CN117363148B - Graphene anticorrosive paint - Google Patents
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- CN117363148B CN117363148B CN202311233919.0A CN202311233919A CN117363148B CN 117363148 B CN117363148 B CN 117363148B CN 202311233919 A CN202311233919 A CN 202311233919A CN 117363148 B CN117363148 B CN 117363148B
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 93
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 66
- 239000003973 paint Substances 0.000 title claims abstract description 28
- 239000003822 epoxy resin Substances 0.000 claims abstract description 17
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229920003180 amino resin Polymers 0.000 claims abstract description 13
- 238000000576 coating method Methods 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 12
- 239000011248 coating agent Substances 0.000 claims abstract description 11
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 10
- 239000003054 catalyst Substances 0.000 claims abstract description 9
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000008367 deionised water Substances 0.000 claims abstract description 6
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 6
- 239000013530 defoamer Substances 0.000 claims abstract description 5
- 239000003112 inhibitor Substances 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims description 42
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 32
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 30
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 30
- 238000006243 chemical reaction Methods 0.000 claims description 28
- 238000002156 mixing Methods 0.000 claims description 27
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 18
- OSDWBNJEKMUWAV-UHFFFAOYSA-N Allyl chloride Chemical compound ClCC=C OSDWBNJEKMUWAV-UHFFFAOYSA-N 0.000 claims description 17
- 239000003607 modifier Substances 0.000 claims description 16
- DCQBZYNUSLHVJC-UHFFFAOYSA-N 3-triethoxysilylpropane-1-thiol Chemical compound CCO[Si](OCC)(OCC)CCCS DCQBZYNUSLHVJC-UHFFFAOYSA-N 0.000 claims description 15
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 13
- 238000010992 reflux Methods 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 12
- HASCQPSFPAKVEK-UHFFFAOYSA-N dimethyl(phenyl)phosphine Chemical compound CP(C)C1=CC=CC=C1 HASCQPSFPAKVEK-UHFFFAOYSA-N 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 10
- 239000012752 auxiliary agent Substances 0.000 claims description 10
- 239000000805 composite resin Substances 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 10
- 238000002390 rotary evaporation Methods 0.000 claims description 10
- 230000001276 controlling effect Effects 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 7
- 230000003301 hydrolyzing effect Effects 0.000 claims description 6
- 230000001105 regulatory effect Effects 0.000 claims description 6
- 238000001694 spray drying Methods 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 238000009835 boiling Methods 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- 239000013049 sediment Substances 0.000 claims description 5
- 229920003270 Cymel® Polymers 0.000 claims description 3
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 3
- 230000000694 effects Effects 0.000 abstract description 12
- 230000008569 process Effects 0.000 abstract description 8
- 239000002344 surface layer Substances 0.000 abstract description 7
- 239000010410 layer Substances 0.000 abstract description 6
- 229910052751 metal Inorganic materials 0.000 abstract description 6
- 239000002184 metal Substances 0.000 abstract description 6
- 239000000758 substrate Substances 0.000 abstract description 6
- 238000004132 cross linking Methods 0.000 abstract description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 4
- 239000004593 Epoxy Substances 0.000 abstract description 3
- LOTCVJJDZFMQGB-UHFFFAOYSA-N [N].[O].[S] Chemical group [N].[O].[S] LOTCVJJDZFMQGB-UHFFFAOYSA-N 0.000 abstract description 2
- 239000000945 filler Substances 0.000 abstract description 2
- 230000003014 reinforcing effect Effects 0.000 abstract description 2
- 230000009920 chelation Effects 0.000 abstract 3
- 238000005260 corrosion Methods 0.000 description 12
- 230000007797 corrosion Effects 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 238000010907 mechanical stirring Methods 0.000 description 6
- 230000007935 neutral effect Effects 0.000 description 6
- 238000007792 addition Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 5
- 230000008878 coupling Effects 0.000 description 4
- 238000010168 coupling process Methods 0.000 description 4
- 238000005859 coupling reaction Methods 0.000 description 4
- CWAFVXWRGIEBPL-UHFFFAOYSA-N ethoxysilane Chemical group CCO[SiH3] CWAFVXWRGIEBPL-UHFFFAOYSA-N 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 3
- 239000000292 calcium oxide Substances 0.000 description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 238000001132 ultrasonic dispersion Methods 0.000 description 3
- 238000007259 addition reaction Methods 0.000 description 2
- 239000002518 antifoaming agent Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000005536 corrosion prevention Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 229920006334 epoxy coating Polymers 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 230000011218 segmentation Effects 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Paints Or Removers (AREA)
Abstract
The invention relates to a graphene anticorrosive paint, and belongs to the technical field of epoxy paint. The coating comprises the following components in parts by weight: 100 parts of water-based epoxy resin, 8-12 parts of amino resin, 1.7-2.1 parts of modified graphene, 0.5-0.6 part of catalyst, 0.3-0.5 part of defoamer, 0.2-0.3 part of flatting agent, 0.1-0.15 part of flash rust inhibitor and 6-8 parts of deionized water; the nitrogen-oxygen-sulfur structure in the modified graphene surface layer structure has a strong chelation effect with a metal substrate, and through the chelation effect, graphene is enriched to the surface layer of the substrate and anchored through chelation, so that a uniform graphene shielding layer is formed, the modified graphene surface layer structure is provided with branch-shaped hydroxyl groups, and the modified graphene surface layer structure participates in epoxy resin crosslinking to crosslink and fix graphene of the enriched layer in the baking and curing process, and meanwhile, dispersed graphene is combined with a substrate through crosslinking, so that the reinforcing effect of the graphene serving as a filler is fully exerted.
Description
Technical Field
The invention belongs to the technical field of epoxy paint, and particularly relates to a graphene anticorrosive paint.
Background
The metal and the alloy are one of the engineering materials with huge consumption, are widely applied to the fields of construction, traffic and the like, play a role in national economy and social progress, however, the metal corrosion reduces the performance of the metal component, and cause economic loss, safety problem and other negative effects.
Among the metal anticorrosion means, the coating is used for anticorrosion, is most economical and effective, is convenient and fast to construct, and is widely applied to various industries, wherein the epoxy coating contains ether groups and hydroxyl groups with very strong polarity, can generate strong interaction force with most substrate interfaces, has stable chemical property, is different in types and good in performance, and is used for coating on the market; with the advent of graphene, graphene is doped into epoxy paint to obtain a more favorable anti-corrosion effect, and research and demonstration prove that the mechanism of the synergy of graphene is mainly as follows: the ultra-micro lamellar graphene is laminated in a staggered manner in the coating to form a labyrinth shielding effect to prevent corrosion graft penetration, so that the effect of isolating corrosion is achieved. However, long-term researches show that graphene is lamellar and dispersed in resin to form a segmentation effect, when the dosage of the graphene exceeds a certain range, the mechanical property of the coating is reduced in a cliff type, and the corrosion prevention effect is not increased along with the increase of the dosage of the graphene, and the analysis is that: the amount of graphene is increased, but the graphene still generates shielding effect by staggered lamination, and a stable and continuous shielding layer cannot be formed.
Disclosure of Invention
In order to solve the technical problems in the background art, the invention aims to provide a graphene anticorrosive paint.
The aim of the invention can be achieved by the following technical scheme:
the graphene anticorrosive paint comprises the following components in parts by weight:
100 parts of water-based epoxy resin, 8-12 parts of amino resin, 1.7-2.1 parts of modified graphene, 0.5-0.6 part of catalyst, 0.3-0.5 part of defoamer, 0.2-0.3 part of flatting agent, 0.1-0.15 part of flash rust inhibitor and 6-8 parts of deionized water.
The modified graphene is prepared by the following method:
step A1: dissolving diethanolamine in acetone, installing an alkaline drying pipe in a reflux device, heating to 45-50 ℃ for reflux, applying 180-240rpm mechanical stirring, slowly adding allyl chloride, controlling the adding reaction time to be 1.6-2.2h, and removing low-boiling substances mainly including acetone and excessive allyl chloride by rotary evaporation after the reaction is finished to obtain an intermediate;
further, the dosage ratio of diethanolamine, allyl chloride and acetone was 0.1mol:0.11-0.13mol:60-75mL, substitution reaction of allyl chloride and diethanolamine, graft double bond structure modification, the specific reaction process can be expressed as follows:
step A2: mixing gamma-mercaptopropyl triethoxysilane, intermediate, dimethyl phenyl phosphine and dimethyl sulfoxide under nitrogen protection, heating to 75-90deg.C, mechanically stirring at 80-120rpm with 500-700W/m 2 Ultraviolet irradiation, constant temperature irradiation stirring reaction for 2-3h, and decompression rotary evaporation to remove dimethyl sulfoxide after the reaction is finished to obtain a modifier;
further, the dosage ratio of gamma-mercaptopropyl triethoxysilane, intermediate, dimethylphenylphosphine and dimethyl sulfoxide was 0.1mol:0.1mol:0.1-0.15g:80-100mL, and under the conditions of dimethylphenylphosphine catalyst and ultraviolet irradiation, gamma-mercaptopropyl triethoxysilane and an intermediate are subjected to click addition reaction, and an ethoxysilane structure is introduced, wherein the specific reaction process can be expressed as follows:
step A3: uniformly mixing a modifier, an ethanol solution and dimethylacetamide, regulating the pH value to be 4 by acetic acid, stirring and hydrolyzing for 1-1.5h, adding graphene oxide, stirring and mixing at a high speed, controlling the stirring speed to be 120-150rpm, regulating to be neutral by ammonia water, standing for 24h at room temperature, taking the bottom sediment, dispersing in water by ultrasonic waves, and spray drying to obtain modified graphene;
further, the dosage ratio of graphene oxide, modifier, ethanol solution and dimethylacetamide is 100g:20-30mmol:200-300mL:50-80mL, wherein the mass fraction of the ethanol solution is 40%, the ethoxysilane structure in the modifier molecule is hydrolyzed under an acidic condition, and then the ethoxysilane structure is coupled with graphene oxide along with the rise of the pH value, and is loaded on the surface of the graphene oxide to modify the graphene oxide.
Further, the model of the aqueous epoxy resin is EPIKOTE 3540-WY-55.
Further, the amino resin is of the type CYMEL 303.
Further, the catalyst is CYCAT 4040.
Further, the model of the antifoaming agent was 901W.
Further, the model of the leveling agent is RM-2020.
Further, the type of the flash rust inhibitor is FA-179.
A graphene anticorrosive paint comprises the following specific preparation methods: and (3) stirring and premixing the aqueous epoxy resin and the amino resin at a low speed to obtain composite resin, stirring and dispersing other raw materials at a high speed to obtain a compound auxiliary agent, adding the compound auxiliary agent into the composite resin in a stirring state, uniformly mixing, and carrying out vacuum defoaming to obtain the graphene anticorrosive paint.
The invention has the beneficial effects that:
according to the invention, epoxy resin is used as a matrix, and modified graphene is compounded to obtain the coating with excellent anti-corrosion performance; according to the modified graphene, double bonds are introduced into a diethanolamine structure through substitution reaction of allyl chloride and diethanolamine, then the double bonds are catalyzed and clicked with gamma-mercaptopropyl triethoxysilane for addition, an ethoxysilane structure is grafted, finally the modified graphene is prepared through coupling and loading on the surface of graphene oxide, the dispersibility of graphene in an epoxy resin matrix is improved by organic groups on the surface of the modified graphene, compared with the existing graphene doped coating, the nitrogen-oxygen-sulfur structure in the surface layer structure of the modified graphene has a strong chelating effect with a metal substrate, and during the coating and curing process, graphene is enriched to the surface layer of the substrate through the chelating effect and is anchored through chelating, so that a uniform graphene shielding layer is formed, and compared with graphene which is distributed in a disordered way, the modified graphene is more beneficial to exerting a high-efficiency corrosion prevention effect; in addition, the modified graphene surface layer structure is provided with branch-shaped hydroxyl groups, and the branch-shaped hydroxyl groups participate in epoxy resin crosslinking in the baking and curing process to crosslink and fix the graphene of the enrichment layer, and meanwhile, the dispersed graphene is combined with the matrix through crosslinking, so that the reinforcing effect of the graphene serving as a filler is fully exerted.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described in the following in conjunction with the embodiments of the present invention, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
The graphene anticorrosive paint prepared by the embodiment has the following specific implementation process:
1) Preparation of modified graphene
1.1, taking diethanolamine and acetone, stirring and mixing, mounting a calcium oxide alkaline drying pipe in a reflux device, heating to 50 ℃ for reflux, applying 240rpm mechanical stirring, slowly adding allyl chloride within 40min, continuing constant-temperature reflux reaction after complete addition, and controlling the addition reaction time to be 1.6h, wherein the dosage ratio of the diethanolamine, the allyl chloride and the acetone is 0.1mol:0.13mol:75mL, and removing low-boiling substances mainly comprising acetone and excessive allyl chloride by rotary evaporation after the reaction is finished, thereby obtaining the intermediate.
1.2 taking gamma-mercaptopropyl triethoxysilane, an intermediate, dimethyl phenyl phosphine and dimethyl sulfoxide, uniformly mixing under the protection of nitrogen, heating to 90 ℃, applying 120rpm mechanical stirring, and assisting with 700W/m 2 Ultraviolet irradiation, constant temperature irradiation stirring reaction for 2 hours, wherein in the reaction, the dosage ratio of gamma-mercaptopropyl triethoxysilane, an intermediate, dimethyl phenyl phosphine and dimethyl sulfoxide is 0.1mol:0.1mol:0.15g:100mL, and removing dimethyl sulfoxide by reduced pressure rotary evaporation after the reaction is finished, thus obtaining the modifier.
1.3, preparing an ethanol solution with the mass fraction of 40%, uniformly mixing a modifier, the ethanol solution and dimethylacetamide, adding acetic acid to adjust the pH value to be 4, stirring and hydrolyzing for 1h, adding graphene oxide (with the sheet diameter of about 2 mu m and provided by Beijing island gold technology Co., ltd.), stirring and mixing at a high speed of 2000rpm for 10min, controlling the stirring speed to be 150rpm, uniformly adding ammonia water (industrial ammonia water with the mass fraction of 25%) to adjust to be neutral, and standing for 24h at room temperature, wherein the dosage ratio of the graphene oxide, the modifier, the ethanol solution and the dimethylacetamide is 100g:30mmol:300mL: and (3) centrifuging after the reaction is finished, taking a bottom sediment, adding water, performing ultrasonic dispersion to form a dispersion liquid with the solid content of 50%, and performing spray drying to obtain the modified graphene.
2) Graphene anticorrosive paint
2.1, the following raw materials are taken according to the weight ratio:
100 parts of aqueous epoxy resin, in the examples a commercially available resin dispersion of the type EPIKOTE 3540-WY-55 was used;
12 parts of amino resin, commercially available resin with the model number CYMEL 303 is used in the examples;
1.7 parts of modified graphene, prepared from the example;
catalyst 0.6 parts, in the examples, CYCAT 4040;
0.3 part of defoaming agent, wherein the model is 901W in the embodiment;
0.2 part of leveling agent, wherein the model number of the leveling agent is RM-2020;
0.15 part of flash rust inhibitor, wherein the model is FA-179 in the embodiment;
6 parts of deionized water.
2.2, adding the aqueous epoxy resin and the amino resin into a batching kettle, stirring and mixing for 1h at a low speed of 60rpm to prepare composite resin, adding the rest raw materials into a stirrer, stirring and dispersing for 10min at a high speed of 1500rpm to prepare a compound auxiliary agent, stirring the composite resin at 80rpm, adding the compound auxiliary agent at a constant speed, mixing for 2h, and then carrying out vacuum defoaming treatment to obtain the graphene anticorrosive paint.
Example 2
The graphene anticorrosive paint prepared by the embodiment has the following specific implementation process:
1) Preparation of modified graphene
1.1, taking diethanolamine and acetone, stirring and mixing, mounting a calcium oxide alkaline drying pipe in a reflux device, heating to 45 ℃ for reflux, applying 180rpm mechanical stirring, slowly adding allyl chloride within 60min, continuing constant-temperature reflux reaction after complete addition, and controlling the adding reaction time to be 2.2h, wherein the dosage ratio of diethanolamine, allyl chloride and acetone is 0.1mol:0.11mol:60mL, and removing low-boiling substances mainly comprising acetone and excessive allyl chloride by rotary evaporation after the reaction is finished, thereby obtaining the intermediate.
1.2 taking gamma-mercaptopropyl triethoxysilane, an intermediate, dimethyl phenyl phosphine and dimethyl sulfoxide, uniformly mixing under the protection of nitrogen, heating to 75 ℃, applying mechanical stirring at 80rpm, and assisting with 500W/m 2 Ultraviolet irradiation, constant temperature irradiation stirring reaction for 3 hours, wherein in the reaction, the dosage ratio of gamma-mercaptopropyl triethoxysilane, an intermediate, dimethyl phenyl phosphine and dimethyl sulfoxide is 0.1mol:0.1mol:0.1g:80mL, and removing dimethyl sulfoxide by reduced pressure rotary evaporation after the reaction is finished, thus obtaining the modifier.
1.3, preparing an ethanol solution with the mass fraction of 40%, uniformly mixing a modifier, the ethanol solution and dimethylacetamide, adding acetic acid to adjust the pH value to be 4, stirring and hydrolyzing for 1.5h, adding graphene oxide, stirring and mixing at a high speed of 2000rpm for 10min, controlling the stirring speed to be 120rpm, adding ammonia water at a constant speed to adjust to be neutral, and standing at room temperature for 24h, wherein the dosage ratio of the graphene oxide, the modifier, the ethanol solution and the dimethylacetamide is 100g in the reaction: 20mmol:200mL: and (3) 80mL, centrifuging after the reaction is finished, taking a bottom sediment, adding water, performing ultrasonic dispersion to form a dispersion liquid with the solid content of 50%, and performing spray drying to obtain the modified graphene.
2) Graphene anticorrosive paint
2.1, the following raw materials are taken according to the weight ratio:
100 parts of aqueous epoxy resin, 8 parts of amino resin, 2.1 parts of modified graphene (prepared in the embodiment), 0.5 part of catalyst, 0.5 part of defoamer, 0.3 part of flatting agent, 0.1 part of anti-flash rust agent and 8 parts of deionized water.
2.2, adding the aqueous epoxy resin and the amino resin into a batching kettle, stirring and mixing for 1h at a low speed of 60rpm to prepare composite resin, adding the rest raw materials into a stirrer, stirring and dispersing for 10min at a high speed of 1500rpm to prepare a compound auxiliary agent, stirring the composite resin at 80rpm, adding the compound auxiliary agent at a constant speed, mixing for 2h, and then carrying out vacuum defoaming treatment to obtain the graphene anticorrosive paint.
Example 3
The graphene anticorrosive paint prepared by the embodiment has the following specific implementation process:
1) Preparation of modified graphene
1.1, taking diethanolamine and acetone, stirring and mixing, mounting a calcium oxide alkaline drying pipe in a reflux device, heating to 48 ℃ for reflux, applying 240rpm mechanical stirring, slowly adding allyl chloride within 50min, and continuing constant-temperature reflux reaction after complete addition, wherein the adding reaction time is controlled to be 2h, and the dosage ratio of the diethanolamine, the allyl chloride and the acetone is 0.1mol:0.12mol:70mL, and removing low-boiling substances mainly comprising acetone and excessive allyl chloride by rotary evaporation after the reaction is finished, thereby obtaining the intermediate.
1.2 taking gamma-mercaptopropyl triethoxysilane, an intermediate, dimethyl phenyl phosphine and dimethyl sulfoxide under the protection of nitrogenMixing, heating to 80deg.C, mechanically stirring at 120rpm, and 600W/m 2 Ultraviolet irradiation, constant temperature irradiation stirring reaction for 2.5h, wherein in the reaction, the dosage ratio of gamma-mercaptopropyl triethoxysilane, an intermediate, dimethyl phenyl phosphine and dimethyl sulfoxide is 0.1mol:0.1mol:0.12g:90mL, and removing dimethyl sulfoxide by reduced pressure rotary evaporation after the reaction is finished, thus obtaining the modifier.
1.3, preparing an ethanol solution with the mass fraction of 40%, uniformly mixing a modifier, the ethanol solution and dimethylacetamide, adding acetic acid to adjust the pH value to be 4, stirring and hydrolyzing for 1.2 hours, adding graphene oxide, stirring and mixing at a high speed of 2000rpm for 10 minutes, controlling the stirring speed to be 150rpm, adding ammonia water at a constant speed to adjust to be neutral, and standing for 24 hours at room temperature, wherein the dosage ratio of the graphene oxide, the modifier, the ethanol solution and the dimethylacetamide is 100g in the reaction: 25mmol:280mL: and (3) centrifuging after the reaction is finished, taking a bottom layer precipitate, adding water for ultrasonic dispersion to form a dispersion liquid with the solid content of 50%, and spray-drying to obtain the modified graphene.
2) Graphene anticorrosive paint
2.1, the following raw materials are taken according to the weight ratio:
100 parts of aqueous epoxy resin, 10 parts of amino resin, 1.9 parts of modified graphene (prepared in the embodiment), 0.6 part of catalyst, 0.4 part of defoamer, 0.2 part of flatting agent, 0.13 part of anti-flash rust agent and 7 parts of deionized water.
2.2, adding the aqueous epoxy resin and the amino resin into a batching kettle, stirring and mixing for 1h at a low speed of 60rpm to prepare composite resin, adding the rest raw materials into a stirrer, stirring and dispersing for 10min at a high speed of 1500rpm to prepare a compound auxiliary agent, stirring the composite resin at 80rpm, adding the compound auxiliary agent at a constant speed, mixing for 2h, and then carrying out vacuum defoaming treatment to obtain the graphene anticorrosive paint.
Comparative example
The modified graphene in the embodiment 3 is replaced by gamma-mercaptopropyl triethoxy silane coupling graphene oxide in the comparative example, and the specific coupling treatment method is as follows: mixing gamma-mercaptopropyl triethoxysilane and graphene oxide according to 5.5mL/100g, mixing gamma-mercaptopropyl triethoxysilane and an ethanol solution with the volume fraction of 50 times of 40% under the protection of nitrogen, regulating the pH value to 3.5 by acetic acid, hydrolyzing for 40min at room temperature, adding graphene oxide, stirring for 10min at a high speed, regulating to be neutral by ammonia water, standing at room temperature, coupling for 24h, centrifuging, taking a bottom sediment, adding water, dispersing by ultrasonic to form a dispersion liquid with the solid content of 50%, and spray drying to obtain coupled graphene, wherein the dosage is 2.0 parts, and the rest is the same as in example 3.
Taking a Q235 sheet with the specification of 100 multiplied by 2mm, wiping and airing the sheet by adopting acetone after degreasing treatment, spreading the prepared coating on the surface of the sheet, placing the sheet in an oven, pre-baking for 30min at 80 ℃, heating to 120 ℃ and baking for 20min, continuously heating to 150 ℃ and baking for 15min, and cooling to obtain a sample;
the method for detecting the relevant performance index of the sample comprises the following steps: coating adhesive force test is carried out according to GB/T9286-2021 standard, impact resistance test is carried out according to GB/T1732-2020 standard, flexibility test is carried out according to GB/T1731-2020 standard, water resistance, acid resistance and alkali resistance test are carried out according to GB/T9274-1988 standard, and neutral salt fog resistance test is carried out according to GB/T1771-2007 standard; the specific test data are shown in table 1:
TABLE 1
As can be seen from the data in Table 1, the coatings prepared in examples and comparative examples all have good combination of properties, and meet the general corrosion protection requirements.
Based on the test data, sampling from the prepared sample to perform electrochemical performance test, and taking a platinum electrode as a counter electrode and Ag/AgCl as a reference electrode, wherein the operation time is 1800s in the open circuit potential test process, the scanning interval is 200mA/s, the voltage range is-600-600 mV in the corrosion electrical parameter test process, and the scanning rate is 2mV/s; the specific tests are shown in table 2:
TABLE 2
| Example 1 | Example 2 | Example 3 | Comparative example | |
| Open circuit potential/mV | 34 | 42 | 40 | -328 |
| Corrosion potential/mV cm -2 | -368 | -280 | -316 | -1042 |
| Corrosion current/. Mu.A.cm -2 | 2.6 | 2.1 | 3.2 | 526 |
As can be seen from the data in table 2, the coatings prepared in the examples have positive open circuit potential, corrosion current and corrosion potential which are significantly higher than those of the comparative examples, and theoretically have more excellent corrosion resistance.
In the description of the present specification, the descriptions of the terms "one embodiment," "example," "specific example," and the like, mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiments or examples. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing is merely illustrative and explanatory of the invention, as various modifications and additions may be made to the particular embodiments described, or in a similar manner, by those skilled in the art, without departing from the scope of the invention or exceeding the scope of the invention as defined in the claims.
Claims (8)
1. The graphene anticorrosive paint is characterized by comprising the following components in parts by weight:
100 parts of water-based epoxy resin, 8-12 parts of amino resin, 1.7-2.1 parts of modified graphene, 0.5-0.6 part of catalyst, 0.3-0.5 part of defoamer, 0.2-0.3 part of flatting agent, 0.1-0.15 part of flash rust inhibitor and 6-8 parts of deionized water;
the modified graphene is prepared by the following method:
step A1: dissolving diethanolamine in acetone, installing an alkaline drying pipe in a reflux device, heating to 45-50 ℃ for reflux, stirring, slowly adding allyl chloride, controlling the adding reaction time to be 1.6-2.2h, and removing low-boiling substances mainly comprising acetone and excessive allyl chloride by rotary evaporation after the reaction is finished to obtain an intermediate;
step A2: mixing gamma-mercaptopropyl triethoxysilane, intermediate, dimethyl phenyl phosphine and dimethyl sulfoxide under nitrogen protection, heating to 75-90deg.C, stirring with 500-700W/m 2 Ultraviolet irradiation, constant temperature irradiation stirring reaction for 2-3h,removing dimethyl sulfoxide by reduced pressure rotary evaporation after the reaction is finished to obtain a modifier;
step A3: mixing modifier, ethanol solution and dimethylacetamide uniformly, regulating pH value to 4 by acetic acid, stirring and hydrolyzing for 1-1.5h, adding graphene oxide, stirring and mixing at high speed, stirring and regulating to neutrality by ammonia water, standing for 24h at room temperature, taking the bottom sediment, dispersing in water by ultrasonic wave, and spray drying to obtain the modified graphene.
2. The graphene anticorrosive paint according to claim 1, wherein the dosage ratio of diethanolamine, allyl chloride and acetone is 0.1mol:0.11-0.13mol:60-75mL.
3. The graphene anticorrosive paint according to claim 2, wherein the dosage ratio of gamma-mercaptopropyl triethoxysilane, intermediate, dimethylphenylphosphine and dimethyl sulfoxide is 0.1mol:0.1mol:0.1-0.15g:80-100mL.
4. A graphene anticorrosive paint according to claim 3, wherein the dosage ratio of graphene oxide, modifier, ethanol solution and dimethylacetamide is 100g:20-30mmol:200-300mL:50-80mL.
5. The graphene anticorrosive paint according to claim 1, wherein the aqueous epoxy resin is of the type EPIKOTE 3540-WY-55.
6. The graphene anticorrosive paint according to claim 5, wherein the amino resin is CYMEL 303.
7. The graphene anticorrosive paint according to claim 6, wherein the catalyst is CYCAT 4040.
8. The graphene anticorrosive paint according to claim 1, wherein the specific preparation method comprises the following steps: premixing the aqueous epoxy resin and the amino resin to obtain composite resin, stirring and dispersing other raw materials to obtain a compound auxiliary agent, adding the compound auxiliary agent into the composite resin in a stirring state, uniformly mixing, and carrying out vacuum defoaming to obtain the graphene anticorrosive coating.
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