CN115418126B - Self-repairing coating and application thereof - Google Patents
Self-repairing coating and application thereof Download PDFInfo
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- CN115418126B CN115418126B CN202211149445.7A CN202211149445A CN115418126B CN 115418126 B CN115418126 B CN 115418126B CN 202211149445 A CN202211149445 A CN 202211149445A CN 115418126 B CN115418126 B CN 115418126B
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- 238000000576 coating method Methods 0.000 title claims abstract description 82
- 239000011248 coating agent Substances 0.000 title claims abstract description 77
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 48
- 238000006243 chemical reaction Methods 0.000 claims abstract description 45
- 238000005260 corrosion Methods 0.000 claims abstract description 36
- 239000007822 coupling agent Substances 0.000 claims abstract description 23
- 230000007797 corrosion Effects 0.000 claims abstract description 19
- 239000003112 inhibitor Substances 0.000 claims abstract description 13
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000003504 photosensitizing agent Substances 0.000 claims abstract description 11
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 claims description 45
- 238000002156 mixing Methods 0.000 claims description 25
- 239000002041 carbon nanotube Substances 0.000 claims description 23
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 23
- 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
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 15
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 14
- 239000003960 organic solvent Substances 0.000 claims description 9
- 238000002360 preparation method Methods 0.000 claims description 7
- 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
- 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 6
- 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
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 claims description 3
- 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 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
- 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
- MDCWDBMBZLORER-UHFFFAOYSA-N triphenyl borate Chemical compound C=1C=CC=CC=1OB(OC=1C=CC=CC=1)OC1=CC=CC=C1 MDCWDBMBZLORER-UHFFFAOYSA-N 0.000 claims description 3
- KGGBUGLHJUGXEF-UHFFFAOYSA-N [6-hydroxy-4-(2-hydroxyethoxy)-6-methylcyclohexa-2,4-dien-1-yl]-phenylmethanone Chemical compound OC1(C(C(=O)C2=CC=CC=C2)C=CC(=C1)OCCO)C KGGBUGLHJUGXEF-UHFFFAOYSA-N 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 10
- 230000008569 process Effects 0.000 abstract description 6
- 239000003795 chemical substances by application Substances 0.000 abstract description 4
- 239000002131 composite material Substances 0.000 abstract description 2
- 238000005698 Diels-Alder reaction Methods 0.000 description 22
- 229920005989 resin Polymers 0.000 description 17
- 239000011347 resin Substances 0.000 description 17
- 150000003573 thiols Chemical class 0.000 description 17
- 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 15
- 238000005507 spraying Methods 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
- 239000000203 mixture 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
- 239000007921 spray Substances 0.000 description 8
- 239000003973 paint Substances 0.000 description 7
- 238000000016 photochemical curing Methods 0.000 description 7
- 239000000758 substrate Substances 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
- 239000007788 liquid Substances 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
- 239000000805 composite resin Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 230000008439 repair process Effects 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 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 description 3
- -1 2-hydroxyethoxy Chemical group 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 238000002390 rotary evaporation Methods 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
- 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 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005286 illumination Methods 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
- 239000010935 stainless steel Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 238000010025 steaming Methods 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 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 description 1
- 229910000975 Carbon steel Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 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
- 239000011247 coating layer Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000005536 corrosion prevention Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 description 1
- 238000004626 scanning electron microscopy Methods 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
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
- 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
-
- 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 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. According to the invention, the coupling agent modified carbon nano tube can be uniformly dispersed in the coating, and is used as a high-efficiency photo-thermal conversion agent to convert solar energy in the environment into heat energy to provide energy for self-repairing, so that the self-repairing of the coating is realized, and no additional mode is needed to provide energy for self-repairing. 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, construction, structural bridges and the like by virtue of excellent mechanical and electrical properties, but the metal structure is irrecoverably damaged by the existence of metal corrosion, great potential safety hazard is generated, and meanwhile, huge economic loss is generated, so that the corrosion prevention problem of the metal is urgent and critical.
At present, a mode of spraying an anti-corrosion coating on the surface of metal is mainly adopted to reduce metal corrosion; the common anti-corrosion paint is a high polymer paint, and a high polymer coating film is formed on the surface of the metal by using the high polymer paint to isolate the metal from corrosion factors in the environment, so that an effective anti-corrosion effect is achieved. However, the method has poor weather resistance, is difficult to repair by self after being scratched and scratched by the outside, and the metal device can be re-exposed to the corrosive environment, so that the anti-corrosion effect is greatly reduced.
In order to realize self-repairing of the anti-corrosion coating, a series of high-molecular anti-corrosion coatings with self-repairing effect appear in recent years, wherein the high-molecular anti-corrosion coating with a D-A (Diels-Alder) repairing structure has outstanding comprehensive performance. However, the existing polymer anticorrosive paint with the D-A repair structure needs to be repaired at a higher temperature of 100-120 ℃, so that the energy required for repair is required to be provided by artificial 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 automatically repair the coating after being damaged under the condition of sunlight illumination, thereby realizing the function of completely self-repairing the anti-corrosion coating.
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:
furfuryl alcohol acrylate and bismaleimide are dissolved in dimethyl sulfoxide to carry out reflux reaction, and a prepolymer with the structure shown in the formula I is obtained.
Preferably, the molar ratio of the furfuryl acrylate to the bismaleimide is 2-2.1:1;
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 nano tube comprises the following steps:
and mixing the carbon nano tube, the silane coupling agent and the organic solvent, and performing a grafting reaction to obtain the coupling agent modified carbon nano tube.
Preferably, the mass ratio of the carbon nano tube to the silane coupling agent is 5-10 g: 8-12 mL;
the mass ratio of the carbon nano tube to the organic solvent is 5-10 g: 90-110 mL.
Preferably, the polyfunctional thiol comprises a trifunctional thiol and/or a tetrafunctional thiol.
Preferably, the photoinitiator comprises 2-hydroxy-4- (2-hydroxyethoxy) -2-methylbenzophenone, 1-hydroxycyclohexylphenyl ketone, 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-isopropyl thioxanthone or 2,4, 6-trimethyl benzoyl-diphenyl phosphine 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 phenylborate photobase generator.
Preferably, the corrosion inhibitor is an organic nitrogen heterocyclic corrosion inhibitor.
The invention also provides application of the self-repairing coating 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 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. According to the invention, the coupling agent modified carbon nano tube can be uniformly dispersed in the coating, and is used as a high-efficiency photo-thermal conversion agent to convert solar energy in the environment into heat energy to provide energy for self-repairing, so that the self-repairing of the coating is realized, and no additional energy is provided for self-repairing. 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 a scratch before and after self-repair of a coating of spray example 1, where a is an SEM image before self-repair and b is an SEM image after self-repair;
fig. 2 is a physical diagram of the coating materials of example 1 and comparative examples 1 to 2 after the anticorrosive coating layer was formed and the salt spray test was performed.
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 tubes, preferably 10-24.5%, and more preferably 16.1-24.3% by mass. In the invention, the preparation method of the coupling agent modified carbon nano tube comprises the following steps:
and mixing the carbon nano tube, the silane coupling agent and the organic solvent, and performing a grafting reaction to obtain the coupling agent modified carbon nano tube.
In the present invention, the mixing preferably includes the steps of:
dispersing carbon nano tubes in an organic solvent to obtain a carbon nano tube dispersion liquid;
a silane coupling agent is added dropwise to the carbon nanotube dispersion.
In the present invention, the average inner diameter of the carbon nanotubes is preferably 3 to 5nm, more preferably 4nm; the average outer diameter of the carbon nanotubes is preferably 8 to 15nm, more preferably 10 to 12nm; the average length of the carbon nanotubes is preferably 3 to 12. Mu.m, more preferably 6 to 11. Mu.m. In the present invention, the organic solvent preferably includes toluene, chloroform or methylene chloride, more preferably toluene. In the present invention, the silane coupling agent preferably includes a silane coupling agent KH570. In the invention, the mass ratio of the carbon nano tube to the silane coupling agent is preferably 5-10 g:8 to 12mL, more preferably 5 to 10g: 10-12 mL; in the embodiment of the invention, the volume ratio of the mass of the carbon nano tube to the silane coupling agent is 5g:10mL or 10g:12mL. In the present invention, the mass ratio of the carbon nanotubes to the organic solvent is preferably 5 to 10g:90 to 110mL, more preferably 5 to 10g:100mL, in the examples of the present invention, the mass of the carbon nanotubes and the volume ratio of the organic solvent were 5g:100mL or 10g:100mL.
In the present invention, the dispersion is preferably performed under stirring; the invention has no special requirements on the rotation speed and time of stirring, and can be uniformly mixed.
The invention has no special requirement on the dripping, so 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 of 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. The stirring is not particularly limited as long as the grafting reaction can be sufficiently performed.
In the present invention, the grafting reaction preferably further comprises: and (3) carrying out solid-liquid separation on the system after the grafting reaction. In the present invention, the solid-liquid separation is preferably filtration. The invention has no special requirement on the filtration, and can be realized 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, avoids the problem of agglomeration of the carbon nano tube in an organic phase, can be uniformly dispersed in a self-repairing coating, and improves the self-repairing efficiency. In the invention, the coupling agent modified carbon nano tube is used as a high-efficiency photo-thermal conversion agent, solar energy in the environment can be converted into heat energy, the temperature of a system is increased under the condition of no need of human intervention, and self-repairing of the coating is realized by providing energy for self-repairing. Meanwhile, double bonds (from silane coupling agent) on the surface of the coupling agent modified carbon nano tube can generate photopolymerization click chemical reaction with double bonds of resin, so that the stability of the coating is improved.
The self-repairing coating provided by the invention comprises 30-40% of polyfunctional mercaptan, preferably 32.2-36.5% by mass. In the present invention, the polyfunctional thiol preferably includes a trifunctional thiol and/or a tetrafunctional thiol, more preferably a trifunctional thiol or a tetrafunctional thiol, 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 a structure represented by formula 2:
in the present invention, a light-striking reaction between the multifunctional thiol and the prepolymer having a D-A structure occurs to achieve self-repairing.
The self-repairing coating provided by the invention comprises 0.01-3% of photoinitiator, preferably 0.02-1%, and more preferably 0.03-0.12% by mass. In the present invention, the photoinitiator preferably includes 2-hydroxy-4- (2-hydroxyethoxy) -2-methylpropenone (photoinitiator 2959), 1-hydroxycyclohexylphenyl ketone, 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-morpholino) -1- [4- (methylthio) phenyl ] -1-propanone, more preferably photoinitiator 2959 or photoinitiator 1173.
The self-repairing coating provided by the invention comprises 0.01-3% of photosensitizer, preferably 0.02-1%, more preferably 0.03-0.12% by mass. In the present invention, the photosensitizer preferably includes 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 photo-alkaline agent, preferably 0.02-1%, more preferably 0.03-0.12% by mass. In the present invention, the photobase generator preferably includes 1,5, 7-triazabicyclo [4.4.0] dec-5-ene (TBD), 1, 8-diazabicyclo (5.4.0) undec-7-ene (DBU), or phenylboronate photobase generator, more preferably 1,5, 7-triazabicyclo [4.4.0] dec-5-ene. In the present invention, the phenylborate photobase generator preferably includes 1,5, 7-triazidine bicyclo (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, preferably 2-4%, and more preferably 2.4-3.2% by mass. In the present invention, the corrosion inhibitor is preferably an organic nitrogen heterocyclic corrosion inhibitor, which preferably includes one or more of imidazole, acridine, quinoline, and quinazoline, more preferably imidazole, acridine, quinoline, or quinazoline, and still more preferably acridine or imidazole.
In the invention, the organic nitrogen heterocyclic corrosion inhibitor can effectively protect a metal substrate and further prolong the corrosion resistance.
The self-repairing coating provided by the invention comprises the balance of prepolymer containing a D-A structure in percentage by mass. In the present invention, the prepolymer having a D-A structure preferably comprises a prepolymer having a structure represented by formula I:
in the present invention, n is an integer of 2 to 30, more preferably an integer of 5 to 20.
In the process for producing the prepolymer having the structure represented by formula I of the present invention, it is preferable that the process comprises the steps of:
furfuryl alcohol acrylate and bismaleimide are dissolved in dimethyl sulfoxide (DMSO) to carry out reflux reaction, and a prepolymer with the structure shown in the formula I is obtained.
In the present invention, the dissolving preferably includes the steps of:
first dissolving furfuryl alcohol acrylate in dimethyl sulfoxide to obtain furfuryl alcohol acrylate solution;
and (3) dissolving the bismaleimide in dimethyl sulfoxide to obtain a bismaleimide solution.
In the invention, the structural formula of the furfuryl alcohol acrylate is shown as formula 3
In the present invention, the bismaleimide preferably has a structure represented by formula 4:
wherein n is preferably an integer of 2 to 30, more preferably an integer of 5 to 20. In an embodiment of the present invention, n is specifically 10 or 20.
In the present invention, the molar ratio of furfuryl acrylate to bismaleimide is preferably 2 to 2.1:1.
After the furfuryl alcohol acrylate solution and the bismaleimide solution are obtained, the furfuryl alcohol acrylate solution is preferably added dropwise to the bismaleimide solution in the present invention. In the present invention, the rate of the dropping 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 of the reflux reaction is preferably 8 to 12 hours, 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 a D-A structure in the reflux reaction process.
In the present invention, the equation of the chemical reaction occurring during the reflux reaction is shown in formula a:
in the present invention, the reflux reaction preferably further comprises: and (5) carrying out rotary steaming on the system after the reflux reaction. The solvent in the system is removed by rotary evaporation, and the method has no special requirement on the rotary evaporation, so long as the solvent in the system can be removed.
In the invention, click chemistry reaction occurs between the polyfunctional thiol and the prepolymer containing the D-A structure, three-functionality thiol is taken as the polyfunctional thiol, the prepolymer with the structure shown in the formula I is taken as the prepolymer containing the D-A structure, and a chemical reaction equation for forming the crosslinked network polymer coating by using click chemistry is shown as the formula b:
the self-repairing coating provided by the invention forms a coating through click chemical reaction, and the self-repairing coating can be repaired again through the click chemical reaction after the coating is damaged. In the present invention, the energy required for the click chemistry reaction is provided by sunlight or ultraviolet light. In the present invention, when the photosensitive resin system is subjected to a certain intensity (more than 10mW/cm 2 ) Click chemistry occurs upon exposure to sunlight or ultraviolet light.
The self-repairing coating provided by the invention can form an anti-corrosion coating through natural illumination on the premise of no human intervention, and can be subjected to self-repairing under sunlight after the anti-corrosion coating is damaged, so that an intelligent self-repairing effect is realized; and the anti-corrosion coating formed by the self-repairing coating provided by the invention has excellent anti-corrosion performance.
In the present invention, the preparation method of the self-repairing paint preferably comprises the following steps:
and mixing the coupling agent modified carbon nano tube, the polyfunctional mercaptan, the photoinitiator, the photosensitizer, the photobase generator, the corrosion inhibitor and the prepolymer containing the D-A structure to obtain the self-repairing coating.
In the present invention, the mixing preferably includes the steps of:
thirdly mixing the prepolymer containing the D-A structure with the polyfunctional mercaptan to obtain a resin mixture;
fourth 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 with the coupling agent modified carbon nano tube to obtain the coating.
The invention carries out third mixing on the prepolymer containing the D-A structure and the polyfunctional 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 as long as the mixing can be uniformly performed.
After the resin mixture is obtained, the resin mixture, the photoinitiator, the photosensitizer, the photobase generator and the corrosion inhibitor are subjected to fourth mixing 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 fourth mixing can be uniformly mixed. In the present invention, the fourth mixing is preferably performed under a dark condition. The invention has no special requirement on the light-shielding mode, and can be realized by adopting a conventional mode in the field. The invention carries out fourth mixing under the light-proof condition, and avoids click chemical reaction between the prepolymer containing the D-A structure and the polyfunctional mercaptan.
After the photosensitive resin system is obtained, the photosensitive resin system and the coupling agent modified carbon nano tube are subjected to fifth mixing to obtain the coating. In the present invention, the fifth mixing is preferably performed under stirring, and the stirring is not particularly limited as long as the fifth mixing can be uniformly mixed. In the present invention, the fifth mixing is preferably performed under a dark condition. The invention carries out fifth mixing under the light-proof condition, and avoids click chemistry reaction between the prepolymer containing the D-A structure and the polyfunctional mercaptan.
The invention also provides application of the self-repairing coating in an anticorrosive coating. In the present invention, the preparation of the high-efficiency anti-corrosion coating preferably comprises the following steps:
and spraying the self-repairing coating on the surface of the substrate, and then carrying out photo-curing to obtain the high-efficiency anti-corrosion 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 ladle steel, more preferably iron sheet or tinplate.
In the present invention, the spray coating is preferably spray coating or blade coating, more preferably spray coating. In the present invention, when the coating means 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 photo-curing is preferably 23-27 mW/cm 2 More preferably 25mW/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the The time of the photo-curing irradiation is preferably 5 to 15 minutes, more preferably 10 to 13 minutes. In the present invention, the light source for photo-curing preferably includes an LED ultraviolet lamp or sunlight, more preferably sunlight.
The technical solutions provided by the present invention are described in detail below in conjunction with examples for further illustrating the present invention, but they should not be construed as limiting the scope of the present invention.
Example 1
20g (0.042 mol) of formulaDissolving bismaleimide in 30mL DMSO to give a bismaleimide solution; 12.9g (0.084 mol) of furfuryl alcohol acrylate was dissolved in 20mL of DMSO to give a furfuryl alcohol acrylate solution; the furfuryl alcohol acrylate solution is dripped into the bismaleimide solution according to the dripping speed of 60 drops/min, the temperature of the mixed solution is ensured to be 100 ℃ in the dripping process, and the reflux reaction is carried out for 12 hours at 100 ℃ after the dripping is completed; rotary steaming after reflux reaction to obtain the final product containingPrepolymers of D-A structure;
5g of carbon nanotubes having an average inner diameter of 4nm, an average outer diameter of 10nm and an average length of 11 μm were dispersed in 100mL of toluene to obtain a carbon nanotube dispersion; after 10mL of silane coupling agent KH570 is added dropwise to the carbon nano-light dispersion, grafting reaction (with stirring) is carried out for 12 hours; filtering to remove solvent after grafting reaction to obtain a coupling agent modified carbon nano tube;
15g of a prepolymer having a D-A structure and 10g of a trifunctional thiol were mixed 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 the light-shielding condition to obtain a photosensitive resin composite system;
and (3) uniformly mixing and stirring 5g of the coupling agent modified carbon nano tube and the photosensitive resin composite system under the light-shielding condition to obtain the self-repairing coating.
Example 2
20g (0.06 mol) of the formulaDissolving bismaleimide in 30mL DMSO to give a bismaleimide solution; 18.24g (0.12 mol) of furfuryl alcohol acrylate was dissolved in 20mL of DMSO to give a furfuryl alcohol acrylate solution; the furfuryl alcohol acrylate solution is dripped into the bismaleimide solution according to the dripping speed of 70 drops/min, the temperature of the mixed solution is ensured to be 110 ℃ in the dripping process, and the reflux reaction is carried out for 8 hours at 110 ℃ after the dripping is completed; carrying out rotary evaporation after the reflux reaction to obtain a prepolymer containing a D-A structure;
10g of carbon nanotubes having an average inner diameter of 4nm, an average outer diameter of 10nm and an average length of 11 μm were dispersed in 100mL of toluene to obtain a carbon nanotube dispersion; 12mL of silane coupling agent KH570 is added dropwise to the carbon nano-optical dispersion liquid, and then grafting reaction (with stirring) is carried out for 12h; filtering to remove solvent after grafting reaction to obtain a coupling agent modified carbon nano tube;
mixing 15g of a prepolymer having a D-A structure with 15g of a 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 the light-shielding condition to obtain a photosensitive resin composite system;
and mixing and stirring 10g of the coupling agent modified carbon nano tube and the photosensitive resin composite system uniformly under the light-shielding condition to obtain the self-repairing coating.
Comparative example 1
The prepolymer containing D-A structure in example 1 was used as a self-repairing paint.
Comparative example 2
15g of the prepolymer having a D-A structure of example 1 and 1g of imidazole were mixed to obtain a self-repairing coating material.
Test case
Self-repairing coatings of example 1 and comparative examples 1 to 2 are respectively sprayed on the surface of a galvanized iron plate (tinplate); the distance between the spray gun nozzle and the surface of the substrate is 15cm during spraying, each spraying time is 5 seconds, and the spraying is repeated for 3 times;
after spraying, the coating was carried out on an LED ultraviolet lamp (light intensity: 25mW/cm 2 ) Irradiating for 10min to perform photo-curing to obtain an anti-corrosion coating;
drying the test board with the anti-corrosion coating, and then utilizing a professional prop to scratch the surface of the coating, wherein the scratch penetrates through the coating to the substrate, and the scratch is in a vertical cross shape;
self-repairing is carried out for 10min by utilizing a laser irradiation scratch position with the wavelength of 808nm, and a salt spray test is carried out for 336h in a salt spray box with the temperature of 35 ℃ after repairing is finished.
SEM images were obtained by scanning electron microscopy observation of scratches before and after self-repairing of the coating of example 1, as shown in fig. 1, wherein a is the SEM image before self-repairing and b is the SEM image after self-repairing. As can be seen from fig. 1, the paint at the scratch by light completes self-repair.
The test solution residue on the surface of the test panel after salt spray test was removed by washing with warm water, and a physical diagram of the surface of the scratch of the test panel after washing is shown in fig. 2. As can be seen from fig. 2, the anti-corrosive coating formed by the self-repairing coating provided by the invention can be self-repaired after being broken, and cannot be corroded.
According to the aboveThe self-repairing coating prepared in example 2 was tested by the method except that the distance from the spray gun nozzle to the substrate surface was 10cm during spraying; after spraying, the coating was carried out on an LED ultraviolet lamp (light intensity: 20mW/cm 2 ) And irradiating for 5min to perform photo-curing to obtain the anti-corrosion coating. The self-healing properties and corrosion resistance of the self-healing coating prepared in example 2 were consistent with example 1.
Although the foregoing embodiments have been described in some, but not all, embodiments of the invention, it should be understood that other embodiments may be devised in accordance with the present embodiments without departing from the spirit and scope of the invention.
Claims (6)
1. The self-repairing coating comprises the following components in percentage by mass:
the multifunctional mercaptan is trifunctional mercaptan and/or tetrafunctional mercaptan;
the prepolymer containing the D-A structure is a prepolymer with a structure shown in a formula I:
the preparation method of the prepolymer with the structure shown in the formula I comprises the following steps:
dissolving furfuryl alcohol acrylate and bismaleimide in dimethyl sulfoxide, and carrying out reflux reaction to obtain a prepolymer with a structure shown in a formula I;
the molar ratio of the furfuryl alcohol acrylate to the bismaleimide is 2-2.1:1;
the temperature of the reflux reaction is 100-150 ℃, and the time of the reflux reaction is 8-12 h.
2. The self-healing coating according to claim 1, wherein the preparation method of the coupling agent modified carbon nanotube comprises the following steps:
and mixing the carbon nano tube, the silane coupling agent and the organic solvent, and performing a grafting reaction to obtain the coupling agent modified carbon nano tube.
3. The self-repairing coating according to claim 2, wherein the mass ratio of the carbon nanotubes to the silane coupling agent is 5-10 g: 8-12 mL;
the mass ratio of the carbon nano tube to the organic solvent is 5-10 g: 90-110 mL.
4. The self-healing coating according to claim 1, wherein the photoinitiator comprises 2-hydroxy-4- (2-hydroxyethoxy) -2-methylbenzophenone, 1-hydroxycyclohexylphenyl ketone, phenylbis (2, 4, 6-trimethylbenzoyl) phosphine oxide, 2-hydroxy-2-methyl-1-phenylpropanone, 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide or 2-methyl-2- (4-morpholino) -1- [4- (methylthio) phenyl ] -1-propanone;
the photosensitizer comprises 2-isopropyl thioxanthone or 2,4, 6-trimethyl benzoyl-diphenyl phosphine 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 phenylborate photobase generator.
5. The self-healing coating according to claim 1, wherein the corrosion inhibitor is an organic nitrogen heterocyclic corrosion inhibitor.
6. Use of the self-healing coating according to any one of claims 1 to 5 in corrosion protection coatings.
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