CN115418126A - Self-repairing coating and application thereof - Google Patents
Self-repairing coating and application thereof Download PDFInfo
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- CN115418126A CN115418126A CN202211149445.7A CN202211149445A CN115418126A CN 115418126 A CN115418126 A CN 115418126A CN 202211149445 A CN202211149445 A CN 202211149445A CN 115418126 A CN115418126 A CN 115418126A
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- 238000000576 coating method Methods 0.000 title claims abstract description 88
- 239000011248 coating agent Substances 0.000 title claims abstract description 82
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 49
- 238000006243 chemical reaction Methods 0.000 claims abstract description 45
- 239000007822 coupling agent Substances 0.000 claims abstract description 23
- 238000005260 corrosion Methods 0.000 claims abstract description 17
- 230000007797 corrosion Effects 0.000 claims abstract description 17
- 239000003112 inhibitor Substances 0.000 claims abstract description 14
- 239000003504 photosensitizing agent Substances 0.000 claims abstract description 11
- 239000002041 carbon nanotube Substances 0.000 claims description 25
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 25
- 238000002156 mixing Methods 0.000 claims description 24
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 20
- 238000010992 reflux Methods 0.000 claims description 18
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 claims description 17
- 229920003192 poly(bis maleimide) Polymers 0.000 claims description 17
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 14
- FCSHDIVRCWTZOX-DVTGEIKXSA-N clobetasol Chemical compound C1CC2=CC(=O)C=C[C@]2(C)[C@]2(F)[C@@H]1[C@@H]1C[C@H](C)[C@@](C(=O)CCl)(O)[C@@]1(C)C[C@@H]2O FCSHDIVRCWTZOX-DVTGEIKXSA-N 0.000 claims description 14
- 239000003960 organic solvent Substances 0.000 claims description 9
- 238000002360 preparation method Methods 0.000 claims description 8
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 claims description 7
- GJKGAPPUXSSCFI-UHFFFAOYSA-N 2-Hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone Chemical compound CC(C)(O)C(=O)C1=CC=C(OCCO)C=C1 GJKGAPPUXSSCFI-UHFFFAOYSA-N 0.000 claims description 6
- KTALPKYXQZGAEG-UHFFFAOYSA-N 2-propan-2-ylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(C(C)C)=CC=C3SC2=C1 KTALPKYXQZGAEG-UHFFFAOYSA-N 0.000 claims description 6
- GQHTUMJGOHRCHB-UHFFFAOYSA-N 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine Chemical compound C1CCCCN2CCCN=C21 GQHTUMJGOHRCHB-UHFFFAOYSA-N 0.000 claims description 5
- FVKFHMNJTHKMRX-UHFFFAOYSA-N 3,4,6,7,8,9-hexahydro-2H-pyrimido[1,2-a]pyrimidine Chemical compound C1CCN2CCCNC2=N1 FVKFHMNJTHKMRX-UHFFFAOYSA-N 0.000 claims description 4
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 claims description 4
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 claims description 3
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 claims description 3
- 239000012957 2-hydroxy-2-methyl-1-phenylpropanone Substances 0.000 claims description 3
- LWRBVKNFOYUCNP-UHFFFAOYSA-N 2-methyl-1-(4-methylsulfanylphenyl)-2-morpholin-4-ylpropan-1-one Chemical compound C1=CC(SC)=CC=C1C(=O)C(C)(C)N1CCOCC1 LWRBVKNFOYUCNP-UHFFFAOYSA-N 0.000 claims description 3
- GUCYFKSBFREPBC-UHFFFAOYSA-N [phenyl-(2,4,6-trimethylbenzoyl)phosphoryl]-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C(=O)C1=C(C)C=C(C)C=C1C GUCYFKSBFREPBC-UHFFFAOYSA-N 0.000 claims description 3
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 claims description 3
- 125000003396 thiol group Chemical class [H]S* 0.000 claims 3
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 abstract description 11
- 238000000034 method Methods 0.000 abstract description 7
- 230000008569 process Effects 0.000 abstract description 4
- 239000003795 chemical substances by application Substances 0.000 abstract description 3
- 239000002131 composite material Substances 0.000 abstract description 2
- 238000005698 Diels-Alder reaction Methods 0.000 description 22
- 229920005989 resin Polymers 0.000 description 18
- 239000011347 resin Substances 0.000 description 18
- 238000005507 spraying Methods 0.000 description 16
- 238000003756 stirring Methods 0.000 description 16
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 15
- 239000000243 solution Substances 0.000 description 14
- 150000003573 thiols Chemical class 0.000 description 14
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 239000002184 metal Substances 0.000 description 11
- 229910052751 metal Inorganic materials 0.000 description 11
- 239000007788 liquid Substances 0.000 description 9
- DZBUGLKDJFMEHC-UHFFFAOYSA-N acridine Chemical compound C1=CC=CC2=CC3=CC=CC=C3N=C21 DZBUGLKDJFMEHC-UHFFFAOYSA-N 0.000 description 8
- 239000006185 dispersion Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 239000007921 spray Substances 0.000 description 8
- 238000000016 photochemical curing Methods 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 238000001878 scanning electron micrograph Methods 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- -1 and more preferably Chemical compound 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000002390 rotary evaporation Methods 0.000 description 5
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 239000003973 paint Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 238000005536 corrosion prevention Methods 0.000 description 3
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 description 3
- 238000005286 illumination Methods 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 230000008439 repair process Effects 0.000 description 3
- 239000005028 tinplate Substances 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000000805 composite resin Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000001678 irradiating effect Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- JWVCLYRUEFBMGU-UHFFFAOYSA-N quinazoline Chemical compound N1=CN=CC2=CC=CC=C21 JWVCLYRUEFBMGU-UHFFFAOYSA-N 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 229910000975 Carbon steel Inorganic materials 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000010962 carbon steel Substances 0.000 description 1
- 238000012650 click reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000002103 nanocoating Substances 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 238000006748 scratching Methods 0.000 description 1
- 230000002393 scratching effect Effects 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000012085 test solution Substances 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
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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
- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D519/00—Heterocyclic compounds containing more than one system of two or more relevant hetero rings condensed among themselves or condensed with a common carbocyclic ring system not provided for in groups C07D453/00 or C07D455/00
-
- 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
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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
- 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
- C09D7/63—Additives non-macromolecular organic
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Inorganic Chemistry (AREA)
- Paints Or Removers (AREA)
Abstract
The invention belongs to the technical field of coatings, and particularly relates to a self-repairing coating and application thereof. The invention provides a self-repairing coating which comprises the following components in percentage by mass: 1 to 25 percent of coupling agent modified carbon nano tube, 30 to 40 percent of polyfunctional group mercaptan, 0.01 to 3 percent of photoinitiator, 0.01 to 3 percent of photosensitizer, 0.01 to 3 percent of photobase generator, 1 to 5 percent of corrosion inhibitor and the balance of prepolymer containing D-A structure. In the invention, the coupling agent modified carbon nano tube can be uniformly dispersed in the coating, can be used as a high-efficiency photo-thermal conversion agent to convert solar energy in the environment into heat energy to provide energy for self-repair, realize self-repair of the coating, and does not need to use an additional mode to provide energy for self-repair. Meanwhile, the coupling agent modified carbon nano tube can also participate in photopolymerization click chemical reaction in the self-repairing process to form an organic/inorganic composite system, so that the stability of the self-repairing coating is improved.
Description
Technical Field
The invention belongs to the technical field of coatings, and particularly relates to a self-repairing coating and application thereof.
Background
The metal material has wide functions in the fields of electric power, aviation, buildings, structural bridges and the like due to excellent mechanical and electrical properties, but the metal corrosion problem causes unrecoverable damage to the metal structure, great potential safety hazards are generated, great economic loss is generated, and the corrosion prevention problem of the metal is urgent and critical.
At present, the mode of spraying an anticorrosive coating on the surface of metal is mainly adopted to reduce metal corrosion; the common anticorrosive paint is a high-molecular paint, and a high-molecular coating film is formed on the surface of metal by utilizing the high-molecular paint to isolate the metal from corrosion factors in the environment, so that an effective anticorrosive effect is achieved. However, the method has poor weather resistance, is difficult to repair by itself after being scratched and scratched by the outside, and the metal device can be exposed in the corrosive environment again, so that the corrosion prevention effect is greatly reduced.
In order to realize self-repairing of an anticorrosive coating, a series of high-molecular anticorrosive coatings with self-repairing effect appear in recent years, wherein the high-molecular anticorrosive coatings with D-A (Diels-Alder) repairing structures have outstanding comprehensive performance. However, the existing high-molecular anticorrosive coating with the D-A repair structure needs to be repaired at a high temperature of 100-120 ℃, so that energy required for repair needs to be provided by manual heating, and self-repair cannot be completely realized.
Disclosure of Invention
In view of the above, the invention provides a self-repairing coating and application thereof, and the coating provided by the invention can be automatically repaired under the condition of solar illumination after the coating is damaged, so that the function of complete self-repairing of an anticorrosive coating is realized.
In order to solve the technical problems, the invention provides a self-repairing coating which comprises the following components in percentage by mass:
preferably, the prepolymer containing D-A structure comprises a prepolymer having a structure represented by formula I:
preferably, the preparation method of the prepolymer with the structure shown in the formula I comprises the following steps:
dissolving furfuryl acrylate and bismaleimide in dimethyl sulfoxide, and carrying out reflux reaction to obtain a prepolymer with a structure shown in a formula I.
Preferably, the molar ratio of the furfuryl acrylate to the bismaleimide is 2-2.1;
the temperature of the reflux reaction is 100-150 ℃, and the time of the reflux reaction is 8-12 h.
Preferably, the preparation method of the coupling agent modified carbon nanotube comprises the following steps:
mixing the carbon nano tube, the silane coupling agent and the organic solvent, and carrying out grafting reaction to obtain the coupling agent modified carbon nano tube.
Preferably, the mass ratio of the carbon nanotubes to the silane coupling agent is 5-10 g: 8-12 mL;
the mass of the carbon nano tube and the volume ratio of the organic solvent are 5-10 g: 90-110 mL.
Preferably, the multifunctional thiol comprises a trifunctional thiol and/or a tetrafunctional thiol.
Preferably, the photoinitiator comprises 2-hydroxy-4- (2-hydroxyethoxy) -2-methylpropiophenone, 1-hydroxycyclohexylphenylketone, phenylbis (2,4,6-trimethylbenzoyl) phosphine oxide, 2-hydroxy-2-methyl-1-phenylpropanone, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide or 2-methyl-2- (4-morpholinyl) -1- [4- (methylthio) phenyl ] -1-propanone;
the photosensitizer comprises 2-isopropylthioxanthone or 2,4,6-trimethylbenzoyl-diphenylphosphine oxide;
the photobase generator comprises 1,5,7-triazabicyclo [4.4.0] dec-5-ene, 1,8-diazabicyclo (5.4.0) undec-7-ene or phenylboronate photobase generators.
Preferably, the corrosion inhibitor is an organic nitrogen heterocyclic corrosion inhibitor.
The invention also provides application of the self-repairing coating in the technical scheme in an anticorrosive coating.
The invention provides a self-repairing coating which comprises the following components in percentage by mass: 1 to 25 percent of coupling agent modified carbon nano tube, 30 to 40 percent of polyfunctional group mercaptan, 0.01 to 3 percent of photoinitiator, 0.01 to 3 percent of photosensitizer, 0.01 to 3 percent of photobase generator, 1 to 5 percent of corrosion inhibitor and the balance of prepolymer containing D-A structure. In the invention, the coupling agent modified carbon nano tube can be uniformly dispersed in the coating, can be used as a high-efficiency photo-thermal conversion agent to convert solar energy in the environment into heat energy to provide energy for self-repair, and can realize self-repair of the coating without additionally providing energy for self-repair. Meanwhile, the coupling agent modified carbon nano tube can also participate in photopolymerization click chemical reaction in the self-repairing process to form an organic/inorganic composite system, so that the stability of the self-repairing coating is improved.
Drawings
FIG. 1 is an SEM image of scratches of the coating of the spraying example 1 before and after self-repair, wherein a is the SEM image before self-repair and b is the SEM image after self-repair;
FIG. 2 is a diagram showing the anticorrosive coatings of the coating materials of example 1 and comparative examples 1 and 2 after salt spray test.
Detailed Description
The invention provides a self-repairing coating which comprises the following components in percentage by mass:
the self-repairing coating provided by the invention comprises 1-25% of coupling agent modified carbon nano tube by mass percentage, preferably 10-24.5%, and more preferably 16.1-24.3%. In the invention, the preparation method of the coupling agent modified carbon nanotube comprises the following steps:
mixing the carbon nano tube, a silane coupling agent and an organic solvent, and carrying out grafting reaction to obtain the coupling agent modified carbon nano tube.
In the present invention, the mixing preferably comprises the steps of:
dispersing carbon nanotubes in an organic solvent to obtain a carbon nanotube dispersion liquid;
and dropwise adding a silane coupling agent to the carbon nanotube dispersion liquid.
In the present invention, the average inner diameter of the carbon nanotube is preferably 3 to 5nm, more preferably 4nm; the average outer diameter of the carbon nano tube is preferably 8 to 15nm, and more preferably 10 to 12nm; the average length of the carbon nanotubes is preferably 3 to 12 μm, and more preferably 6 to 11 μm. In the present invention, the organic solvent preferably includes toluene, chloroform or dichloromethane, and more preferably toluene. In the present invention, the silane coupling agent preferably includes a silane coupling agent KH570. In the present invention, the ratio of the mass of the carbon nanotube to the volume of the silane coupling agent is preferably 5 to 10g:8 to 12mL, more preferably 5 to 10g: 10-12 mL; in the embodiment of the present invention, the ratio of the mass of the carbon nanotube to the volume of the silane coupling agent is 5g:10mL or 10g:12mL. In the present invention, the ratio of the mass of the carbon nanotube to the volume of the organic solvent is preferably 5 to 10g:90 to 110mL, more preferably 5 to 10g:100mL, in the embodiment of the present invention, the ratio of the mass of the carbon nanotube to the volume of the organic solvent is 5g:100mL or 10g:100mL.
In the present invention, the dispersion is preferably carried out under stirring; the invention has no special requirements on the rotating speed and the time of stirring, and can be used as long as the stirring can be uniformly mixed.
The invention has no special requirement on the dropping, as long as the silane coupling agent can be ensured to be uniformly dispersed in the carbon nano tube dispersion liquid.
In the present invention, the time for the grafting reaction is preferably 8 to 12 hours, more preferably 9 to 11 hours. In the present invention, the grafting reaction is preferably accompanied by stirring. In the present invention, the stirring is not particularly limited as long as the graft reaction can be sufficiently performed.
In the present invention, it is preferable that the graft reaction further comprises: and carrying out solid-liquid separation on the system after the grafting reaction. In the present invention, the solid-liquid separation is preferably filtration. The present invention has no special requirements for the filtration, and can be carried out by adopting a conventional mode in the field.
In the invention, the coupling agent modified carbon nano tube has good dispersibility in a resin system, the problem of agglomeration of the carbon nano tube in an organic phase is avoided, the carbon nano tube can be uniformly dispersed in the self-repairing coating, and the self-repairing efficiency is improved. In the invention, the coupling agent modified carbon nanotube is used as a high-efficiency photo-thermal conversion agent, can convert solar energy in the environment into heat energy, raises the temperature of the system without human intervention, provides energy for self-repair and realizes self-repair of the coating. Meanwhile, double bonds (from a silane coupling agent) on the surface of the carbon nano tube modified by the coupling agent and double bonds of resin can generate photopolymerization click chemical reaction, so that the stability of the coating is improved.
The self-repairing coating provided by the invention comprises 30-40% of multifunctional mercaptan by mass percentage, preferably 32.2-36.5%. In the present invention, the multifunctional thiol preferably includes a trifunctional thiol and/or a tetrafunctional thiol, more preferably a trifunctional thiol or a tetrafunctional thiol, and still more preferably a trifunctional thiol.
In the present invention, the trifunctional thiol has a structure represented by formula 1:
in the present invention, the tetrafunctional thiol has the structure of formula 2:
in the invention, the self-repairing can be realized by the light click reaction between the multifunctional thiol and the prepolymer containing the D-A structure.
The self-repairing coating provided by the invention comprises 0.01-3% of photoinitiator by mass, preferably 0.02-1% of photoinitiator by mass, and more preferably 0.03-0.12% of photoinitiator by mass. In the present invention, the photoinitiator preferably includes 2-hydroxy-4- (2-hydroxyethoxy) -2-methylpropiophenone (photoinitiator 2959), 1-hydroxycyclohexylphenylketone, phenylbis (2,4,6-trimethylbenzoyl) phosphine oxide, 2-hydroxy-2-methyl-1-phenylpropanone (photoinitiator 1173), 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, or 2-methyl-2- (4-morpholinyl) -1- [4- (methylthio) phenyl ] -1-propanone, and more preferably, photoinitiator 2959 or photoinitiator 1173.
The self-repairing coating provided by the invention comprises 0.01-3% of photosensitizer by mass, preferably 0.02-1%, and more preferably 0.03-0.12%. In the present invention, the photosensitizer preferably comprises 2-Isopropylthioxanthone (ITX) or 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (TPO), more preferably 2-isopropylthioxanthone.
The self-repairing coating provided by the invention comprises 0.01-3% of photobase generator by mass percentage, preferably 0.02-1%, and more preferably 0.03-0.12%. In the present invention, the photobase generator preferably comprises 1,5,7-triazabicyclo [4.4.0] dec-5-ene (TBD), 1,8-diazabicyclo (5.4.0) undec-7-ene (DBU), or a phenylboronate type photobase generator, more preferably 1,5,7-triazabicyclo [4.4.0] dec-5-ene. In the present invention, the photobase generators of the phenylboronate type preferably include 1,5,7-triazabicyclo (4.4.0) -5-decene tetraphenylborate (TBD. HBPh 4) or 1,8-diazabicyclo (5.4.0) undec-7-ene tetraphenylborate (DBU. HBPh 4).
The self-repairing coating provided by the invention comprises 1-5% of corrosion inhibitor by mass percentage, preferably 2-4%, and more preferably 2.4-3.2%. In the present invention, the corrosion inhibitor is preferably an organic nitrogen heterocyclic corrosion inhibitor, and the organic nitrogen heterocyclic corrosion inhibitor preferably includes one or more of imidazole, acridine, quinoline and quinazoline, more preferably imidazole, acridine, quinoline or quinazoline, and even more preferably acridine or imidazole.
In the invention, the organic nitrogen heterocyclic corrosion inhibitor can effectively protect the metal base material and further prolong the anticorrosion effect.
The self-repairing coating provided by the invention comprises a prepolymer containing a D-A structure in balance by mass percentage. In the present invention, the prepolymer containing D-A structure preferably comprises a prepolymer having a structure represented by formula I:
in the present invention, n is any one of 2 to 30, and more preferably any one of 5 to 20.
The preparation method of the prepolymer with the structure shown in the formula I preferably comprises the following steps:
furfuryl acrylate and bismaleimide are dissolved in dimethyl sulfoxide (DMSO) to carry out reflux reaction, and a prepolymer with a structure shown in a formula I is obtained.
In the present invention, the dissolution preferably comprises the steps of:
dissolving furfuryl acrylate in dimethyl sulfoxide to obtain furfuryl acrylate solution;
and secondly, dissolving the bismaleimide into dimethyl sulfoxide to obtain a bismaleimide solution.
In the invention, the structural formula of the furfuryl acrylate is shown as a formula 3
In the present invention, the bismaleimide preferably has a structure represented by formula 4:
among them, n is preferably an integer of 2 to 30, more preferably an integer of 5 to 20. In an embodiment of the invention, n is specifically 10 or 20.
In the present invention, the molar ratio of furfuryl acrylate to bismaleimide is preferably 2 to 2.1.
After obtaining the furfuryl acrylate ester solution and the bismaleimide solution, the present invention preferably adds the furfuryl acrylate ester solution dropwise to the bismaleimide solution. In the present invention, the dropping rate is preferably 50 to 80 drops/min, more preferably 60 to 70 drops/min.
In the present invention, the temperature of the reflux reaction is preferably 100 to 150 ℃, more preferably 110 to 130 ℃; the time for the reflux reaction is preferably 8 to 12 hours, and more preferably 9 to 10 hours. In the present invention, the time of the reflux reaction is calculated from the completion of the dropwise addition.
The invention forms the D-A structure in the reflux reaction process.
In the present invention, the chemical reaction occurring during the reflux reaction has the equation shown in formula a:
in the present invention, it is preferable that the reflux reaction further comprises: and (4) carrying out rotary evaporation on the system after the reflux reaction. The solvent in the system is removed by rotary evaporation, and the rotary evaporation has no special requirement as long as the solvent in the system can be removed.
In the invention, click chemical reaction can occur between polyfunctional mercaptan and prepolymer containing D-A structure, taking trifunctional mercaptan as polyfunctional mercaptan and taking prepolymer with structure shown in formula I as prepolymer containing D-A structure as an example, the chemical reaction equation for forming crosslinked network polymer coating by click chemistry is shown in formula b:
the self-repairing coating provided by the invention forms a coating through a click chemical reaction, and when the coating is damaged, the self-repairing coating can be self-repaired through the click chemical reaction again. In the present invention, the energy required for the click chemistry reaction is provided by sunlight or ultraviolet light. In the present invention, the photosensitive resin system is subjected to a certain intensity (more than 10 mW/cm) 2 ) The click chemical reaction occurs upon irradiation of sunlight or ultraviolet rays.
The self-repairing coating provided by the invention can form an anticorrosive coating under natural illumination on the premise of no human intervention, and can be self-repaired under the sun illumination after the anticorrosive coating is damaged, so that an intelligent self-repairing effect is realized; and the anticorrosive coating formed by the self-repairing coating provided by the invention has excellent anticorrosive performance.
In the present invention, the preparation method of the self-repairing coating preferably includes the following steps:
and mixing the coupling agent modified carbon nano tube, polyfunctional group mercaptan, photoinitiator, photosensitizer, photobase generator, corrosion inhibitor and prepolymer containing D-A structure to obtain the self-repairing coating.
In the present invention, the mixing preferably comprises the steps of:
thirdly mixing the prepolymer containing the D-A structure and polyfunctional group mercaptan to obtain a resin mixture;
fourthly, mixing the resin mixture, the photoinitiator, the photosensitizer, the photobase generator and the corrosion inhibitor to obtain a photosensitive resin system;
and fifthly, mixing the photosensitive resin system and the coupling agent modified carbon nano tube to obtain the coating.
The method comprises the step of carrying out third mixing on a prepolymer containing a D-A structure and polyfunctional group mercaptan to obtain a resin mixture. In the present invention, the third mixing is preferably performed under stirring, and the stirring is not particularly limited in the present invention as long as the third mixing can be uniformly mixed.
After obtaining the resin mixture, the photoinitiator, the photosensitizer, the photobase generator and the corrosion inhibitor are mixed for the fourth time to obtain the photosensitive resin system. In the present invention, the fourth mixing is preferably performed under stirring, and the stirring is not particularly limited as long as the mixing can be performed uniformly. In the present invention, the fourth mixing is preferably performed under light-shielding conditions. The invention has no special requirement on the light-proof mode and can be realized by adopting a conventional mode in the field. The fourth mixing is carried out under the condition of avoiding light, so that the prepolymer containing the D-A structure and the polyfunctional group mercaptan are prevented from generating click chemical reaction.
After the photosensitive resin system is obtained, the photosensitive resin system and the coupling agent modified carbon nano tube are mixed for the fifth time to obtain the coating. In the present invention, the fifth mixing is preferably performed under stirring, and the stirring is not particularly limited in the present invention as long as the mixing can be performed uniformly. In the present invention, the fifth mixing is preferably performed under light-shielding conditions. The fifth mixing is carried out under the condition of keeping out of the sun, so that the prepolymer containing the D-A structure and the polyfunctional group mercaptan are prevented from generating click chemical reaction.
The invention also provides application of the self-repairing coating in the technical scheme in an anticorrosive coating. In the present invention, the preparation of the high-efficiency anticorrosive coating preferably comprises the steps of:
and (3) spraying the self-repairing coating on the surface of the substrate, and then carrying out photocuring to obtain the high-efficiency anticorrosive coating.
In the present invention, the substrate is preferably a metal; the metal preferably comprises iron sheet, carbon steel, tinplate, copper-clad steel, stainless steel or stainless steel-clad steel, more preferably iron sheet or tinplate.
In the present invention, the spraying is preferably spraying or blade coating, more preferably spraying. In the present invention, when the coating mode is spray coating, the distance from the nozzle of the spray gun for spray coating to the surface of the substrate is preferably 13 to 17cm, more preferably 15cm; the number of spraying is preferably 2 to 4, more preferably 3.
In the present invention, the wavelength of the light for photocuring is preferably 365 to 400nm, more preferably 365nm or 400nm; the light intensity of the light for photocuring is preferably 23-27 mW/cm 2 More preferably 25mW/cm 2 (ii) a The time for the photocuring irradiation is preferably 5 to 15min, and more preferably 10 to 13min. In the present invention, the light source for photocuring preferably includes an LED ultraviolet lamp or sunlight, more preferably sunlight.
In order to further illustrate the present invention, the following embodiments are described in detail, but they should not be construed as limiting the scope of the present invention.
Example 1
20g (0.042 mol) of a compound represented by the formula
Dissolving bismaleimide into 30mL DMSO to obtain bismaleimide solution; dissolving 12.9g (0.084 mol) furfuryl acrylate in 20mL DMSO to obtain furfuryl acrylate solution; dripping the furfuryl alcohol acrylate solution into the bismaleimide solution at a dripping rate of 60 drops/min, ensuring the temperature of the mixed solution to be 100 ℃ in the dripping process, and performing reflux reaction at 100 ℃ for 12 hours after finishing dripping; performing rotary evaporation after reflux reaction to obtain a prepolymer containing a D-A structure;
dispersing 5g of carbon nanotubes with average inner diameter of 4nm, average outer diameter of 10nm and average length of 11 microns in 100mL of toluene to obtain carbon nanotube dispersion liquid; 10mL of silane coupling agent KH570 is dripped into the carbon nano light dispersion liquid, and then grafting reaction (with stirring) is carried out for 12h; filtering to remove the solvent after the grafting reaction to obtain a coupling agent modified carbon nano tube;
mixing 15g of prepolymer containing a D-A structure and 10g of trifunctional thiol to obtain a resin mixture;
uniformly stirring the resin mixture, 0.01g of ITX photosensitizer, 0.01g of photoinitiator 2959, 0.01g of photobase generator TBD and 1g of imidazole under a dark condition to obtain a photosensitive resin composite system;
5g of the coupling agent modified carbon nanotube and photosensitive resin complex system are mixed and stirred uniformly under the condition of keeping out of the sun, and the self-repairing coating is obtained.
Example 2
20g (0.06 mol) of a compound of the formula
Dissolving bismaleimide into 30mL DMSO to obtain bismaleimide solution; dissolving 18.24g (0.12 mol) of furfuryl acrylate in 20mL of DMSO to obtain a furfuryl acrylate solution; dripping the furfuryl acrylate solution into the bismaleimide solution at a dripping speed of 70 drops/min, ensuring the temperature of the mixed solution to be 110 ℃ in the dripping process, and performing reflux reaction for 8 hours at 110 ℃ after finishing dripping; performing rotary evaporation after reflux reaction to obtain a prepolymer containing a D-A structure;
dispersing 10g of carbon nanotubes with average inner diameter of 4nm, average outer diameter of 10nm and average length of 11 microns in 100mL of toluene to obtain carbon nanotube dispersion liquid; dripping 12mL of silane coupling agent KH570 into the carbon nano light dispersion liquid, and then carrying out grafting reaction (with stirring) for 12h; filtering to remove the solvent after the grafting reaction to obtain a coupling agent modified carbon nano tube;
mixing 15g of prepolymer containing a D-A structure and 15g of trifunctional thiol to obtain a resin mixture;
uniformly stirring the resin mixture, 0.05g of ITX photosensitizer, 0.05g of photoinitiator 1173, 0.05g of photobase generator TBD and 1g of acridine under a dark condition to obtain a photosensitive resin composite system;
and (3) mixing and stirring 10g of the coupling agent modified carbon nanotube and photosensitive resin complex system uniformly under the condition of keeping out of the sun to obtain the self-repairing coating.
Comparative example 1
The prepolymer containing the D-A structure in example 1 was used as a self-healing coating.
Comparative example 2
A self-healing coating was prepared by mixing 15g of the prepolymer containing the D-A structure of example 1 with 1g of imidazole.
Test example
The self-repairing coatings of the embodiment 1 and the comparative examples 1-2 are respectively sprayed on the surface of a galvanized iron plate (tinplate); when spraying, the distance between the spray gun nozzle and the surface of the substrate is 15cm, 5s of spraying is carried out each time, and the spraying is repeated for 3 times;
spraying on an LED ultraviolet lamp with the wavelength of 365nm (the light intensity is 25 mW/cm) 2 ) Irradiating for 10min for photocuring to obtain an anticorrosive coating;
drying the test plate with the anticorrosive coating, and scratching the surface of the anticorrosive coating by using a special tool, wherein the scratch penetrates through the coating to the substrate and is vertical cross;
and (3) performing self-repairing on the scratched part by utilizing laser irradiation with the wavelength of 808nm for 10min, and performing a salt spray test for 336h in a salt spray box at 35 ℃ after the repairing is completed.
Scanning electron microscope observation is carried out on the scratch positions before and after the self-repairing of the coating of the spraying example 1 to obtain an SEM image, and as shown in FIG. 1, a is the SEM image before the self-repairing, and b is the SEM image after the self-repairing. As can be seen from fig. 1, the coating at the place where the scratch is scratched by light completes self-repairing.
The test plate after the salt spray test was rinsed with warm water to remove the test solution residue on the surface, and the physical pattern of the surface of the scratched portion of the rinsed test plate is shown in FIG. 2. As can be seen from FIG. 2, the anticorrosive coating formed by the self-repairing coating provided by the invention can be self-repaired after being damaged, and cannot be corroded.
The self-repairing coating prepared in the example 2 is tested according to the method, and the difference is that the distance between the spray nozzle of the spray gun and the surface of the substrate is 10cm during spraying; spraying the paint on an LED ultraviolet lamp (light intensity is 20 mW/cm) with the wavelength of 400nm 2 ) And irradiating for 5min for photocuring to obtain the anticorrosive coating. The self-repairing performance and the corrosion prevention performance of the self-repairing coating prepared in the example 2 are consistent with those of the example 1.
Although the present invention has been described in detail with reference to the above embodiments, it is only a part of the embodiments of the present invention, not all of the embodiments, and other embodiments can be obtained without inventive step according to the embodiments, and the embodiments are within the scope of the present invention.
Claims (10)
1. The self-repairing coating comprises the following components in percentage by mass:
2. the self-repairing coating of claim 1, wherein the prepolymer containing a D-A structure comprises a prepolymer having a structure represented by formula I:
3. the self-repairing coating of claim 2, wherein the preparation method of the prepolymer with the structure shown in the formula I comprises the following steps:
dissolving furfuryl acrylate and bismaleimide in dimethyl sulfoxide, and carrying out reflux reaction to obtain a prepolymer with a structure shown in a formula I.
4. The self-repairing coating of claim 3, wherein the molar ratio of furfuryl acrylate to bismaleimide is 2-2.1;
the temperature of the reflux reaction is 100-150 ℃, and the time of the reflux reaction is 8-12 h.
5. The self-repairing coating of claim 1, wherein the preparation method of the coupling agent modified carbon nanotube comprises the following steps:
mixing the carbon nano tube, a silane coupling agent and an organic solvent, and carrying out grafting reaction to obtain the coupling agent modified carbon nano tube.
6. The self-repairing coating of claim 5, wherein the mass ratio of the carbon nanotubes to the silane coupling agent is 5-10 g: 8-12 mL;
the mass of the carbon nano tube and the volume ratio of the organic solvent are 5-10 g: 90-110 mL.
7. The self-healing coating of claim 1, wherein the multifunctional thiol comprises a tri-functional thiol and/or a tetra-functional thiol.
8. The self-healing coating of claim 1, wherein the photoinitiator comprises 2-hydroxy-4- (2-hydroxyethoxy) -2-methylpropiophenone, 1-hydroxycyclohexylphenylketone, phenylbis (2,4,6-trimethylbenzoyl) phosphine oxide, 2-hydroxy-2-methyl-1-phenylpropanone, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, or 2-methyl-2- (4-morpholinyl) -1- [4- (methylthio) phenyl ] -1-propanone;
the photosensitizer comprises 2-isopropylthioxanthone or 2,4,6-trimethylbenzoyl-diphenylphosphine oxide;
the photobase generator comprises 1,5,7-triazabicyclo [4.4.0] dec-5-ene, 1,8-diazabicyclo (5.4.0) undec-7-ene or phenylboronate photobase generators.
9. The self-repairing coating of claim 1, wherein the corrosion inhibitor is an organic nitrogen heterocyclic corrosion inhibitor.
10. Use of the self-healing coating of any one of claims 1 to 9 in an anti-corrosive coating.
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