CN116496676A - Self-early-warning coating based on charge transfer compound and preparation method thereof - Google Patents
Self-early-warning coating based on charge transfer compound and preparation method thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000000243 solution Substances 0.000 claims abstract description 40
- 239000002775 capsule Substances 0.000 claims abstract description 31
- 239000007864 aqueous solution Substances 0.000 claims abstract description 23
- 238000002156 mixing Methods 0.000 claims abstract description 21
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000011259 mixed solution Substances 0.000 claims abstract description 18
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims abstract description 16
- -1 polyethylene maleic anhydride copolymer Polymers 0.000 claims abstract description 16
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000003822 epoxy resin Substances 0.000 claims abstract description 14
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- 239000003094 microcapsule Substances 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 15
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 9
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- 230000001105 regulatory effect Effects 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- KBPLFHHGFOOTCA-UHFFFAOYSA-N caprylic alcohol Natural products CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 2
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- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims 3
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- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 4
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 4
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 4
- TXCDCPKCNAJMEE-UHFFFAOYSA-N dibenzofuran Chemical compound C1=CC=C2C3=CC=CC=C3OC2=C1 TXCDCPKCNAJMEE-UHFFFAOYSA-N 0.000 description 4
- IYYZUPMFVPLQIF-UHFFFAOYSA-N dibenzothiophene Chemical compound C1=CC=C2C3=CC=CC=C3SC2=C1 IYYZUPMFVPLQIF-UHFFFAOYSA-N 0.000 description 4
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
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- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 4
- 238000001338 self-assembly Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- FAAXSAZENACQBT-UHFFFAOYSA-N benzene-1,2,4,5-tetracarbonitrile Chemical compound N#CC1=CC(C#N)=C(C#N)C=C1C#N FAAXSAZENACQBT-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
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- VIXRAZODEODOJF-UHFFFAOYSA-N 1,2,4,5-tetrafluoro-3,6-diiodobenzene Chemical compound FC1=C(F)C(I)=C(F)C(F)=C1I VIXRAZODEODOJF-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000013590 bulk material Substances 0.000 description 1
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- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229920006334 epoxy coating Polymers 0.000 description 1
- 238000002189 fluorescence spectrum Methods 0.000 description 1
- 238000004770 highest occupied molecular orbital Methods 0.000 description 1
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- 229910052742 iron Inorganic materials 0.000 description 1
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- 238000000465 moulding Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000001151 other effect Effects 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
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- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- UGNWTBMOAKPKBL-UHFFFAOYSA-N tetrachloro-1,4-benzoquinone Chemical compound ClC1=C(Cl)C(=O)C(Cl)=C(Cl)C1=O UGNWTBMOAKPKBL-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
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
- 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
- C09D5/22—Luminous 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
- C09D7/63—Additives non-macromolecular organic
-
- 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
- C09D7/70—Additives characterised by shape, e.g. fibres, flakes or microspheres
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Manufacturing Of Micro-Capsules (AREA)
Abstract
The invention discloses a self-early-warning coating based on a charge transfer compound and a preparation method thereof, belonging to the field of coatings, wherein the self-early-warning coating based on the charge transfer compound comprises a capsule A, a capsule B and an epoxy resin coating, and the capsule A, the capsule B and the epoxy resin coating are mixed according to the mass ratio of 1:1:25; the capsule A is prepared by mixing an electron acceptor A compound solution, a mixed solution and a formaldehyde solution, filtering, washing and drying; the capsule B is prepared by mixing an electron donor D compound solution, a mixed solution and a formaldehyde solution, filtering, washing and drying; the mixed solution is prepared by mixing a mixed aqueous solution of urea, resorcinol and ammonium chloride with an aqueous solution of polyethylene maleic anhydride copolymer, and can be used for realizing that an electron acceptor A compound and an electron donor D compound are combined together to form a base (CTCs) which is used as a light and color response functional factor of a self-early-warning coating, has good stability and simple and stable structure, and is suitable for long-term storage.
Description
Technical Field
The invention relates to the field of coatings, in particular to a self-early warning coating based on a charge transfer compound and a preparation method thereof.
Background
Organic coatings have become one of the most commonly used methods in metal protection, and are applied to various fields such as corrosion protection, aerospace, precision instruments, new energy sources and the like, wherein epoxy resin coatings are most widely applied. However, under the external conditions of various chemical environments, ultraviolet rays, mechanical force, heat and the like, the epoxy resin coating is prone to aging and damage without sound, so that the protection performance is gradually lost, and finally, the metal material is invalid. Therefore, the Self-warning function (Self-warning) is given to the epoxy resin coating material, namely, the damage site is warned through light, color and other changes, people can be helped to find timely and take reasonable measures to carry out manual repair, and the Self-warning coating material is an effective way for prolonging the service life of the metal material, so that the development of the Self-warning coating material has important research significance and application value;
in recent years, the microcapsule is favored in the field of self-early warning coatings due to the good chemical stability, mechanical property, loading capacity and intelligence of environmental response, and the basic principle of the microcapsule applied in the field of self-early warning coatings is that light and color early warning factors are packaged in a microcapsule container and emitted under certain conditions, so that the early warning function is exerted;
at present, light and color early warning functional factors developed based on microcapsule technology mainly comprise four types: 1) A dye or fluorescent molecule; 2) A catalytic reaction system; 3) A metal complexing indicator; 4) Aggregation Induced Emission (AIE), dye or fluorescent molecule has the same color or optical property inside and outside the microcapsule, especially when the introduction amount is high, the mutual interference between the damaged position of the coating and the material body is easy to cause the phenomenon of misjudgment, therefore, in the practical application process, an ultraviolet shielding protective layer is often required to be added on the surface of the microcapsule to prevent pseudo fluorescence feedback, but the processing of the microcapsule has certain challenges, the synthesis condition is harsh, and a universal synthesis method is difficult to form. The second type adopts colorless indicator molecules and other reagents or catalysts embedded in a bulk material to generate color change for early warning, but the reactions depend on a special catalytic reaction system, so that the application range is limited to a certain extent, the metal complexing indicator is fluorescent molecules with selective response to metal ions such as iron, aluminum and the like, the early warning mechanism is based on the fluorescence change effect between corrosion products and the indicator, the AIE fluorescent molecule self-warning coating is formed by packaging a solution dissolved with the AIE fluorescent molecules in a microcapsule, when the coating is damaged, the microcapsule releases the solution, and along with volatilization of the solvent and aggregation of the molecules, fluorescent early warning is emitted, and although the metal complexing indicator and the AIE have better early warning performance, the action mechanism shows slightly insufficient timeliness of early warning response;
based on the problems, the invention provides the thought of constructing the self-early warning coating by taking Charge Transfer Complexes (CTCs) as light and color response functional factors of the self-early warning coating, encapsulating the self-early warning coating in microcapsules and doping the self-early warning coating in an organic coating.
Disclosure of Invention
1. Technical problem to be solved
Aiming at the problems existing in the prior art, the invention aims to provide a self-early-warning coating based on a charge transfer compound and a preparation method thereof, which can be realized by adopting a common combination of an electron acceptor A compound and an electron donor D compound as a base (CTCs), has good stability as a light and color response functional factor of the self-early-warning coating, has a simple and stable structure, and is suitable for long-term storage.
2. Technical proposal
In order to solve the problems, the invention adopts the following technical scheme.
A self-early warning coating based on a charge transfer compound, the self-early warning coating comprises a capsule A, a capsule B and an epoxy resin coating, wherein the capsule A, the capsule B and the epoxy resin coating are mixed in a mass ratio of 1:1:25;
the capsule A is prepared by mixing an electron acceptor A compound solution, a mixed solution and a formaldehyde solution, filtering, washing and drying;
the capsule B is prepared by mixing an electron donor D compound solution, a mixed solution and a formaldehyde solution, filtering, washing and drying;
the mixed solution is prepared by mixing a mixed aqueous solution of urea, resorcinol and ammonium chloride with an aqueous solution of polyethylene maleic anhydride copolymer.
A preparation method of a self-early warning coating based on a charge transfer compound comprises the following steps:
s1, dissolving a compound: respectively dissolving an electron donor D compound and an electron acceptor A compound in toluene to respectively obtain an electron donor D compound solution and an electron acceptor A compound solution;
s2, preparing a solution: mixing urea, resorcinol and ammonium chloride to obtain a mixed aqueous solution, mixing the mixed aqueous solution with an aqueous solution of polyethylene maleic anhydride copolymer, stirring and uniformly mixing, regulating pH to obtain a mixed solution, and preserving heat at 40 ℃;
s3, preparing capsules: respectively adding the electron donor D compound solution and the electron acceptor A compound solution into the mixed solution, stirring, dropwise adding the formaldehyde solution, continuously stirring at 55 ℃, stopping heating after the reaction is finished, cooling to room temperature overnight, and respectively obtaining microcapsules for wrapping the electron donor D compound and the electron acceptor A compound through filtering, washing and drying;
s4, mixing the coating: the electron donor D compound and the microcapsules encapsulating the electron acceptor a compound are doped into an epoxy resin coating.
3. Advantageous effects
Compared with the prior art, the invention has the advantages that:
(1) The invention adopts the common combination of the electron acceptor A compound and the electron donor D compound as the base (CTCs), has good stability as the light and color response functional factors of the self-early-warning coating, and D, A belongs to organic micromolecules with wide sources, has simple and stable structure, is suitable for long-term storage, has obvious light and color changes, and most D, A molecules are colorless or pale, so that the CTCs can show abundant fluorescence spectra and even color changes which can be recognized by naked eyes after being generated, are packaged in microcapsules and doped into organic coatings to construct the self-early-warning coating, and when the coating is damaged, the microcapsules release solution, and the solvent volatilizes and the molecules gather, thereby giving out fluorescence early warning.
(2) According to the scheme, an electron donor D compound (500 mg) and an electron acceptor A compound (500 mg) are respectively dissolved in 60ml of toluene to respectively obtain an electron donor D compound solution and an electron acceptor A compound solution, the D/A self-assembly reaction molar ratio is not strictly required, and the detection step of the D/A mass ratio in the preparation process of the product can be saved.
(3) The CTCs of the scheme has adjustable light and color, and the implementation way is that the D/A molecular structure such as substituent groups, hetero atoms and the like are regulated, and the D/A composition and the component proportion in a multi-component assembly system are regulated.
(4) The reaction of the coating preparation is rapid, the D/A self-assembly belongs to a non-chemical reaction process, and stable CTCs can be formed in a few seconds to a few minutes.
Drawings
FIG. 1 is a block diagram of the components of a self-early warning coating based on a charge transfer complex;
FIG. 2 is a fluorescence plot of the components of a self-early warning coating based on a charge transfer complex;
FIG. 3 is a method flow diagram of a method for preparing a self-early warning coating based on a charge transfer complex.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention; it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments, and that all other embodiments obtained by persons of ordinary skill in the art without making creative efforts based on the embodiments in the present invention are within the protection scope of the present invention.
Examples:
referring to fig. 1-2, a self-early warning coating based on a charge transfer compound, the self-early warning coating comprises a capsule a, a capsule B and an epoxy resin coating, wherein the capsule a, the capsule B and the epoxy resin coating are mixed in a mass ratio of 1:1:25;
the capsule A is prepared by mixing an electron acceptor A compound solution, a mixed solution and a formaldehyde solution, filtering, washing and drying, wherein the electron acceptor A compound is 1,2,4, 5-tetracyanobenzene (CTNB), and four strong electron withdrawing groups cyano directly connected with benzene rings are contained in molecules to form a plane conjugated structure, and the electron nucleophilicity is 2.20eV, so that the capsule A has strong electron withdrawing characteristic;
the capsule B is prepared by mixing an electron donor D compound solution, a mixed solution and a formaldehyde solution, filtering, washing and drying, wherein the electron donor D compound is Carbazole (CARB), dibenzothiophene (DBZP) and Dibenzofuran (DBZF), the charge transfer compound is a molecular compound composed of an electron donor (D) and an electron acceptor (A), D, A generally takes an aromatic ring as a matrix, pi electrons in the D aromatic ring are aggregated, the HOMO energy level is higher, pi electrons of the A aromatic ring are delocalized, the LUMO energy level is lower, a D-A-D ordered CTCs structure is formed under the drive of the HOMO-LUMO transition, namely pi electron migration, the electron acceptor A compound and the electron donor D compound are combined together to form a base (CTCs) which is taken as a self-early warning coating light and color response functional factor, has good stability, D, A belongs to organic micromolecules with wide sources, and forms CARB-TCNB, DBZP-TCNB, DBZF-TCNB and the like, has simple and stable structure, is suitable for long-term storage, has obvious light and color change, and most D, A molecules are colorless or pale, and after CTCs are generated, the CTCs are packaged in microcapsules and doped into organic coatings to form self-early-warning coatings, when the coatings are damaged to cause the microcapsules to release solution, fluorescent early warning is emitted along with solvent volatilization and molecular aggregation, further, CTCs light and color are adjustable, firstly, benzene, naphthalene, anthracene, phenanthrene, one, fluorene and the like have pi conjugated structures and are commonly used as skeleton structures of D/A by adjusting D/A molecular structures such as substituent groups, heteroatoms and the like, for example, a represented by 1,2,4, 5-tetracyanobenzene, 1, 4-diiodotetrafluorobenzene, octafluoronaphthalene, and tetrachlorobenzoquinone, and D represented by naphthalene, anthracene, phenanthrene, and fluorene; secondly, the D/A composition and the component proportion in the multi-component assembly system are regulated, and through fluorescent images, the combination of different electron acceptors-donors can be truly realized, the change of fluorescence (even visible light) can be realized to realize the early warning function, and the light change of different combinations is different, namely, the light and tone control is carried out through the change of the electron donor-acceptor combination;
the mixed solution is prepared by mixing a mixed aqueous solution of urea, resorcinol and ammonium chloride with an aqueous solution of polyethylene maleic anhydride copolymer.
Referring to fig. 3, a self-warning coating based on a charge transfer complex and a preparation method thereof, the preparation method comprises the following steps:
s1, dissolving a compound: the electron donor D compound (500 mg) and the electron acceptor A compound (500 mg) are respectively dissolved in 60ml of toluene to respectively obtain an electron donor D compound solution and an electron acceptor A compound solution, the D/A self-assembly reaction molar ratio has no strict requirement, and the detection step of the D/A mass ratio in the preparation process of the product can be saved;
s2, preparing a solution: taking urea, resorcinol and ammonium chloride in a ratio of 10:1:1 into a mixed aqueous solution, wherein the concentration of urea in the mixed aqueous solution is 0.025g/ml, so that the molding of the polyethylene maleic anhydride copolymer can be promoted, and the mixed aqueous solution and the aqueous solution of the polyethylene maleic anhydride copolymer are mixed according to the volume ratio of 1-2: 1, wherein the polyethylene maleic anhydride copolymer is taken as a main body to construct a shell of the capsule, the mass concentration of the aqueous solution of the polyethylene maleic anhydride copolymer is 1.0-5.0wt%, the higher content of the polyethylene maleic anhydride copolymer is kept, so that the shell of the capsule is rapidly formed, the mixture is stirred and evenly mixed, the pH is regulated to 3.5 by 1mol NaOH solution, the mixed solution is obtained, the temperature is kept at 40 ℃, the polyethylene maleic anhydride copolymer is kept oily in an acidic environment, and the hardening moment is delayed;
s3, preparing capsules: firstly, respectively dripping 1-2 drops of n-octanol solution into the electron donor D compound solution and the electron acceptor A compound solution to reduce the surface tension of the solution, respectively adding 60ml of the electron donor D compound solution and the electron acceptor A compound solution into the mixed solution at 5-10 min, stirring, then dripping 40% of formaldehyde solution with the commercial mass concentration dropwise, dripping the formaldehyde solution with the formaldehyde concentration of 0.05-0.075 g/ml, continuing stirring at 55 ℃ for 4-5 h, stirring at 500rpm, stirring at medium speed for a long time, uniformly distributing polyethylene maleic anhydride copolymer, forming a shallow and uniform capsule structure outside D/A, stopping heating after the reaction, cooling to room temperature overnight, and respectively obtaining microcapsules for wrapping the electron donor D compound and the electron acceptor A compound after filtering, washing and drying, wherein the microcapsules have good stability, D, A belong to organic small molecules with wide sources, have simple and stable structures, and are suitable for long-term storage, and the water, the solvent and the acetone can be sequentially washed when the solvents are used for respective times;
s4, mixing the coating: the method comprises the steps of doping an electron donor D compound and a microcapsule wrapping an electron acceptor A compound into an epoxy resin coating, reacting rapidly, enabling D/A self-assembly to belong to a non-chemical reaction process, forming stable CTCs in a few seconds to a few minutes, and after the epoxy coating is damaged, releasing the electron donor D compound and the electron acceptor A compound through permeation and diffusion of a microcapsule film or film rupture or film degradation and other effects due to the change of chemical microenvironment, so that the electron donor D compound and the electron acceptor A compound react rapidly to generate fluorescence or color change, thereby obtaining the coating with a self-warning function after the coating is damaged.
The above description is only of the preferred embodiments of the present invention; the scope of the invention is not limited in this respect. Any person skilled in the art, within the technical scope of the present disclosure, may apply to the present invention, and the technical solution and the improvement thereof are all covered by the protection scope of the present invention.
Claims (10)
1. A self-early warning coating based on a charge transfer complex, characterized by: the self-warning coating comprises a capsule A, a capsule B and an epoxy resin coating, wherein the capsule A, the capsule B and the epoxy resin coating are mixed in a mass ratio of 1:1:25;
the capsule A is prepared by mixing an electron acceptor A compound solution, a mixed solution and a formaldehyde solution, filtering, washing and drying;
the capsule B is prepared by mixing an electron donor D compound solution, a mixed solution and a formaldehyde solution, filtering, washing and drying;
the mixed solution is prepared by mixing a mixed aqueous solution of urea, resorcinol and ammonium chloride with an aqueous solution of polyethylene maleic anhydride copolymer.
2. A preparation method of a self-early-warning coating based on a charge transfer compound is characterized by comprising the following steps of: a method for preparing a self-early warning coating based on a charge transfer complex as defined in claim 1, said method comprising the steps of:
s1, dissolving a compound: respectively dissolving an electron donor D compound and an electron acceptor A compound in toluene to respectively obtain an electron donor D compound solution and an electron acceptor A compound solution;
s2, preparing a solution: mixing urea, resorcinol and ammonium chloride to obtain a mixed aqueous solution, mixing the mixed aqueous solution with an aqueous solution of polyethylene maleic anhydride copolymer, stirring and uniformly mixing, regulating pH to obtain a mixed solution, and preserving heat at 40 ℃;
s3, preparing capsules: respectively adding the electron donor D compound solution and the electron acceptor A compound solution into the mixed solution, stirring, dropwise adding the formaldehyde solution, continuously stirring at 55 ℃, stopping heating after the reaction is finished, cooling to room temperature overnight, and respectively obtaining microcapsules for wrapping the electron donor D compound and the electron acceptor A compound through filtering, washing and drying;
s4, mixing the coating: the electron donor D compound and the microcapsules encapsulating the electron acceptor a compound are doped into an epoxy resin coating.
3. The method for preparing the self-early-warning coating based on the charge transfer compound according to claim 2, which is characterized by comprising the following steps: the step S2 of adjusting the pH is to adjust the pH to 3.5 by 1mol NaOH solution.
4. The method for preparing the self-early-warning coating based on the charge transfer compound according to claim 2, which is characterized by comprising the following steps: urea, resorcinol and ammonium chloride in step S2 are mixed in an amount of 10:1:1, and the concentration of urea in the mixed aqueous solution is 0.025g/ml.
5. The method for preparing the self-early-warning coating based on the charge transfer compound according to claim 2, which is characterized by comprising the following steps: the mass concentration of the aqueous solution of the polyethylene maleic anhydride copolymer in the step S2 is 1.0-5.0wt%.
6. The method for preparing the self-early-warning coating based on the charge transfer compound according to claim 2, which is characterized by comprising the following steps: in the step S2, the volume ratio of the mixed aqueous solution to the polyethylene maleic anhydride copolymer aqueous solution is 1-2: 1.
7. the method for preparing the self-early-warning coating based on the charge transfer compound according to claim 2, which is characterized by comprising the following steps: and in the step S3, 1-2 drops of n-octanol solution are firstly dripped into the electron donor D compound solution and the electron acceptor A compound solution.
8. The method for preparing the self-early-warning coating based on the charge transfer compound according to claim 2, which is characterized by comprising the following steps: in the step S3, stirring is continued for 4-5 hours at 55 ℃ and the stirring rotating speed is 500rpm.
9. The method for preparing the self-early-warning coating based on the charge transfer compound according to claim 2, which is characterized by comprising the following steps: in the step S3, washing is sequentially performed with a proper amount of water, acetone, and dichloromethane solvent, respectively.
10. The method for preparing the self-early-warning coating based on the charge transfer compound according to claim 2, which is characterized by comprising the following steps: the mass concentration of the formaldehyde solution in the step S3 is 40%, and the concentration of the formaldehyde is 0.05-0.075 g/ml after the formaldehyde solution is added dropwise.
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Citations (3)
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| CN109103435A (en) * | 2018-08-25 | 2018-12-28 | 安徽师范大学 | A kind of self-repairing microcapsule lithium ion battery electrode material and preparation method thereof, negative electrode of lithium ion battery and lithium ion battery |
| CN115897251A (en) * | 2022-10-16 | 2023-04-04 | 武汉纺织大学 | Photoinitiated microcapsule coating fabric with self-warning and self-repairing functions and preparation method thereof |
| CN116694196A (en) * | 2023-07-05 | 2023-09-05 | 北京科技大学 | Self-early-warning self-repairing integrated coating and preparation method thereof |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109103435A (en) * | 2018-08-25 | 2018-12-28 | 安徽师范大学 | A kind of self-repairing microcapsule lithium ion battery electrode material and preparation method thereof, negative electrode of lithium ion battery and lithium ion battery |
| CN115897251A (en) * | 2022-10-16 | 2023-04-04 | 武汉纺织大学 | Photoinitiated microcapsule coating fabric with self-warning and self-repairing functions and preparation method thereof |
| CN116694196A (en) * | 2023-07-05 | 2023-09-05 | 北京科技大学 | Self-early-warning self-repairing integrated coating and preparation method thereof |
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