Environment-friendly aggregation-induced emission enhancement super-hydrophobic anticorrosive coating and preparation method thereof

Abstract

The application adopts modified urea-formaldehyde resin microcapsules to coat the aggregation-induced emission enhanced fluorescent material, and prepares a series of environment-friendly aggregation-induced emission enhanced super-hydrophobic corrosion-resistant coatings. The coating has excellent hydrophobicity, temperature resistance, hardness, adhesion and corrosion resistance, and can simultaneously exhibit excellent stimulus response performance under multiple external stimuli. Under the action of pressure, the coating can change from red to dark red, and can restore the original fluorescent color under the conditions of solvent fumigation or heating to realize cyclic indication. With the increase of relative humidity in the air from 10% to 90%, the fluorescent intensity of the coating shows a downward trend, which can indicate the water absorption of the coating in time. In addition, the fumigation of HCl gas on the surface of the coating realizes the change of the coating from red to orange red, and the color changed coating can restore the original color under the condition of passing equal amount of ammonia gas.

Description

TECHNICAL FIELD

[0001] The present application relates to a super-hydrophobic anticorrosive coating, in particular to an environmentally friendly aggregation-induced emission super-hydrophobic anticorrosive coating and a preparation method thereof. BACKGROUND

[0002] Stimuli-responsive fluorescent materials are a class of intelligent materials that change their own color under external condition stimulation. Currently, they can be specifically divided into two categories: traditional stimuli-responsive materials and new aggregation-induced emission stimuli-responsive materials. Due to their variable color effect under light, electricity, heat, solvent, pressure, pH, humidity, etc., they can be applied in many fields such as anti-counterfeiting, pressure sensing, OLED, memory chip, etc., and are a promising intelligent material. Compared with traditional stimuli-responsive materials, aggregation-induced emission fluorescent materials can effectively overcome the aggregation-induced quenching effect, and therefore have more practical application prospects.

[0003] Through continuous exploration by scientists, aggregation-induced emission stimuli-responsive materials (AIE) and even aggregation-induced emission enhancement (AEE) materials have emerged in many cutting-edge fields. However, there are few industrial applications of the above-mentioned "intelligent" materials, especially in the field of coatings. Due to the relatively complex mechanism of aggregation-induced emission materials, which is easily affected by multiple factors, and the difficulty in automatically restoring the color after response, aggregation-induced emission stimuli-responsive coatings, especially environmentally friendly aggregation-induced emission enhancement super-hydrophobic anticorrosive coatings with high sensitivity, are extremely rare.

[0004] Currently, we have developed a series of stimuli-responsive aggregation-induced emission coatings (CN115505308B, CN116004060B). The core is to use urea-formaldehyde resin as the shell structure and aggregation-induced emission material as the core layer to prepare urea-formaldehyde resin microcapsules to protect AIE molecules and make them exhibit better color change effect. However, due to the shortcomings of urea-formaldehyde resin such as excessive formaldehyde release, poor water resistance, poor flexibility, and poor acid and alkali resistance, the use effect of AIE microcapsule color-changing materials is limited. Therefore, it is urgent to develop a modified urea-formaldehyde resin microcapsule to overcome the shortcomings of the original microcapsule. SUMMARY

[0005] The present application aims to provide an environmentally friendly aggregation-induced emission enhancement super-hydrophobic anticorrosive coating and a preparation method thereof. The coating has excellent pressure-induced color change, humidity-induced color change, and acid and alkali-induced color change performance. The above color change phenomena do not affect each other and are easy to distinguish, and can provide timely warning for external stimuli.

[0006] An environmentally friendly aggregation-induced emission enhancement super-hydrophobic anticorrosive coating, all in parts by weight, comprises the following components:

[0007] Film-forming resin 90-120 parts, hydrophobic micro-nano particles 2-8 parts, filler 40-50 parts, modified aggregation-induced emission enhancement urea-formaldehyde microcapsule 1-2 parts, wetting agent 1-1.5 parts, defoaming agent 0.8-1.2 parts, leveling agent 0.7-1.0 parts, anti-settling agent 0.8-1.4 parts, mildew-proof agent 0.8-1 part, anti-rust agent 5-8 parts, diluent 46-50 parts.

[0008] The environmentally friendly aggregation-induced emission enhancement super-hydrophobic anti-corrosion paint according to the present application, wherein the film-forming resin comprises fluorocarbon resin or silicone resin.

[0009] The environmentally friendly aggregation-induced emission enhancement super-hydrophobic anti-corrosion paint according to the present application, wherein the hydrophobic micro-nano particles comprise two or more of hydrophobic titanium dioxide, diamond, carbon nanotube, silicon dioxide, silicon powder and graphite with a particle size of 10 nm-10 μm.

[0010] The environmentally friendly aggregation-induced emission enhancement super-hydrophobic anti-corrosion paint according to the present application, wherein the filler comprises two or more of mica powder, barium sulfate, calcium carbonate, talc, attapulgite, kaolin, quartz powder, aluminum hydroxide, diatomite and montmorillonite.

[0011] The environmentally friendly aggregation-induced emission enhancement super-hydrophobic anti-corrosion paint according to the present application, wherein the modified aggregation-induced emission enhancement urea-formaldehyde microcapsule comprises an aggregation-induced emission enhancement fluorescent material as a core material structure and a modified urea-formaldehyde resin as a shell material structure.

[0012] The core material structure comprises the following AEE fluorescent molecules, the structure is as shown below, and the preparation method of the AEE fluorescent molecules is described in detail in the patent (ZL202310635730.8).

[0013]

[0014] The environmentally friendly aggregation-induced emission enhancement super-hydrophobic anti-corrosion paint according to the present application, wherein the wetting agent is a polyacrylic acid copolymer potassium salt.

[0015] The environmentally friendly aggregation-induced emission enhancement super-hydrophobic anti-corrosion paint according to the present application, wherein the defoaming agent is one or more of silicone defoaming agent, polyether defoaming agent or polyether modified silicone defoaming agent.

[0016] The environmentally friendly aggregation-induced emission enhancement super-hydrophobic anti-corrosion paint according to the present application, wherein the leveling agent is one or more of silicone modified polysiloxane or polyether siloxane.

[0017] The environmentally friendly aggregation-induced emission enhancement super-hydrophobic anti-corrosion paint according to the present application, wherein the anti-settling agent is organic bentonite.

[0018] The environment-friendly aggregation-induced emission enhancement super-hydrophobic anti-corrosion coating according to the present application, wherein the antifungal agent is one or more of phenolic compounds, sulfur-containing organic compounds or nitrogen-containing organic compounds.

[0019] The environment-friendly aggregation-induced emission enhancement super-hydrophobic anti-corrosion coating according to the present application, wherein the antirust agent is one or more of aluminum tripolyphosphate or zinc phosphate.

[0020] The environment-friendly aggregation-induced emission enhancement super-hydrophobic anti-corrosion coating according to the present application, wherein the diluent is one or more of cyclohexanone, n-butanol, ethylene glycol butyl ether or propylene glycol methyl ether.

[0021] The environment-friendly aggregation-induced emission enhancement super-hydrophobic anti-corrosion coating according to the present application, wherein the preparation method of the modified aggregation-induced emission enhancement urea-formaldehyde microcapsule comprises the following steps:

[0022] (1) A certain amount of sodium dodecyl benzene sulfonate, sodium lignosulfonate and deionized water are added into a 250 mL three-necked flask, and stirred for 0.5 h to fully mix and dissolve. A certain amount of urea, polyhydric alcohol ether and a small amount of melamine are slowly added into the above mixed solution, and the pH is adjusted to 3-5 with dilute hydrochloric acid. After stirring for 2 h, it is ready for use.

[0023] (2) The AEE solid is dissolved in a small amount of toluene, and high-speed dispersion is performed to fully dissolve, to form a core material dispersion liquid;

[0024] (3) The core material dispersion liquid is added into the mixed solution in step 1, and stirred at 10000-15000 r / min for 20-30 min by using a high-speed shearing emulsifier. The emulsified mixed liquid is transferred into a three-necked flask, and a certain amount of formaldehyde solution with a mass fraction of 37% is added drop by drop. The reaction is carried out at 50-80°C for 4-8 h. After cooling to room temperature, the solution is adjusted to neutral with sodium hydroxide solution, to obtain a modified aggregation-induced emission enhancement urea-formaldehyde microcapsule suspension. After cooling to room temperature, washing and suction filtration, the modified aggregation-induced emission enhancement urea-formaldehyde microcapsule A-A, B-B and C-C prepared are placed in a vacuum drying oven and dried at 40°C for 48 h, and then stored in a desiccator for standby use.

[0025] The environment-friendly aggregation-induced emission enhancement super-hydrophobic anti-corrosion coating according to the present application, wherein the polyhydric alcohol ether includes diethylene glycol ether, polyethylene glycol ether, polyvinyl alcohol, polyether polyol, polypropylene glycol and amine-terminated polyether, etc.

[0026] The application provides a preparation method of an environmentally-friendly aggregation-induced emission enhancement super-hydrophobic anticorrosive coating, comprising the following steps: mixing and placing film-forming resin, hydrophobic micro-nano particles, fillers, wetting agents, defoaming agents, leveling agents, anti-settling agents, mildew-proof agents, anti-rust agents, diluents in a dispersing machine in parts by weight, and fully stirring at 1000-2000 revolutions per minute for 40-60 minutes. After uniform mixing, modified aggregation-induced emission enhancement urea-formaldehyde microcapsule material is added, and stirring is carried out at 400-600 revolutions per minute for another 30 minutes. After sufficient stirring, filtration, packaging and entering the finished product warehouse, a label is marked.

[0027] The application also provides application of the above-mentioned environmentally-friendly aggregation-induced emission enhancement super-hydrophobic anticorrosive coating to medical devices, precision instruments and biosensors exposed to acid-base scenes.

[0028] The application has the advantages that the polyol ether is used to modify the urea-formaldehyde microcapsule, the proportion of flexible segments in the molecule is increased, the flexibility and anti-aging performance of the microcapsule are significantly improved, the introduction of sodium lignosulfonate can control the crosslinking degree of the resin by acetalization reaction with the hydroxymethyl carbon cation produced in the condensation stage, the generation of free formaldehyde is reduced, the addition of appropriate diatomite can effectively absorb free formaldehyde, and the environmental protection performance is improved in multiple aspects, the introduction of the lignin base can improve the heat resistance and mechanical properties of the film layer, and most importantly, the coating is mainly applied to acid-base response scenes, the strong acid and alkali resistance of the lignin base is introduced into the microcapsule shell structure, the shortcomings of the urea-formaldehyde resin in terms of acid and alkali resistance can be overcome, the outflow of the AEE fluorescent agent caused by shell layer rupture can be effectively prevented, and the indicating effect is reduced. In terms of technical effects, the coating has excellent hydrophobicity, temperature resistance, hardness, adhesion and corrosion resistance, and can exhibit excellent stimulus response performance under multiple external stimuli. Under the action of pressure, the coating can change from red to dark red, and can restore the original fluorescent color under the conditions of solvent fumigation or heating to realize cyclic indication. With the increase of the relative humidity in the air from 10% to 90%, the fluorescent intensity of the coating shows a downward trend, and the water absorption of the coating can be responded in time. In addition, the coating changes from red to orange red after fumigation of HCl gas on the surface of the coating, and the color of the coating after color change can be restored to the original color under the condition of passing in an equal amount of ammonia gas. The pressure-sensitive color change, humidity-sensitive color change and acid-base color change are different and easy to distinguish, the coating integrates artistic beauty and non-interfering response, and can timely warn of the environmental changes on the surface of the coating. DETAILED DESCRIPTION

[0029] In order to better illustrate the purposes, technical solutions and advantages of the application, the application will be further described below in combination with specific examples.

[0030] Example 1

[0031] The formula of the environmentally friendly aggregation-induced emission enhancement super-hydrophobic anticorrosive coating of the present embodiment is as follows, all in parts by weight:

[0032] Fluorocarbon resin 90 parts, hydrophobic titanium dioxide 1 part, hydrophobic diamond 1 part, mica powder 10 parts, barium sulfate 10 parts, calcium carbonate 10 parts, diatomite 10 parts, modified aggregation-induced emission enhancement urea-formaldehyde microcapsule A-A 1 part, polyacrylic acid copolymer potassium salt 1 part, silicone defoamer 0.8 part, silicone modified polysiloxane 0.7 part, organic bentonite 0.8 part, phenolic compound 0.8 part, aluminum tripolyphosphate 5 parts, cyclohexanone 20 parts, ethylene glycol butyl ether 26 parts.

[0033] The preparation method of the modified aggregation-induced emission enhancement urea-formaldehyde microcapsule includes the following steps:

[0034] (1) A certain amount of sodium dodecyl benzene sulfonate, sodium lignosulfonate and deionized water were added into a 250 mL three-necked flask, and stirred for 0.5 h to fully mix and dissolve. A certain amount of urea, diethylene glycol ether and a small amount of melamine were slowly added into the above mixed solution, and the pH was adjusted to 3-5 with dilute hydrochloric acid. After stirring for 2 h, it was ready for use.

[0035] (2) AEE solid A-A was dissolved in a small amount of toluene, and high-speed dispersion was performed to fully dissolve it, forming a core material dispersion liquid;

[0036] (3) The core material dispersion liquid was added to the mixed solution in step 1, and stirred at 10000-15000 r / min for 20-30 min with a high-speed shearing emulsifier. The emulsified mixed liquid was transferred to a three-necked flask, and a certain amount of formaldehyde solution with a mass fraction of 37% was added dropwise. The reaction was carried out at 50-80°C for 4-8 h, and then cooled to room temperature. Neutralization was performed with sodium hydroxide solution to obtain a modified aggregation-induced emission enhancement urea-formaldehyde microcapsule suspension. After cooling to room temperature, washing, suction filtration and drying in a vacuum drying oven at 40°C for 48 h, the prepared modified aggregation-induced emission enhancement urea-formaldehyde microcapsule A-A was placed in a desiccator for standby use.

[0037] The coating preparation method includes the following steps: the fluorocarbon resin, hydrophobic titanium dioxide, hydrophobic diamond, mica powder, barium sulfate, calcium carbonate, diatomite, polyacrylic acid copolymer potassium salt, silicone defoamer, silicone modified polysiloxane, organic bentonite, phenolic compound, aluminum tripolyphosphate, cyclohexanone and ethylene glycol butyl ether were mixed in a disperser and stirred at 1000-2000 rpm for 40-60 min. After mixing evenly, the modified aggregation-induced emission enhancement urea-formaldehyde microcapsule A-A was added and stirred at 400-600 rpm for another 30 min. After sufficient stirring, filtration, packaging and entering the finished product warehouse, the product was labeled with a table mark.

[0038] Example 2

[0039] The formula of the environmentally friendly aggregation-induced emission enhancement super-hydrophobic anticorrosive coating of the present embodiment is as follows, all in parts by weight:

[0040] 100 parts of silicone resin, 1 part of hydrophobic carbon nanotube, 2 parts of hydrophobic silica, 8 parts of talc, 12 parts of attapulgite, 10 parts of kaolin, 12 parts of diatomite, 1.2 parts of modified aggregation-induced emission enhancement urea-formaldehyde microcapsule A-A, 1.1 parts of polyacrylic acid copolymer potassium salt, 0.9 parts of polyether defoaming agent, 0.9 parts of silicone modified polysiloxane, 0.9 parts of organic bentonite, 0.9 parts of sulfur-containing organic matter, 6 parts of zinc phosphate, 25 parts of ethylene glycol butyl ether, and 22 parts of n-butanol.

[0041] The preparation method of the modified aggregation-induced emission enhancement urea-formaldehyde microcapsule includes the following steps:

[0042] (1) A certain amount of sodium dodecyl benzene sulfonate, sodium lignosulfonate and deionized water were added into a 250 mL three-necked flask, and stirred for 0.5 h to fully mix and dissolve. A certain amount of urea, polyethylene glycol ether and a small amount of melamine were slowly added into the above mixed solution, and the pH was adjusted to 3-5 with dilute hydrochloric acid. After stirring for 2 h, it was ready for use.

[0043] (2) The AEE solid A-A was dissolved in a small amount of toluene, and high-speed dispersion was performed to fully dissolve it, forming a core material dispersion;

[0044] (3) The core material dispersion was added to the mixed solution in step 1, and stirred at 10000-15000 r / min for 20-30 min with a high-speed shearing emulsifier. The emulsified mixed solution was transferred to a three-necked flask, and a certain amount of formaldehyde solution with a mass fraction of 37% was added dropwise. The reaction was carried out at 50-80°C for 4-8 h, and then cooled to room temperature. The neutralization was performed with sodium hydroxide solution to obtain a modified aggregation-induced emission enhancement urea-formaldehyde microcapsule suspension. After cooling to room temperature, washing, suction filtration, and drying in a vacuum drying oven at 40°C for 48 h, the prepared modified aggregation-induced emission enhancement urea-formaldehyde microcapsule A-A was placed in a desiccator for standby use.

[0045] The coating preparation method includes the following steps: the silicone resin, hydrophobic carbon nanotube, hydrophobic silica, talc, attapulgite, kaolin, diatomite, polyacrylic acid copolymer potassium salt, polyether defoaming agent, silicone modified polysiloxane, organic bentonite, sulfur-containing organic matter, zinc phosphate, ethylene glycol butyl ether, and n-butanol were mixed in a disperser and stirred at 1000-2000 rpm for 40-60 min. After uniform mixing, the modified aggregation-induced emission enhancement urea-formaldehyde microcapsule A-A was added and stirred at 400-600 rpm for another 30 min. After sufficient stirring, filtration, packaging, and entering the finished product warehouse, the product was labeled with a table.

[0046] Example 3

[0047] The formula of the environmentally friendly aggregation-induced emission enhancement super-hydrophobic anticorrosive coating of this embodiment is as follows, all in parts by weight:

[0048] Fluorocarbon resin 100 parts, hydrophobic silicon powder 2 parts, hydrophobic graphite 2 parts, quartz powder 11 parts, aluminum hydroxide 12 parts, diatomite 10 parts, montmorillonite 11 parts, modified aggregation-induced emission enhancement urea-formaldehyde microcapsule B-B 1.5 parts, polyacrylic acid copolymer potassium salt 1.3 parts, polyether modified silicone defoamer 1 part, polyether siloxane 1 part, organic bentonite 1.2 parts, nitrogen-containing organic matter 1 part, zinc phosphate 7 parts, propylene glycol methyl ether 23 parts, n-butanol 25 parts.

[0049] The preparation method of the modified aggregation-induced emission enhancement urea-formaldehyde microcapsule includes the following steps:

[0050] (1) A certain amount of sodium dodecyl benzene sulfonate, sodium lignosulfonate and deionized water were added into a 250 mL three-necked flask, and stirred for 0.5 h to fully mix and dissolve. A certain amount of urea, polyvinyl alcohol and a small amount of melamine were slowly added into the above mixed solution, and the pH was adjusted to 3-5 with dilute hydrochloric acid. After stirring for 2 hours, it was ready for use.

[0051] (2) AEE solid B-B was dissolved in a small amount of toluene, and high-speed dispersion was performed to fully dissolve, forming a core material dispersion;

[0052] (3) The core material dispersion was added to the mixed solution in step 1, and stirred at 10000-15000 r / min for 20-30 min with a high-speed shearing emulsifier. The emulsified mixed solution was transferred to a three-necked flask, and a certain amount of formaldehyde solution with a mass fraction of 37% was added dropwise. The reaction was carried out at 50-80°C for 4-8 hours, and then cooled to room temperature. The neutralization was performed with sodium hydroxide solution to obtain a modified aggregation-induced emission enhancement urea-formaldehyde microcapsule suspension. After cooling to room temperature, washing, suction filtration, and drying in a vacuum drying oven at 40°C for 48 h, the prepared modified aggregation-induced emission enhancement urea-formaldehyde microcapsule B-B was placed in a desiccator for standby use.

[0053] The coating preparation method includes the following steps: the fluorocarbon resin, hydrophobic silicon powder, hydrophobic graphite, quartz powder, aluminum hydroxide, diatomite, montmorillonite, polyacrylic acid copolymer potassium salt, polyether modified silicone defoamer, polyether siloxane, organic bentonite, nitrogen-containing organic matter, zinc phosphate, propylene glycol methyl ether, and n-butanol were mixed in a disperser and stirred at 1000-2000 rpm for 40-60 min. After mixing evenly, the modified aggregation-induced emission enhancement urea-formaldehyde microcapsule B-B was added and stirred at 400-600 rpm for another 30 min. After sufficient stirring, filtration, packaging, and entering the finished product warehouse, the label was marked.

[0054] Example 4

[0055] The formula of the environmentally friendly aggregation-induced emission enhancement super-hydrophobic anticorrosive coating of the present embodiment is as follows, all in parts by weight:

[0056] Silicone resin 110 parts, hydrophobic titanium dioxide 3 parts, hydrophobic graphite 2 parts, mica powder 13 parts, attapulgite 11 parts, kaolin 8 parts, diatomite 14 parts, modified aggregation-induced emission enhancement urea-formaldehyde microcapsule B-B 1.7 parts, polyacrylic acid copolymer potassium salt 1.2 parts, silicone defoaming agent 1.2 parts, silicone modified polysiloxane 0.9 parts, organic bentonite 1.3 parts, phenolic compound 0.9 parts, aluminum tripolyphosphate 7 parts, cyclohexanone 23 parts, ethylene glycol butyl ether 24 parts.

[0057] The preparation method of the modified aggregation-induced emission enhancement urea-formaldehyde microcapsule includes the following steps:

[0058] (1) A certain amount of sodium dodecyl benzene sulfonate, sodium lignosulfonate and deionized water were added to a 250 mL three-necked flask, and stirred for 0.5 h to fully mix and dissolve. A certain amount of urea, polyether polyol and a small amount of melamine were slowly added to the above mixed solution, and the pH was adjusted to 3-5 with dilute hydrochloric acid. After stirring for 2 hours, it was used.

[0059] (2) AEE solid B-B was dissolved in a small amount of toluene, and high-speed dispersion was performed to fully dissolve, forming a core material dispersion;

[0060] (3) The core material dispersion was added to the mixed solution in step 1, and stirred at 10000-15000 r / min for 20-30 min with a high-speed shearing emulsifier. The emulsified mixed solution was transferred to a three-necked flask, and a certain amount of 37% formaldehyde solution was added dropwise, and reacted at 50-80°C for 4-8 hours. After cooling to room temperature, it was adjusted to neutral with sodium hydroxide solution to obtain a modified aggregation-induced emission enhancement urea-formaldehyde microcapsule suspension. After cooling to room temperature, washing, suction filtration, and drying in a vacuum drying oven at 40°C for 48 h, the prepared modified aggregation-induced emission enhancement urea-formaldehyde microcapsule B-B was placed in a desiccator for standby.

[0061] The coating preparation method comprises the following steps: mixing and placing the silicone resin, hydrophobic titanium dioxide, hydrophobic graphite, mica powder, attapulgite, kaolin, diatomite, polyacrylic acid copolymer potassium salt, silicone defoamer, silicone modified polysiloxane, organic bentonite, phenolic compound, aluminum tripolyphosphate, cyclohexanone and ethylene glycol butyl ether in a disperser at 1000-2000 revolutions per minute for 40-60 minutes. After uniform mixing, the modified aggregation-induced emission enhancement urea-formaldehyde microcapsule B-B is added and stirred at 400-600 revolutions per minute for 30 minutes. After sufficient stirring, filtration and packaging, the product is placed in the finished product warehouse and labeled with the identification table.

[0062] Example 5

[0063] The formula of the environmentally friendly aggregation-induced emission enhancement super-hydrophobic anticorrosive coating of the present embodiment is as follows, all in parts by weight:

[0064] Fluorocarbon resin 110 parts, hydrophobic diamond 4 parts, hydrophobic silicon powder 4 parts, barium sulfate 12 parts, kaolin 12 parts, quartz powder 13 parts, diatomite 13 parts, modified aggregation-induced emission enhancement urea-formaldehyde microcapsule C-C 2 parts, polyacrylic acid copolymer potassium salt 1.4 parts, polyether defoamer 1.1 parts, polyether siloxane 0.9 parts, organic bentonite 1.3 parts, sulfur-containing organic matter 0.9 parts, zinc phosphate 7 parts, cyclohexanone 24 parts, propylene glycol methyl ether 24 parts.

[0065] The preparation method of the modified aggregation-induced emission enhancement urea-formaldehyde microcapsule comprises the following steps:

[0066] (1) A certain amount of sodium dodecyl benzene sulfonate, sodium lignosulfonate and deionized water are added to a 250 mL three-necked flask, stirred for 0.5 h to fully mix and dissolve. A certain amount of urea, polypropylene glycol and a small amount of melamine are slowly added to the above mixed solution, and the pH is adjusted to 3-5 with dilute hydrochloric acid. After stirring for 2 hours, it is ready for use.

[0067] (2) Dissolve AEE solid C-C in a small amount of toluene, disperse at high speed to fully dissolve, and form a core material dispersion;

[0068] (3) Add the core material dispersion to the mixed solution in step 1, and stir at 10000-15000 r / min with a high-speed shearing emulsifier for 20-30 min. Transfer the emulsified mixed solution to a three-necked flask, and dropwise add a certain amount of 37% mass fraction formaldehyde solution. React at 50-80°C for 4-8 hours, cool to room temperature, adjust to neutral with sodium hydroxide solution, and obtain a modified aggregation-induced emission enhancement urea-formaldehyde microcapsule suspension. After cooling to room temperature, washing, suction filtration, and placing in a vacuum drying oven at 40°C for 48 h, the prepared modified aggregation-induced emission enhancement urea-formaldehyde microcapsule C-C is placed in a desiccator for standby use.

[0069] The coating preparation method comprises the following steps: mixing fluorocarbon resin, hydrophobic diamond, hydrophobic silica powder, barium sulfate, kaolin, quartz powder, diatomite, polyacrylic acid copolymer potassium salt, polyether defoamer, polyether siloxane, organic bentonite, sulfur-containing organic matter, zinc phosphate, cyclohexanone, and propylene glycol methyl ether in parts by weight, and placing them in a disperser, and stirring them at 1000-2000 revolutions per minute for 40-60 minutes. After uniform mixing, modified aggregation-induced emission enhancement urea-formaldehyde microcapsule C-C is added, and stirring is carried out at 400-600 revolutions per minute for 30 minutes. After sufficient stirring, filtration and packaging are carried out, and the product is placed in a finished product warehouse, and a label is affixed.

[0070] Example 6

[0071] The formula of the environmentally friendly aggregation-induced emission enhancement super-hydrophobic anticorrosive coating of the present example is as follows, all in parts by weight:

[0072] Silicone resin 120 parts, hydrophobic carbon nanotube 4 parts, hydrophobic silicon dioxide 4 parts, aluminum hydroxide 20 parts, diatomite 14 parts, montmorillonite 12 parts, talc powder 12 parts, modified aggregation-induced emission enhancement urea-formaldehyde microcapsule C-C 2 parts, polyacrylic acid copolymer potassium salt 1.5 parts, polyether modified silicone defoamer 1.2 parts, organosilicon modified polysiloxane 1 part, organic bentonite 1.4 parts, nitrogen-containing organic matter 1 part, aluminum tripolyphosphate 8 parts, n-butanol 25 parts, and ethylene glycol butyl ether 25 parts.

[0073] The preparation method of the modified aggregation-induced emission enhancement urea-formaldehyde microcapsule comprises the following steps:

[0074] (1) A certain amount of sodium dodecyl benzene sulfonate, sodium lignosulfonate, and deionized water are added to a 250 mL three-necked flask, and stirred for 0.5 h to fully mix and dissolve. A certain amount of urea, amine-terminated polyether, and a small amount of melamine are slowly added to the above mixed solution, and the pH is adjusted to 3-5 with dilute hydrochloric acid. After stirring for 2 hours, it is ready for use.

[0075] (2) AEE solid C-C is dissolved in a small amount of toluene, and high-speed dispersion is carried out to fully dissolve, forming a core material dispersion liquid;

[0076] (3) The core material dispersion liquid is added to the mixed solution in step 1, and stirred at 10000-15000 r / min for 20-30 min with a high-speed shearing emulsifier. The emulsified mixed liquid is transferred to a three-necked flask, and a certain amount of 37% mass fraction formaldehyde solution is added dropwise, and reacted at 50-80°C for 4-8 hours. After cooling to room temperature, neutralization is carried out with sodium hydroxide solution to obtain a modified aggregation-induced emission enhancement urea-formaldehyde microcapsule suspension. After cooling to room temperature, washing, and suction filtration, it is placed in a vacuum drying oven at 40°C and dried for 48 h. The prepared modified aggregation-induced emission enhancement urea-formaldehyde microcapsule C-C is placed in a desiccator for standby use.

[0077] The coating preparation method comprises the following steps: mixing and placing the silicone resin, hydrophobic carbon nanotube, hydrophobic silicon dioxide, aluminum hydroxide, diatomite, montmorillonite, talc powder, polyacrylic acid copolymer potassium salt, polyether modified silicone defoamer, silicone modified polysiloxane, organic bentonite, nitrogen-containing organic matter, aluminum tripolyphosphate, n-butanol and ethylene glycol butyl ether in a disperser at 1000-2000 revolutions per minute for 40-60 minutes. After uniform mixing, the modified aggregation-induced emission enhancement urea-formaldehyde microcapsule C-C is added and stirred at 400-600 revolutions per minute for another 30 minutes. After sufficient stirring, filtration and packaging, the product is placed in a finished product warehouse and labeled with a table.

[0078] Comparative Example 1

[0079] The formula of the environmental protection type aggregation-induced emission enhancement super-hydrophobic anticorrosive coating of the present comparative example is as follows, all in parts by weight:

[0080] Fluorocarbon resin 90 parts, hydrophobic titanium dioxide 1 part, hydrophobic diamond 1 part, mica powder 10 parts, barium sulfate 10 parts, calcium carbonate 10 parts, diatomite 10 parts, aggregation-induced emission enhancement urea-formaldehyde microcapsule A-A 1 part, polyacrylic acid copolymer potassium salt 1 part, silicone defoamer 0.8 parts, silicone modified polysiloxane 0.7 parts, organic bentonite 0.8 parts, phenolic compound 0.8 parts, aluminum tripolyphosphate 5 parts, cyclohexanone 20 parts, ethylene glycol butyl ether 26 parts.

[0081] The preparation method of the aggregation-induced emission enhancement urea-formaldehyde microcapsule A-A comprises the following steps:

[0082] (1) A certain amount of sodium dodecyl benzene sulfonate and deionized water are added to a 250 mL three-necked flask, and stirred for 0.5 h to fully mix and dissolve. A certain amount of urea and a small amount of melamine are slowly added to the above mixed solution, and the pH is adjusted to 3-5 with dilute hydrochloric acid. After stirring for 2 hours, it is used.

[0083] (2) AEE solid A-A is dissolved in a small amount of toluene, and high-speed dispersion is performed to fully dissolve it, forming a core material dispersion liquid;

[0084] (3) The core material dispersion liquid is added to the mixed solution in step 1, and stirred at 10000-15000 r / min for 20-30 min with a high-speed shearing emulsifier. The emulsified mixed liquid is transferred to a three-necked flask, and a certain amount of 37% mass fraction formaldehyde solution is added dropwise. The reaction is carried out at 50-80°C for 4-8 hours, and after cooling to room temperature, it is adjusted to neutral with sodium hydroxide solution to obtain an aggregation-induced emission enhancement urea-formaldehyde microcapsule suspension. After cooling to room temperature, washing, suction filtration, and placing in a vacuum drying oven at 40°C for 48 h, the prepared aggregation-induced emission enhancement urea-formaldehyde microcapsule A-A is placed in a desiccator for standby use.

[0085] The coating preparation method comprises the following steps: mixing fluorocarbon resin, hydrophobic titanium dioxide, hydrophobic diamond, mica powder, barium sulfate, calcium carbonate, diatomite, polyacrylic acid copolymer potassium salt, silicone defoamer, silicone modified polysiloxane, organic bentonite, phenolic compound, aluminum tripolyphosphate, cyclohexanone, and ethylene glycol butyl ether in parts by weight, and placing them in a disperser, and stirring at 1000-2000 revolutions per minute for 40-60 minutes. After uniform mixing, add the aggregation-induced emission enhancement urea-formaldehyde microcapsule A-A, and stir at 400-600 revolutions per minute for another 30 minutes. After sufficient stirring, filter and package, and put into the finished product warehouse, and mark the identification.

[0086] Comparative Example 2

[0087] The formula of the environmental protection type aggregation-induced emission enhancement super-hydrophobic anticorrosive coating of the present comparative example is as follows, all in parts by weight:

[0088] fluorocarbon resin 100 parts, hydrophobic silicon powder 2 parts, hydrophobic graphite 2 parts, quartz powder 11 parts, aluminum hydroxide 12 parts, diatomite 10 parts, montmorillonite 11 parts, aggregation-induced emission enhancement urea-formaldehyde microcapsule B-B 1.5 parts, polyacrylic acid copolymer potassium salt 1.3 parts, polyether modified silicone defoamer 1 part, polyether siloxane 1 part, organic bentonite 1.2 parts, nitrogen-containing organic matter 1 part, zinc phosphate 7 parts, propylene glycol methyl ether 23 parts, and n-butanol 25 parts.

[0089] The preparation method of the aggregation-induced emission enhancement urea-formaldehyde microcapsule B-B comprises the following steps:

[0090] (1) A certain amount of sodium dodecyl benzene sulfonate and deionized water are added to a 250 mL three-necked flask, and stirred for 0.5 h to fully mix and dissolve. A certain amount of urea and a small amount of melamine are slowly added to the above mixed solution, and the pH is adjusted to 3-5 with dilute hydrochloric acid, and stirred for 2 hours before use.

[0091] (2) AEE solid B-B is dissolved in a small amount of toluene, and high-speed dispersion is performed to fully dissolve, forming a core material dispersion liquid;

[0092] (3) The core material dispersion liquid is added to the mixed solution in step 1, and stirred at 10000-15000 r / min for 20-30 min with a high-speed shearing emulsifier. The emulsified mixed liquid is transferred to a three-necked flask, and a certain amount of 37% mass fraction formaldehyde solution is added dropwise, and reacted at 50-80°C for 4-8 hours. After cooling to room temperature, neutralization is performed with sodium hydroxide solution to obtain an aggregation-induced emission enhancement urea-formaldehyde microcapsule suspension. After cooling to room temperature, washing, and suction filtration, it is placed in a vacuum drying oven at 40°C and dried for 48 h. The prepared aggregation-induced emission enhancement urea-formaldehyde microcapsule A-A is placed in a desiccator for standby use.

[0093] The preparation method comprises the following steps: mixing fluorocarbon resin, hydrophobic silicon powder, hydrophobic graphite, quartz powder, aluminum hydroxide, diatomite, montmorillonite, polyacrylic acid copolymer potassium salt, polyether modified silicone defoamer, polyether siloxane, organic bentonite, nitrogen-containing organic matter, zinc phosphate, propylene glycol methyl ether and n-butanol in parts by weight and placing them in a disperser, and stirring them at 1000-2000 revolutions per minute for 40-60 minutes. After uniform mixing, add the aggregation-induced emission enhancement urea-formaldehyde microcapsule B-B and stir at 400-600 revolutions per minute for another 30 minutes. After sufficient stirring, filter and package, and store in the finished product warehouse, and mark the identification.

[0094] Comparative Example 3

[0095] The formula of the environment-friendly aggregation-induced emission enhancement super-hydrophobic anticorrosive coating of the present example is as follows, all in parts by weight:

[0096] fluorocarbon resin 110 parts, hydrophobic diamond 4 parts, hydrophobic silicon powder 4 parts, barium sulfate 12 parts, kaolin 12 parts, quartz powder 13 parts, diatomite 13 parts, aggregation-induced emission enhancement urea-formaldehyde microcapsule C-C 2 parts, polyacrylic acid copolymer potassium salt 1.4 parts, polyether defoamer 1.1 parts, polyether siloxane 0.9 parts, organic bentonite 1.3 parts, sulfur-containing organic matter 0.9 parts, zinc phosphate 7 parts, cyclohexanone 24 parts, propylene glycol methyl ether 24 parts.

[0097] The preparation method of the aggregation-induced emission enhancement urea-formaldehyde microcapsule C-C comprises the following steps:

[0098] (1) A certain amount of sodium dodecyl benzene sulfonate and deionized water are added to a 250 mL three-necked flask, and stirred for 0.5 h to fully mix and dissolve. A certain amount of urea and a small amount of melamine are slowly added to the above mixed solution, and the pH is adjusted to 3-5 with dilute hydrochloric acid, and stirred for 2 hours before use.

[0099] (2) Dissolve AEE solid C-C in a small amount of toluene, and disperse at high speed to fully dissolve, forming a core material dispersion;

[0100] (3) Add the core material dispersion to the mixed solution in step 1, and stir at 10000-15000 r / min with a high-speed shearing emulsifier for 20-30 min. Transfer the emulsified mixed solution to a three-necked flask, and add a certain amount of 37% mass fraction formaldehyde solution dropwise, and react at 50-80°C for 4-8 hours. After cooling to room temperature, adjust to neutral with sodium hydroxide solution to obtain an aggregation-induced emission enhancement urea-formaldehyde microcapsule suspension. After cooling to room temperature, washing, and suction filtration, place it in a vacuum drying oven at 40°C for 48 h. The prepared aggregation-induced emission enhancement urea-formaldehyde microcapsule C-C is placed in a desiccator for standby use.

[0101] The preparation method comprises the following steps: mixing fluorocarbon resin, hydrophobic diamond, hydrophobic silicon powder, barium sulfate, kaolin, quartz powder, diatomite, polyacrylic acid copolymer potassium salt, polyether defoaming agent, polyether siloxane, organic bentonite, sulfur-containing organic matter, zinc phosphate, cyclohexanone and propylene glycol methyl ether in parts by weight, and placing them in a dispersing machine, and stirring at 1000-2000 revolutions / minute for 40-60 minutes. After uniform mixing, add the aggregation-induced emission enhancement urea-formaldehyde microcapsule C-C and stir at 400-600 revolutions / minute for another 30 minutes. After sufficient stirring, filter and package, and enter the finished product warehouse, and mark the identification.

[0102] The coatings obtained from examples 1 to comparative example 3 are subjected to performance detection, and the detection results are as follows:

[0103]

[0104]

[0105]

[0106] A series of environmentally friendly aggregation-induced emission enhancement super-hydrophobic anticorrosive coatings are prepared by using the modified urea-formaldehyde resin microcapsule to coat the AEE fluorescent material. Compared with ordinary urea-formaldehyde resin microcapsules, the modified urea-formaldehyde resin microcapsules prepared by using polyhydric alcohol ether and sodium lignosulfonate have stronger anti-aging, flexibility, environmental protection and mechanical properties. At the same time, since the coating of the application is mainly applied to acid-base response scenes, the strong acid and alkali resistance lignin base is introduced into the microcapsule shell structure, which can overcome the shortcomings of the urea-formaldehyde resin itself not resistant to acid and alkali, effectively prevent the AEE fluorescent agent from flowing out due to the shell layer rupture and reduce the indication effect. In terms of technical effect, the coating has good hardness, adhesion, gasoline resistance, salt spray resistance, temperature resistance, acid and alkali resistance, formaldehyde purification performance and super-hydrophobicity, and can simultaneously exhibit excellent stimulus response performance under multiple external stimuli. Under the action of pressure, the coating can change from red to dark red, and can restore the original fluorescent color under the conditions of solvent fumigation or heating to realize cyclic indication. With the increase of the relative humidity in the air from 10% to 90%, the fluorescent intensity of the coating shows a downward trend, which can respond to the water absorption of the coating in time. In addition, the coating realizes the change from red to orange-red after fumigating HCl gas on the surface of the coating, and the coating after color change can restore the original color under the condition of passing in equal amount of ammonia gas. The above pressure-sensitive color change, humidity-sensitive color change and acid-base color change are different and easy to distinguish, and are integrated with the artistic beauty of the coating and non-interfering response, which can timely warn the environmental changes on the surface of the coating.

[0107] The specific embodiments of the present application are described above. It needs to be understood that the present application is not limited to the specific embodiments described above, and various modifications and changes can be made by those skilled in the art within the scope of the claims, which do not affect the essence of the present application.

Claims

1. An environmentally friendly aggregation-induced emission enhancement super-hydrophobic anticorrosive coating, each in parts by weight, comprising the following components: 90-120 parts of a film-forming resin, 2-8 parts of hydrophobic micro-nano particles, 40-50 parts of a filler, 1-2 parts of modified aggregation-induced emission enhancement urea-formaldehyde microcapsules, 1-1.5 parts of a wetting agent, 0.8-1.2 parts of a defoaming agent, 0.7-1.0 parts of a leveling agent, 0.8-1.4 parts of an anti-settling agent, 0.8-1 part of an anti-mildew agent, 5-8 parts of an anti-rust agent, and 46-50 parts of a diluent. The modified aggregation-induced emission enhancement urea-formaldehyde microcapsules comprise aggregation-induced emission enhancement fluorescent materials as core materials and modified urea-formaldehyde resins as shell materials, and a preparation method of the modified aggregation-induced emission enhancement urea-formaldehyde microcapsules comprises the following steps: (1) A certain amount of sodium dodecyl benzene sulfonate, sodium lignosulfonate and deionized water are added into a 250 mL three-necked flask, stirred for 0.5 h to fully mix and dissolve; a certain amount of urea, bridging compound and a small amount of melamine are slowly added into the mixed solution, the pH is adjusted to 3-5 with dilute hydrochloric acid, and stirring is performed for 2 h before use; (2) The aggregation-induced emission enhancement solids A-A, B-B and C-C are respectively dissolved in a small amount of toluene, fully dissolved by high-speed dispersion, and a core material dispersion liquid is formed; (3) The core material dispersion liquid is added into the mixed solution obtained in step 1, stirred at 10000-15000 r / min for 20-30 min by using a high-speed shearing emulsifier; the emulsified mixed liquid is transferred into a three-necked flask, a certain amount of formaldehyde solution with a mass fraction of 37% is added drop by drop, and the reaction is performed at 50-80℃ for 4-8 h; after cooling to room temperature, the solution is adjusted to neutral with sodium hydroxide solution, and a modified aggregation-induced emission enhancement urea-formaldehyde microcapsule suspension is obtained; after cooling to room temperature, washing, suction filtration and drying in a vacuum drying oven at 40℃ for 48 h, the prepared modified aggregation-induced emission enhancement urea-formaldehyde microcapsules A-A, B-B and C-C are placed in a desiccator for standby use; The bridging compound is diethylene glycol ether, polyvinyl alcohol, polyether polyol and amine-terminated polyether. The structures of the aggregation-induced emission enhancement solids A-A, B-B and C-C are as follows: 。 2.The environmentally-friendly aggregation-induced emission enhancement (AIEE) superhydrophobic anticorrosive coating according to claim 1, characterized in that, The film-forming resin comprises fluorocarbon resin or silicone resin. 3.The environmentally-friendly aggregation-induced emission enhancement (AIEE) superhydrophobic anticorrosive coating according to claim 1, characterized in that, The hydrophobic micro-nano particles comprise two or more of hydrophobic titanium dioxide, diamond, carbon nanotube, silicon dioxide, silicon powder and graphite with a particle size of 10 nm-10 μm. 4.The environmentally-friendly aggregation-induced emission enhancement (AIEE) superhydrophobic anticorrosive coating according to claim 1, characterized in that, The filler comprises two or more of mica powder, barium sulfate, calcium carbonate, talc, attapulgite, kaolin, quartz powder, aluminum hydroxide, diatomite and montmorillonite. 5.The environmentally friendly aggregation-induced emission enhancement superhydrophobic anticorrosive coating according to claim 1, characterized in that, The wetting agent is polyacrylic acid copolymer potassium salt; the defoaming agent is one or more of silicone defoaming agent and polyether defoaming agent; the leveling agent is one or more of silicone-modified polysiloxane and polyether siloxane; and the anti-settling agent is organic bentonite. 6.The environmentally-friendly aggregation-induced emission enhancement (AIEE) superhydrophobic anticorrosive coating according to claim 1, wherein, The anti-mildew agent is one or more of phenolic compounds, sulfur-containing organic compounds and nitrogen-containing organic compounds; the anti-rust agent is one or more of aluminum tripolyphosphate and zinc phosphate; and the diluent is one or more of cyclohexanone, n-butanol, ethylene glycol butyl ether and propylene glycol methyl ether.

7. A method for preparing the environmentally friendly aggregation-induced emission enhancement super-hydrophobic anticorrosive coating according to any one of claims 1-6, comprising the following steps: mixing and placing the film-forming resin, hydrophobic micro-nano particles, fillers, wetting agents, defoamers, leveling agents, anti-settling agents, mildewcides, rust inhibitors, diluents in a dispersing machine in parts by weight, and stirring at 1000-2000 rpm for 40-60 minutes; after mixing evenly, adding modified aggregation-induced emission enhancement urea-formaldehyde microcapsules, and stirring at 400-600 rpm for another 30 minutes; after sufficient stirring, filtering, packaging, entering the finished product warehouse, and marking the table identity.

8. Use of the environmentally friendly aggregation-induced emission enhancement super-hydrophobic anticorrosive coating according to any one of claims 1-6 on medical devices and precision instruments exposed to acid-base scenarios.

9. Use of the environmentally friendly aggregation-induced emission enhancement super-hydrophobic anticorrosive coating according to any one of claims 1-6 on biosensors exposed to acid-base scenarios.

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