove air in a reaction system, and stirring at low temperature for 30min to obtain a mixed solution D;
s224: and dropwise adding the dispersion liquid C of the S222 into the mixed liquid D in the S223, reacting for 1-2h at 0-50 ℃, filtering, washing and drying in vacuum to obtain the amino modified graphene oxide powder.
S3: preparation of epoxy resin-graphene/graphene oxide composite coating
S31: adding the organic silicon modified graphene dispersion liquid obtained in the step S12 into 740g of epoxy resin E51, 60g of n-butanol and 180g of xylene, and performing ultrasonic dispersion for 30min to obtain a component A;
s32: adding 0.16g of the amino modified graphene oxide powder obtained in the step S224 into 800g of polyetheramine D230 and 3g of defoaming agent, and ultrasonically stirring for 2 hours to obtain a component B;
s33: and adding the component B obtained in the step S32 into the component A in the step S31, stirring for 10min, and vacuumizing for 10min to obtain the epoxy resin-graphene/graphene oxide composite coating.
Example 3
The production was carried out by the method of example 1 except that the amount of the silicone-modified graphene powder in the silicone-modified graphene dispersion liquid of step S12 was 0.8 g.
Example 4
Production was carried out by the method of example 1 except that the amount of the amine-group-modified graphene oxide powder of step S32 was 0.45g
Comparative example 1
The production was carried out by the method of example 1, except that the composite coating did not contain silicone-modified graphene.
Comparative example 2
The production was carried out by the method of example 1, except that the composite coating did not contain amine-modified graphene oxide.
Comparative example 3
The preparation method of example 1 is adopted, and the difference is that the composite coating does not contain organic silicon modified graphene and amino group modified graphene oxide.
Comparative example 4
The production is carried out by adopting the method of example 1, except that the graphene is not modified by organic silicon, 0.2g of graphene powder is directly added into 20ml of acetone for ultrasonic dispersion, and then added into 740g of epoxy resin E21, 60g of n-butyl alcohol and 180g of xylene for ultrasonic dispersion for 30min, so as to obtain the component A.
Comparative example 5
The production was carried out by the method of example 1, except that the graphene oxide was not modified with amine groups, 0.12g of graphene oxide powder was added to 597g of polyetheramine D230 and 3g of defoamer, and stirred ultrasonically for 2h to obtain component B.
The experimental method comprises the following steps:
1. surface treatment of template substrate
The base steel plate used in the experiment is a tin plate with the specification of 150mm multiplied by 70mm multiplied by 2mm, the sample plate is subjected to surface treatment before the experiment, sand paper is used for polishing the sample plate to 120 meshes, absorbent cotton is used for wiping off scrap iron on the surface, then absolute ethyl alcohol and acetone are used for wiping the surface clean, and the sample plate is placed into a vacuum drying oven for drying.
2. Spraying of paint
Adding the coating with the adjusted viscosity into a spray gun, adjusting the air output of the spray gun to enable the coating to reach the spraying requirement, spraying the coating on the surface of the substrate according to the spraying requirement when the distance between the spray gun and the sample plate is about 20cm, and ensuring the thickness of the dry film to be consistent (about 120 um). The sample was left at room temperature for 7 days.
3. Performance testing
(1) Adhesion test
The experiment adopts a circle drawing method: the measurements are carried out according to the provisions of the national Standard GB/T9286-1998 test for marking test for paint and varnish films. Defining a round rolling line on the sample plate by using the adhesive layer, and evaluating the adhesive force of the coating by taking scratches on the upper side of the sample plate as a detection target;
(2) impact resistance test
The method for testing the impact resistance of the paint film is specified according to the national standard GB/T1732-93 'determination method for the impact resistance of the paint film'. The paint film impact resistance is expressed by the maximum height at which a weight of fixed mass falls on the test panel without causing damage to the paint film;
(3) hardness test
The measurement is carried out according to the national standard GB/T6739-1996 'method for measuring pencil hardness of paint film';
(4) combustion test
The determination is carried out according to the national standard GB/T16172-2007 test method for the heat release rate of the building material, and the test result is shown in figure 1;
(5) neutral salt spray resistance test
According to the national standard GB/T1771-2007 determination of the colored paint and varnish-neutral salt spray resistance performance, the test results are shown in figure 2.
(6) Thermal stability
The thermal degradation processes of examples 1 to 5, comparative examples 1 to 5 were investigated by thermogravimetric analysis, and the test results are shown in fig. 3.
The hardness, adhesion and impact resistance test results are shown in Table 1
| Hardness of | Adhesion force | Impact resistance/50 kg.cm | |
| Example 1 | 2H | Level 1 | No crack |
| Example 2 | 2H | Level 1 | No crack |
| Example 3 | 2H | Level 1 | No crack |
| Example 4 | 2H | Level 1 | No crack |
| Comparative example 1 | 2H | Stage 2 | No crack |
| Comparative example 2 | 2H | Level 1 | No crack |
| Comparative example 3 | 3H | Stage 2 | Has cracks |
| Comparative example 4 | 2H | Stage 2 | No crack |
| Comparative example 5 | 2H | Stage 2 | No crack |
The data show that the epoxy resin-graphene/graphene oxide composite coating prepared by the method improves the flame retardant property of the epoxy resin coating, and simultaneously improves the strength, toughness, heat resistance and corrosion resistance of the extracted material; meanwhile, the graphene oxide with rich amino groups on the surface enables the epoxy resin coating to generate stronger bonding effect with the section of a coating.
Although the present application has been described with reference to a few embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the application as defined by the appended claims.
Claims (9)
1. The preparation method of the epoxy resin-graphene/graphene oxide composite coating is characterized by comprising the following steps:
s1: preparation of graphene modification liquid
S11: adding graphene and dicyclohexylcarbodiimide into 3-aminopropyltriethoxysilane, ultrasonically dispersing for 1h, then reacting for 12h at 75 ℃, cooling, centrifuging, washing, and vacuum drying to obtain organosilicon modified graphene powder;
s12: adding the organic silicon modified graphene powder obtained in the step S11 into acetone for ultrasonic dispersion for 30min to obtain organic silicon modified graphene dispersion liquid;
s2: preparation of graphene oxide modification liquid
S21: carrying out a photo-grafting reaction on graphene oxide and 4, 4' -diazobutyric acid to prepare carboxyl modified graphene oxide powder;
s22: converting carboxyl on the surface of the carboxyl modified graphene oxide prepared by the step S21 into acyl chloride, and then preparing amino modified graphene oxide powder by reacting the acyl chloride with epoxy groups and amino groups;
s3: preparation of epoxy resin-graphene/graphene oxide composite coating
S31: adding the organic silicon modified graphene dispersion liquid obtained in the step S12 into epoxy resin and a mixed solvent, and performing ultrasonic dispersion for 30min to obtain a component A;
s32: adding the amino modified graphene oxide powder obtained in the step S22 into a curing agent and a defoaming agent, and ultrasonically stirring for 2 hours to obtain a component B;
s33: and adding the component B obtained in the step S32 into the component A in the step S31, stirring for 10min, and vacuumizing for 10min to obtain the epoxy resin-graphene/graphene oxide composite coating.
2. The method for preparing the epoxy resin-graphene/graphene oxide composite coating according to claim 1, wherein the step of preparing the carboxyl-modified graphene oxide in the step S21 comprises the following specific steps:
s211: adding graphene oxide into trichloromethane, performing ultrasonic dispersion for 15min, adding 4, 4' -diazobutyric acid, and performing magnetic stirring for 15min to obtain a dispersion liquid A;
s212: and (3) placing the dispersion liquid A under UV illumination, magnetically stirring to react for 2h, filtering, washing and drying in vacuum to obtain carboxyl modified graphene oxide powder.
3. The method for preparing the epoxy resin-graphene/graphene oxide composite coating according to claim 2, wherein the step S22 of preparing the amine-modified graphene oxide comprises the following specific steps:
s221: adding thionyl chloride into the carboxyl modified graphene oxide powder obtained in the step S212, sealing and ultrasonically dispersing for 10min, introducing nitrogen to remove air in a reaction system, adding acetone, magnetically stirring for reaction for 10min at room temperature, heating to 30 ℃, magnetically stirring for reaction for 2h under the protection of nitrogen, filtering, washing and vacuum drying to obtain powder B;
s222: adding the powder B obtained in the step S221 into trichloromethane, performing ultrasonic dispersion for 15min,
obtaining a dispersion liquid C;
s223: adding triethylamine and an accelerator into the polyetheramine, introducing nitrogen to remove air in a reaction system, and stirring at a low temperature for 30min to obtain a mixed solution D;
s224: and dropwise adding the dispersion liquid C of the S222 into the mixed liquid D in the S223, reacting for 1-2h at 0-50 ℃, filtering, washing and drying in vacuum to obtain the amino modified graphene oxide powder.
4. The preparation method of the epoxy resin-graphene/graphene oxide composite coating according to claim 1, wherein the amount of the organosilicon modified graphene powder is 0.02-0.2% of the weight of the component A, the amount of the amine-modified graphene oxide powder is 0.02-0.08% of the weight of the component B, and the weight ratio of the component A to the component B is (10-13): (6-9).
5. The method for preparing the epoxy resin-graphene/graphene oxide composite coating according to claim 1, wherein the mass ratio of the graphene, dicyclohexylcarbodiimide and 3-aminopropyltriethoxysilane in step S11 is 2: 1: 1.
6. the method for preparing the epoxy resin-graphene/graphene oxide composite coating according to claim 5, wherein the mass ratio of the organosilicon modified graphene powder to acetone in step S12 is 1: 100.
7. The method for preparing the epoxy resin-graphene/graphene oxide composite coating according to claim 3, wherein the mass ratio of the graphene oxide to the chloroform-neutralized 4, 4' -diazobutyric acid in the step S211 is 0.1: 25: 4.
8. the method for preparing the epoxy resin-graphene/graphene oxide composite coating according to claim 7, wherein the mass ratio of the carboxyl-modified graphene oxide powder, the thionyl chloride, the acetone and the polyether amine in the step S21 is 0.08:80:8: 30.
9. An epoxy resin-graphene/graphene oxide composite coating, which is characterized by being prepared according to any one of claims 1 to 8.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110530313.8A CN113444420A (en) | 2021-05-14 | 2021-05-14 | Epoxy resin-graphene/graphene oxide composite coating and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110530313.8A CN113444420A (en) | 2021-05-14 | 2021-05-14 | Epoxy resin-graphene/graphene oxide composite coating and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113444420A true CN113444420A (en) | 2021-09-28 |
Family
ID=77809858
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110530313.8A Pending CN113444420A (en) | 2021-05-14 | 2021-05-14 | Epoxy resin-graphene/graphene oxide composite coating and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113444420A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN120118591A (en) * | 2025-03-24 | 2025-06-10 | 宁波派特勒新材料股份有限公司 | Epoxy resin powder coating with high heat dissipation performance and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105906842A (en) * | 2016-04-29 | 2016-08-31 | 四川大学 | Modified graphene oxide and epoxy resin composite material and method for preparing same |
| CN106497311A (en) * | 2016-09-29 | 2017-03-15 | 沈阳化工大学 | A kind of preparation method of Graphene fire-resisting coating material |
| WO2018095360A1 (en) * | 2016-11-23 | 2018-05-31 | 厦门大学 | Water-based intumescent fire-resistant coating based on modified graphene oxide, and method for fabrication thereof |
| CN108659467A (en) * | 2018-05-07 | 2018-10-16 | 武汉理工大学 | The method of SiC/ graphene oxide compound modification of epoxy resin |
| CN110172157A (en) * | 2018-08-01 | 2019-08-27 | 江苏华夏制漆科技有限公司 | A kind of modified organic silicone resin and its preparation method and application |
-
2021
- 2021-05-14 CN CN202110530313.8A patent/CN113444420A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105906842A (en) * | 2016-04-29 | 2016-08-31 | 四川大学 | Modified graphene oxide and epoxy resin composite material and method for preparing same |
| CN106497311A (en) * | 2016-09-29 | 2017-03-15 | 沈阳化工大学 | A kind of preparation method of Graphene fire-resisting coating material |
| WO2018095360A1 (en) * | 2016-11-23 | 2018-05-31 | 厦门大学 | Water-based intumescent fire-resistant coating based on modified graphene oxide, and method for fabrication thereof |
| CN108659467A (en) * | 2018-05-07 | 2018-10-16 | 武汉理工大学 | The method of SiC/ graphene oxide compound modification of epoxy resin |
| CN110172157A (en) * | 2018-08-01 | 2019-08-27 | 江苏华夏制漆科技有限公司 | A kind of modified organic silicone resin and its preparation method and application |
Non-Patent Citations (1)
| Title |
|---|
| 段文鹏: "石墨烯/环氧树脂多维界面层构筑及其复合材料高性能化研究", 《中国优秀博士学位论文全文数据库（电子期刊） 工程科技Ⅰ辑》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN120118591A (en) * | 2025-03-24 | 2025-06-10 | 宁波派特勒新材料股份有限公司 | Epoxy resin powder coating with high heat dissipation performance and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109554036B (en) | A kind of room temperature curing power special superhydrophobic coating and preparation and use method thereof | |
| CN107868567B (en) | Epoxy zinc powder primer, paint matching composition and application | |
| CN103724558B (en) | A kind of strawberry type structure inorganic/organic fluoride-containing microballoon and preparation method thereof and application | |
| CN113956700B (en) | A kind of graphene-based polymer composite material and its preparation method and application | |
| CN111793407B (en) | Preparation method of super-hydrophobic flame-retardant coating with excellent performance | |
| CN111944387A (en) | Graphene anticorrosive paint | |
| CN106634264A (en) | Graphene-reinforced superhydrophobic finish-coat paint and preparation method thereof | |
| CN115947886A (en) | Fluorine-containing epoxy acrylate polymer, photocuring transparent super-hydrophobic coating and preparation method | |
| CN113444420A (en) | Epoxy resin-graphene/graphene oxide composite coating and preparation method thereof | |
| CN102827528B (en) | Organic fluorosilicon epoxy paint and preparation method thereof | |
| CN117327449A (en) | Friction-resistant self-drying fluorine-silicon coating material for fastener and preparation method thereof | |
| CN108587068B (en) | A kind of hydrophobic flame-retardant epoxy resin and preparation method thereof | |
| CN103951773A (en) | Long-side-chain fluorine-containing acrylic epoxy resin and coating prepared from resin as raw material | |
| CN114273188B (en) | Fluorine-carbon aluminum veneer and preparation method thereof | |
| CN112877034B (en) | Environment-friendly flame-retardant composite material and preparation method thereof | |
| CN118652606B (en) | A fireproof heat-insulating coating material and its preparation process | |
| CN104789177A (en) | Nano-modified flame-retardant epoxy electronic pouring sealant and preparation method thereof | |
| CN114058083A (en) | Zirconium-based magnesium hydroxide and preparation method and application thereof | |
| CN109370374B (en) | A kind of anti-corrosion and anti-radiation water-based two-component epoxy coating containing polyetheretherketone | |
| CN115353703B (en) | Outdoor anti-aging acrylic plate and preparation process thereof | |
| CN118291010A (en) | A kind of metal powder coating with high weather resistance and preparation method thereof | |
| EP4644121A1 (en) | Negative oxygen ion epoxy coiled material and preparation method therefor | |
| CN117025050A (en) | A kind of magnolol-based epoxy resin anti-corrosion coating and preparation method thereof | |
| CN111363468B (en) | Paint spraying process for surface of automobile support | |
| CN116042056A (en) | A high-solid content environment-friendly and safe transformer pouring paint and its preparation method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210928 |
|
| RJ01 | Rejection of invention patent application after publication |