Environment-friendly aggregation-induced emission flame-retardant coating and preparation method thereof

Abstract

The application adopts fire-resistant modified urea-formaldehyde resin microcapsules to coat AIE fluorescent materials, and prepares a series of environment-friendly aggregation-induced emission flame-retardant coatings. Compared with ordinary urea-formaldehyde resin microcapsules, the modified urea-formaldehyde resin microcapsules prepared by using polyhydric alcohol ether, sodium lignosulfonate and reactive phosphazene have stronger anti-aging, flexibility, environmental protection, mechanical property and flame retardance. In terms of technical effect, the coating has excellent temperature resistance, hardness, adhesion, corrosion resistance and flame retardance. Under the action of different temperatures, the coatings added with CN-BIVB 14 , CN-BIVB 16 and TPI microcapsules can realize color change under high-temperature conditions, and have excellent flame retardance and early warning performance. Among them, the coating added with TPI series microcapsules can even exhibit gradually linear discoloration effect under different temperatures. The above-mentioned environment-friendly aggregation-induced emission flame-retardant coating integrates artistic beauty, flame retardance and temperature early warning, and can timely early warn external temperature change.

Description

Technical Field

[0001] This invention relates to a flame-retardant coating, specifically to an environmentally friendly aggregation-induced light-emitting flame-retardant coating and its preparation method. Background Technology

[0002] Stimulus-responsive materials are a class of smart materials whose color changes in response to external stimuli. They can be broadly classified into two categories: traditional stimulus-responsive materials and novel aggregation-induced emission (AIE) stimulus-responsive materials. Because they exhibit color-changing effects in response to stimuli such as light, electricity, heat, solvents, pressure, pH, and humidity, they have applications in numerous fields including anti-counterfeiting, pressure sensing, OLEDs, and memory chips, making them a highly promising type of smart material. Compared to traditional stimulus-responsive materials, AIE effectively overcomes the aggregation-induced quenching effect, thus offering greater potential for practical applications.

[0003] Through continuous exploration by scientists, aggregation-induced emission (AIE) stimulus-responsive materials have begun to emerge in various cutting-edge fields. However, research on the industrial application of these "smart" materials, especially in the field of coatings, is extremely limited. Due to the relatively complex mechanism of AIE, its susceptibility to multiple factors, and the difficulty in automatically restoring the color after the response, AIE stimulus-responsive coatings, especially highly sensitive environmentally friendly AIE flame-retardant coatings, are extremely rare.

[0004] Currently, we have developed a series of stimulus-responsive aggregation-induced light-emitting (AIE) coatings (CN115505308B, CN116004060B). The core of these coatings is the use of urea-formaldehyde resin as the shell structure and aggregation-induced light-emitting material as the core layer, to prepare urea-formaldehyde resin microcapsules, thereby protecting AIE molecules and enhancing their color-changing effect. However, urea-formaldehyde resin has drawbacks such as excessive formaldehyde release, poor water resistance, poor flexibility, and poor fire resistance and acid / alkali resistance, which limit the effectiveness of AIE microcapsule color-changing materials. Therefore, there is an urgent need to develop a modified urea-formaldehyde resin microcapsule to overcome the shortcomings of existing microcapsules. Summary of the Invention

[0005] The purpose of this invention is to provide an environmentally friendly aggregation-induced light-emitting flame-retardant coating and its preparation method. This coating exhibits excellent thermochromic properties and can provide timely early warning responses to changes in external temperature.

[0006] An environmentally friendly, aggregation-induced luminescence flame-retardant coating, comprising the following components by weight:

[0007] Film-forming resin 100-130 parts, filler 30-50 parts, refractory modified aggregation-induced light-emitting urea-formaldehyde microcapsules 1-3 parts, wetting agent 1-2 parts, defoamer 1-2 parts, leveling agent 1-1.5 parts, anti-settling agent 0.5-1.5 parts, mildew inhibitor 0.8-1 part, rust inhibitor 1-2 parts, diluent 40-50 parts.

[0008] According to the present invention, the environmentally friendly aggregation-induced light-emitting flame-retardant coating comprises two or more of the following: fluorocarbon resin, silicone resin, polyurethane resin, polyester resin, and acrylic resin.

[0009] According to the present invention, the environmentally friendly aggregation-induced light-emitting flame-retardant coating comprises two or more of the following fillers: mica powder, barium sulfate, calcium carbonate, talc powder, attapulgite, kaolin, quartz powder, aluminum hydroxide, diatomaceous earth, and montmorillonite.

[0010] According to the present invention, the environmentally friendly aggregation-induced light emission flame-retardant coating comprises an aggregation-induced light emission fluorescent material as the core structure and a fire-resistant modified urea-formaldehyde resin as the shell structure.

[0011] The core material structure includes the following AIE fluorescent molecules: CN-BIVB n The series and TPI, with structures shown below, are described in detail in the papers "Synthesis and Thermochromic Properties of Cyano-Modified 1,4-Di((E)-2-(1H-indol-3-yl)vinyl)benzene Derivatives" and "Highly Sensitive Sensing of Polarity, Temperature, and Acid Gases by a Smart Fluorescent Molecule".

[0012]

[0013] The environmentally friendly aggregation-induced light-emitting flame-retardant coating according to the present invention comprises a wetting agent being a potassium salt of polyacrylic acid copolymer.

[0014] According to the present invention, the environmentally friendly aggregation-induced light-emitting flame-retardant coating is wherein the defoamer is one or more of an organosilicon defoamer, a polyether defoamer, or a polyether-modified silicone defoamer.

[0015] According to the present invention, the environmentally friendly aggregation-induced luminescence flame-retardant coating comprises one or more of organosilicon-modified polysiloxane or polyether siloxane.

[0016] The environmentally friendly aggregation-induced light-emitting flame-retardant coating according to the present invention comprises an anti-settling agent being organobentonite.

[0017] According to the present invention, the environmentally friendly aggregation-induced light-emitting flame-retardant coating contains a mildew inhibitor that is one or more of phenolic compounds, sulfur-containing organic compounds, or nitrogen-containing organic compounds.

[0018] According to the present invention, the environmentally friendly aggregation-induced light-emitting flame-retardant coating contains one or more of aluminum tripolyphosphate and zinc phosphate as the rust inhibitor.

[0019] The environmentally friendly aggregation-induced light-emitting flame-retardant coating of the present invention comprises, wherein the diluent is one or more of cyclohexanone, n-butanol, ethylene glycol butyl ether, and propylene glycol methyl ether.

[0020] According to the present invention, the environmentally friendly aggregation-induced light-emitting flame-retardant coating, wherein the preparation method of the fire-resistant modified aggregation-induced light-emitting urea-formaldehyde microcapsules includes the following steps:

[0021] (1) Add a certain amount of sodium dodecylbenzenesulfonate, sodium lignosulfonate, polyol ether and deionized water to a 250mL three-necked flask, and stir for 0.5h to ensure thorough mixing and dissolution. Slowly add a certain amount of urea, reactive phosphazene and a small amount of melamine to the above mixed solution, adjust the pH to 3-6 with dilute hydrochloric acid, stir for 2 hours and set aside for use.

[0022] (2) Dissolve different AIE solids in a small amount of toluene and disperse them at high speed to ensure complete dissolution, forming a core material dispersion;

[0023] (3) Add different core material dispersions to the mixed solution in step 1, and stir for 20-30 min at 10000-15000 r / min using a high-speed shear emulsifier. Transfer the emulsified mixture to a three-necked flask, add a certain amount of 37% formaldehyde solution dropwise, react at 50-100℃ for 4-8 hours, cool to room temperature, and adjust to neutral with sodium hydroxide solution to obtain a suspension of refractory-modified aggregation-induced luminescence urea-formaldehyde microcapsules. After cooling to room temperature, washing, and filtration, place in a vacuum drying oven and dry at 40℃ for 48 h. Place the obtained refractory-modified aggregation-induced luminescence urea-formaldehyde microcapsules in a desiccator for later use.

[0024] According to the present invention, the environmentally friendly aggregation-induced light-emitting flame-retardant coating contains polyol ethers including polyethylene glycol ether, polyvinyl alcohol, polyether polyol, polypropylene glycol, and terminal amine polyethers.

[0025] According to the present invention, the environmentally friendly aggregation-induced light-emitting flame-retardant coating, wherein the reactive phosphazene has the structural formula shown below: AE

[0026]

[0027] This invention provides a method for preparing an environmentally friendly aggregation-induced light-emitting flame-retardant coating, comprising the following steps: mixing film-forming resin, filler, wetting agent, defoamer, leveling agent, anti-settling agent, mildew inhibitor, rust inhibitor, and diluent according to parts by weight and placing them in a disperser, and stirring thoroughly at 1000-2000 rpm for 40-60 minutes. After uniform mixing, adding refractory-modified aggregation-induced light-emitting urea-formaldehyde microcapsule material, and stirring again at 500-800 rpm for 30 minutes. After thorough stirring, filtering, packaging, and placing in the finished product warehouse, and labeling.

[0028] This invention also provides the application of the above-mentioned environmentally friendly aggregation-induced light-emitting flame-retardant coating in fire-resistant materials, valves, and instruments.

[0029] The beneficial effects of this invention are as follows: This invention modifies urea-formaldehyde microcapsules with polyol ethers, increasing the proportion of flexible segments in the molecule and significantly enhancing the flexibility and anti-aging properties of the microcapsules. Furthermore, the introduction of sodium lignosulfonate can, on the one hand, react with the hydroxymethyl carbocation acetalization reaction generated during the polycondensation stage, controlling the degree of resin crosslinking and reducing the generation of free formaldehyde; on the other hand, the introduction of lignin groups can improve the heat resistance, mechanical properties, and acid and alkali resistance of the film layer, making the modified microcapsule shell more adaptable to acidic conditions and fire-resistant environments. Simultaneously, this invention creatively introduces reactive phosphazenes into the AIE microcapsule shell. As is well known, phosphazene compounds have excellent flame-retardant properties. The functional groups in reactive phosphazenes can chemically bond with the groups in the modified urea-formaldehyde resin, thereby introducing phosphazene segments into the microcapsule shell. These phosphazene segments, combined with heat-resistant lignin groups, can synergistically exhibit superior flame-retardant and fire-resistant effects. Since the coating of this invention is mainly used in flame-retardant and fire-resistant applications, the aforementioned fire-resistant modified aggregation-induced luminescence urea-formaldehyde microcapsules can effectively prevent the leakage of AIE fluorescent agents due to shell rupture caused by high temperatures, thus preventing a reduction in the indicating effect. In terms of technical effects, the coating of this invention exhibits excellent temperature resistance, hardness, adhesion, corrosion resistance, and flame-retardant properties. Under heating conditions, the addition of CN-BIVB... 14 CN-BIVB 16 Both coatings containing TPI microcapsules and coatings with these materials exhibit noticeable color changes, demonstrating excellent flame retardant and early warning properties. In particular, coatings with added TPI microcapsules can even show a gradual linear color change effect at different temperatures. These environmentally friendly, aggregation-induced light-emitting flame-retardant coatings integrate aesthetic appeal, flame retardancy, and temperature warning, providing timely alerts for changes in external temperature. Detailed Implementation

[0030] To better illustrate the inventive purpose, technical solution, and advantages of this invention, the invention will be further described below in conjunction with specific embodiments.

[0031] Example 1

[0032] The formulation of the environmentally friendly aggregation-induced light-emitting flame-retardant coating in this embodiment is as follows, all by weight:

[0033] 40 parts fluorocarbon resin, 60 parts organosilicon resin, 10 parts mica powder, 10 parts barium sulfate, 10 parts calcium carbonate, 1 part refractory modified aggregation-induced luminescence urea-formaldehyde microcapsules CN-BIVB8, 1 part potassium salt of polyacrylic acid copolymer, 1 part organosilicon defoamer, 1 part organosilicon modified polysiloxane, 0.5 parts organobentonite, 0.8 parts phenolic compounds, 1 part aluminum tripolyphosphate, 22 parts cyclohexanone, and 18 parts ethylene glycol butyl ether.

[0034] The preparation method of refractory modified aggregation-induced luminescence urea-formaldehyde microcapsules CN-BIVB8 includes the following steps:

[0035] (1) Add a certain amount of sodium dodecylbenzenesulfonate, sodium lignosulfonate, terminal amine polyether and deionized water to a 250mL three-necked flask, and stir for 0.5h to ensure thorough mixing and dissolution. Slowly add a certain amount of urea, reactive phosphazene A and a small amount of melamine to the above mixed solution, adjust the pH to 3-6 with dilute hydrochloric acid, stir for 2 hours and set aside for use.

[0036] (2) Dissolve CN-BIVB8 in a small amount of toluene and disperse it at high speed to ensure complete dissolution, forming a core material dispersion;

[0037] (3) Add the core material dispersion of CN-BIVB8 to the mixed solution in step 1, and stir for 20-30 min at 10000-15000 r / min using a high-speed shear emulsifier. Transfer the emulsified mixture to a three-necked flask, and add a certain amount of formaldehyde solution with a mass fraction of 37% dropwise. React at 50-100℃ for 4-8 hours. After cooling to room temperature, adjust to neutral with sodium hydroxide solution to obtain a suspension of refractory-modified aggregation-induced light-emitting urea-formaldehyde microcapsules. After cooling to room temperature, washing, and filtration, place in a vacuum drying oven and dry at 40℃ for 48 h. Place the obtained refractory-modified aggregation-induced light-emitting urea-formaldehyde microcapsules CN-BIVB8 in a desiccator for later use.

[0038] The coating preparation method includes the following steps: Fluorocarbon resin, silicone resin, mica powder, barium sulfate, calcium carbonate, potassium salt of polyacrylic acid copolymer, silicone defoamer, silicone-modified polysiloxane, organobentonite, phenolic compounds, aluminum tripolyphosphate, cyclohexanone, and ethylene glycol butyl ether are mixed in parts by weight and placed in a disperser, and stirred thoroughly at 1000-2000 rpm for 40-60 minutes. After uniform mixing, refractory-modified aggregation-induced light-emitting urea-formaldehyde microcapsules CN-BIVB8 are added and stirred again at 400-600 rpm for 30 minutes. After thorough stirring, the mixture is filtered, packaged, and placed in the finished product warehouse, with labeling and identification.

[0039] Example 2

[0040] The formulation of the environmentally friendly aggregation-induced light-emitting flame-retardant coating in this embodiment is as follows, all by weight:

[0041] 50 parts silicone resin, 55 parts polyurethane resin, 10 parts talc, 12 parts attapulgite, 10 parts kaolin, and refractory-modified aggregation-induced luminescence urea-formaldehyde microcapsules CN-BIVB 10 1.3 parts, potassium salt of polyacrylic acid copolymer 1.1 parts, polyether defoamer 1.3 parts, organosilicon modified polysiloxane 1.1 parts, organobentonite 0.7 parts, sulfur-containing organic matter 0.9 parts, zinc phosphate 1.5 parts, ethylene glycol butyl ether 21 parts, n-butanol 22 parts.

[0042] Refractory modified aggregation-induced light-emitting urea-formaldehyde microcapsules CN-BIVB 10 The preparation method includes the following steps:

[0043] (1) Add a certain amount of sodium dodecylbenzenesulfonate, sodium lignosulfonate, polyethylene glycol ether and deionized water to a 250mL three-necked flask, and stir for 0.5h to ensure thorough mixing and dissolution. Slowly add a certain amount of urea, reactive phosphazene E and a small amount of melamine to the above mixed solution, adjust the pH to 3-6 with dilute hydrochloric acid, stir for 2 hours and set aside for use.

[0044] (2) CN-BIVB 10 Dissolve in a small amount of toluene and disperse at high speed to ensure complete dissolution, forming a core material dispersion;

[0045] (3) Add CN-BIVB to the mixed solution in step 1 10 The core material dispersion was stirred for 20-30 minutes using a high-speed shear emulsifier at 10000-15000 r / min. The emulsified mixture was transferred to a three-necked flask, and a certain amount of 37% formaldehyde solution was added dropwise. The mixture was reacted at 50-100℃ for 4-8 hours. After cooling to room temperature, the solution was adjusted to neutral with sodium hydroxide solution to obtain a suspension of refractory-modified aggregation-induced light-emitting urea-formaldehyde microcapsules. After cooling to room temperature, washing, and filtration, the suspension was dried in a vacuum drying oven at 40℃ for 48 hours. The resulting refractory-modified aggregation-induced light-emitting urea-formaldehyde microcapsules (CN-BIVB) were then prepared. 10 Store in a desiccator for later use.

[0046] The coating preparation method includes the following steps: In accordance with the weight proportions, organosilicon resin, polyurethane resin, talc powder, attapulgite, kaolin, potassium salt of polyacrylic acid copolymer, polyether defoamer, organosilicon-modified polysiloxane, organobentonite, sulfur-containing organic compounds, zinc phosphate, ethylene glycol butyl ether, and n-butanol are mixed and placed in a disperser, and stirred thoroughly at 1000-2000 rpm for 40-60 minutes. After uniform mixing, refractory-modified aggregation-induced light-emitting urea-formaldehyde microcapsules CN-BIVB are added. 10 Stir for another 30 minutes at 400-600 rpm. After thorough stirring, filter, package, and store in the finished product warehouse, labeling as described.

[0047] Example 3

[0048] The formulation of the environmentally friendly aggregation-induced light-emitting flame-retardant coating in this embodiment is as follows, all by weight:

[0049] 50 parts polyurethane resin, 60 parts polyester resin, 11 parts quartz powder, 12 parts aluminum hydroxide, 14 parts diatomaceous earth, and refractory-modified aggregation-induced luminescence urea-formaldehyde microcapsules CN-BIVB 12 1.7 parts, potassium salt of polyacrylic acid copolymer 1.3 parts, polyether modified silicone defoamer 1.5 parts, polyether siloxane 1.3 parts, organobentonite 1.2 parts, nitrogen-containing organic matter 1 part, zinc phosphate 1.4 parts, propylene glycol methyl ether 23 parts, n-butanol 25 parts.

[0050] Refractory modified aggregation-induced light-emitting urea-formaldehyde microcapsules CN-BIVB 12 The preparation method includes the following steps:

[0051] (1) Add a certain amount of sodium dodecylbenzenesulfonate, sodium lignosulfonate, polyvinyl alcohol and deionized water to a 250mL three-necked flask, and stir for 0.5h to make them fully mixed and dissolved. Slowly add a certain amount of urea, reactive phosphazene C and a small amount of melamine to the above mixed solution, adjust the pH to 3-6 with dilute hydrochloric acid, stir for 2 hours and set aside for use.

[0052] (2) CN-BIVB 12 Dissolve in a small amount of toluene and disperse at high speed to ensure complete dissolution, forming a core material dispersion;

[0053] (3) Add CN-BIVB to the mixed solution in step 1 12The core material dispersion was stirred for 20-30 minutes using a high-speed shear emulsifier at 10000-15000 r / min. The emulsified mixture was transferred to a three-necked flask, and a certain amount of 37% formaldehyde solution was added dropwise. The mixture was reacted at 50-100℃ for 4-8 hours. After cooling to room temperature, the solution was adjusted to neutral with sodium hydroxide solution to obtain a suspension of refractory-modified aggregation-induced light-emitting urea-formaldehyde microcapsules. After cooling to room temperature, washing, and filtration, the suspension was dried in a vacuum drying oven at 40℃ for 48 hours. The resulting refractory-modified aggregation-induced light-emitting urea-formaldehyde microcapsules (CN-BIVB) were then prepared. 12 Store in a desiccator for later use.

[0054] The coating preparation method includes the following steps: Polyurethane resin, polyester resin, quartz powder, aluminum hydroxide, diatomaceous earth, potassium salt of polyacrylic acid copolymer, polyether-modified silicone defoamer, polyether siloxane, organobentonite, nitrogen-containing organic compounds, zinc phosphate, propylene glycol methyl ether, and n-butanol are mixed in parts by weight and placed in a disperser, and stirred thoroughly at 1000-2000 rpm for 40-60 minutes. After uniform mixing, refractory-modified aggregation-induced light-emitting urea-formaldehyde microcapsules (CN-BIVB) are added. 12 Stir for another 30 minutes at 400-600 rpm. After thorough stirring, filter, package, and store in the finished product warehouse, labeling as described.

[0055] Example 4

[0056] The formulation of the environmentally friendly aggregation-induced light-emitting flame-retardant coating in this embodiment is as follows, all by weight:

[0057] 50 parts polyester resin, 70 parts acrylic resin, 22 parts aluminum hydroxide, 9 parts diatomaceous earth, 11 parts montmorillonite, and refractory-modified aggregation-induced luminescence urea-formaldehyde microcapsules CN-BIVB 14 2.3 parts, potassium salt of polyacrylic acid copolymer 1.7 parts, silicone defoamer 1.7 parts, silicone modified polysiloxane 1.3 parts, organobentonite 1.3 parts, phenolic compound 0.9 parts, aluminum tripolyphosphate 1.8 parts, cyclohexanone 25 parts, ethylene glycol butyl ether 24 parts.

[0058] Refractory modified aggregation-induced light-emitting urea-formaldehyde microcapsules CN-BIVB 14 The preparation method includes the following steps:

[0059] (1) Add a certain amount of sodium dodecylbenzenesulfonate, sodium lignosulfonate, polyether polyol and deionized water to a 250mL three-necked flask, and stir for 0.5h to ensure thorough mixing and dissolution. Slowly add a certain amount of urea, reactive phosphazene D and a small amount of melamine to the above mixed solution, adjust the pH to 3-6 with dilute hydrochloric acid, stir for 2 hours and set aside for use.

[0060] (2) CN-BIVB14 Dissolve in a small amount of toluene and disperse at high speed to ensure complete dissolution, forming a core material dispersion;

[0061] (3) Add CN-BIVB to the mixed solution in step 1 14 The core material dispersion was stirred for 20-30 minutes using a high-speed shear emulsifier at 10000-15000 r / min. The emulsified mixture was transferred to a three-necked flask, and a certain amount of 37% formaldehyde solution was added dropwise. The mixture was reacted at 50-100℃ for 4-8 hours. After cooling to room temperature, the solution was adjusted to neutral with sodium hydroxide solution to obtain a suspension of refractory-modified aggregation-induced light-emitting urea-formaldehyde microcapsules. After cooling to room temperature, washing, and filtration, the suspension was dried in a vacuum drying oven at 40℃ for 48 hours. The resulting refractory-modified aggregation-induced light-emitting urea-formaldehyde microcapsules (CN-BIVB) were then prepared. 14 Store in a desiccator for later use.

[0062] The coating preparation method includes the following steps: Polyester resin, acrylic resin, aluminum hydroxide, diatomaceous earth, montmorillonite, potassium salt of polyacrylic acid copolymer, organosilicon defoamer, organosilicon-modified polysiloxane, organobentonite, phenolic compounds, aluminum tripolyphosphate, cyclohexanone, and ethylene glycol butyl ether are mixed according to weight parts and placed in a disperser, and stirred thoroughly at 1000-2000 rpm for 40-60 minutes. After uniform mixing, refractory-modified aggregation-induced light-emitting urea-formaldehyde microcapsules CN-BIVB are added. 14 Stir for another 30 minutes at 400-600 rpm. After thorough stirring, filter, package, and store in the finished product warehouse, labeling as described.

[0063] Example 5

[0064] The formulation of the environmentally friendly aggregation-induced light-emitting flame-retardant coating in this embodiment is as follows, all by weight:

[0065] 70 parts polyurethane resin, 60 parts acrylic resin, 22 parts barium sulfate, 11 parts kaolin, 17 parts quartz powder, and refractory-modified aggregation-induced luminescence urea-formaldehyde microcapsules CN-BIVB 16 3 parts, potassium salt of polyacrylic acid copolymer 2 parts, polyether defoamer 2 parts, polyether siloxane 1.5 parts, organobentonite 1.5 parts, sulfur-containing organic compound 1 part, zinc phosphate 2 parts, cyclohexanone 25 parts, propylene glycol methyl ether 25 parts.

[0066] Refractory modified aggregation-induced light-emitting urea-formaldehyde microcapsules CN-BIVB 16 The preparation method includes the following steps:

[0067] (1) Add a certain amount of sodium dodecylbenzenesulfonate, sodium lignosulfonate, polypropylene glycol and deionized water to a 250mL three-necked flask, and stir for 0.5h to ensure thorough mixing and dissolution. Slowly add a certain amount of urea, reactive phosphazene B and a small amount of melamine to the above mixed solution, adjust the pH to 3-6 with dilute hydrochloric acid, stir for 2 hours and set aside for use.

[0068] (2) CN-BIVB 16 Dissolve in a small amount of toluene and disperse at high speed to ensure complete dissolution, forming a core material dispersion;

[0069] (3) Add CN-BIVB to the mixed solution in step 1 16 The core material dispersion was stirred for 20-30 minutes using a high-speed shear emulsifier at 10000-15000 r / min. The emulsified mixture was transferred to a three-necked flask, and a certain amount of 37% formaldehyde solution was added dropwise. The mixture was reacted at 50-100℃ for 4-8 hours. After cooling to room temperature, the solution was adjusted to neutral with sodium hydroxide solution to obtain a suspension of refractory-modified aggregation-induced light-emitting urea-formaldehyde microcapsules. After cooling to room temperature, washing, and filtration, the suspension was dried in a vacuum drying oven at 40℃ for 48 hours. The resulting refractory-modified aggregation-induced light-emitting urea-formaldehyde microcapsules (CN-BIVB) were then prepared. 16 Store in a desiccator for later use.

[0070] The coating preparation method includes the following steps: Polyurethane resin, acrylic resin, barium sulfate, kaolin, quartz powder, potassium salt of polyacrylic acid copolymer, polyether defoamer, polyether siloxane, organobentonite, sulfur-containing organic compounds, zinc phosphate, cyclohexanone, and propylene glycol methyl ether are mixed according to weight parts and placed in a disperser, and stirred thoroughly at 1000-2000 rpm for 40-60 minutes. After uniform mixing, refractory-modified aggregation-induced light-emitting urea-formaldehyde microcapsules CN-BIVB are added. 16 Stir for another 30 minutes at 400-600 rpm. After thorough stirring, filter, package, and store in the finished product warehouse, labeling as described.

[0071] Example 6

[0072] The formulation of the environmentally friendly aggregation-induced light-emitting flame-retardant coating in this embodiment is as follows, all by weight:

[0073] 70 parts polyurethane resin, 60 parts acrylic resin, 22 parts barium sulfate, 11 parts kaolin, 17 parts quartz powder, 3 parts refractory modified aggregation-induced light-emitting urea-formaldehyde microcapsules (TPI), 2 parts potassium salt of polyacrylic acid copolymer, 2 parts polyether defoamer, 1.5 parts polyether siloxane, 1.5 parts organobentonite, 1 part sulfur-containing organic compound, 2 parts zinc phosphate, 25 parts cyclohexanone, and 25 parts propylene glycol methyl ether.

[0074] The preparation method of refractory modified aggregation-induced light-emitting urea-formaldehyde microcapsules (TPI) includes the following steps:

[0075] (1) Add a certain amount of sodium dodecylbenzenesulfonate, sodium lignosulfonate, polypropylene glycol and deionized water to a 250mL three-necked flask, and stir for 0.5h to ensure thorough mixing and dissolution. Slowly add a certain amount of urea, reactive phosphazene B and a small amount of melamine to the above mixed solution, adjust the pH to 3-6 with dilute hydrochloric acid, stir for 2 hours and set aside for use.

[0076] (2) Dissolve TPI in a small amount of toluene and disperse it at high speed to ensure complete dissolution, forming a core material dispersion;

[0077] (3) Add the TPI core material dispersion to the mixed solution in step 1, and stir for 20-30 min at 10000-15000 r / min using a high-speed shear emulsifier. Transfer the emulsified mixture to a three-necked flask, and add a certain amount of 37% formaldehyde solution dropwise. React at 50-100℃ for 4-8 hours. After cooling to room temperature, adjust to neutral with sodium hydroxide solution to obtain a refractory-modified aggregation-induced light-emitting urea-formaldehyde microcapsule suspension. After cooling to room temperature, washing, and filtration, place in a vacuum drying oven and dry at 40℃ for 48 h. Place the obtained refractory-modified aggregation-induced light-emitting urea-formaldehyde microcapsule TPI in a desiccator for later use.

[0078] The coating preparation method includes the following steps: Polyurethane resin, acrylic resin, barium sulfate, kaolin, quartz powder, potassium salt of polyacrylic acid copolymer, polyether defoamer, polyether siloxane, organobentonite, sulfur-containing organic compounds, zinc phosphate, cyclohexanone, and propylene glycol methyl ether are mixed according to weight parts and placed in a disperser, and stirred thoroughly at 1000-2000 rpm for 40-60 minutes. After uniform mixing, refractory-modified aggregation-induced light-emitting urea-formaldehyde microcapsules (TPI) are added, and the mixture is stirred again at 400-600 rpm for 30 minutes. After thorough stirring, the mixture is filtered, packaged, and placed in the finished product warehouse, with labeling and identification.

[0079] Comparative Example 1

[0080] The formulation of this comparative environmentally friendly aggregation-induced luminescence flame-retardant coating is as follows, all by weight:

[0081] 70 parts polyurethane resin, 60 parts acrylic resin, 22 parts barium sulfate, 11 parts kaolin, 17 parts quartz powder, and lignin-modified aggregation-induced luminescence urea-formaldehyde microcapsules CN-BIVB 16 3 parts, potassium salt of polyacrylic acid copolymer 2 parts, polyether defoamer 2 parts, polyether siloxane 1.5 parts, organobentonite 1.5 parts, sulfur-containing organic compound 1 part, zinc phosphate 2 parts, cyclohexanone 25 parts, propylene glycol methyl ether 25 parts.

[0082] Lignin-modified aggregation-induced luminescence urea-formaldehyde microcapsules CN-BIVB 16 The preparation method includes the following steps:

[0083] (1) Add a certain amount of sodium dodecylbenzenesulfonate, sodium lignosulfonate, polypropylene glycol and deionized water to a 250mL three-necked flask, and stir for 0.5h to ensure thorough mixing and dissolution. Slowly add a certain amount of urea and a small amount of melamine to the above mixed solution, adjust the pH to 3-6 with dilute hydrochloric acid, stir for 2 hours and set aside for use.

[0084] (2) CN-BIVB 16 Dissolve in a small amount of toluene and disperse at high speed to ensure complete dissolution, forming a core material dispersion;

[0085] (3) Add CN-BIVB to the mixed solution in step 1 16 The core material dispersion was stirred for 20-30 minutes using a high-speed shear emulsifier at 10000-15000 r / min. The emulsified mixture was transferred to a three-necked flask, and a certain amount of 37% formaldehyde solution was added dropwise. The mixture was reacted at 50-100℃ for 4-8 hours. After cooling to room temperature, the solution was adjusted to neutral with sodium hydroxide solution to obtain a lignin-modified aggregation-induced emission urea-formaldehyde microcapsule suspension. After cooling to room temperature, washing, and filtration, the suspension was dried in a vacuum drying oven at 40℃ for 48 hours. The resulting lignin-modified aggregation-induced emission urea-formaldehyde microcapsules (CN-BIVB) were then prepared. 16 Store in a desiccator for later use.

[0086] The coating preparation method includes the following steps: Polyurethane resin, acrylic resin, barium sulfate, kaolin, quartz powder, potassium salt of polyacrylic acid copolymer, polyether defoamer, polyether siloxane, organobentonite, sulfur-containing organic compounds, zinc phosphate, cyclohexanone, and propylene glycol methyl ether are mixed according to weight parts and placed in a disperser, and stirred thoroughly at 1000-2000 rpm for 40-60 minutes. After uniform mixing, lignin-modified aggregation-induced luminescence urea-formaldehyde microcapsules CN-BIVB are added. 16 Stir for another 30 minutes at 400-600 rpm. After thorough stirring, filter, package, and store in the finished product warehouse, labeling as described.

[0087] Comparative Example 2

[0088] The formulation of this comparative environmentally friendly aggregation-induced luminescence flame-retardant coating is as follows, all by weight:

[0089] 70 parts polyurethane resin, 60 parts acrylic resin, 22 parts barium sulfate, 11 parts kaolin, 17 parts quartz powder, and phosphazene-modified aggregation-induced luminescence urea-formaldehyde microcapsules CN-BIVB 163 parts, potassium salt of polyacrylic acid copolymer 2 parts, polyether defoamer 2 parts, polyether siloxane 1.5 parts, organobentonite 1.5 parts, sulfur-containing organic compound 1 part, zinc phosphate 2 parts, cyclohexanone 25 parts, propylene glycol methyl ether 25 parts.

[0090] Phosphazene-modified aggregation-induced luminescence urea-formaldehyde microcapsules CN-BIVB 16 The preparation method includes the following steps:

[0091] (1) Add a certain amount of sodium dodecylbenzenesulfonate, polypropylene glycol and deionized water to a 250mL three-necked flask, and stir for 0.5h to ensure thorough mixing and dissolution. Slowly add a certain amount of urea, reactive phosphazene B and a small amount of melamine to the above mixed solution, adjust the pH to 3-6 with dilute hydrochloric acid, stir for 2 hours and set aside for use.

[0092] (2) CN-BIVB 16 Dissolve in a small amount of toluene and disperse at high speed to ensure complete dissolution, forming a core material dispersion;

[0093] (3) Add CN-BIVB to the mixed solution in step 1 16 The core material dispersion was stirred for 20-30 minutes using a high-speed shear emulsifier at 10000-15000 r / min. The emulsified mixture was transferred to a three-necked flask, and a certain amount of 37% formaldehyde solution was added dropwise. The mixture was reacted at 50-100℃ for 4-8 hours. After cooling to room temperature, the solution was adjusted to neutral with sodium hydroxide solution to obtain a phosphazene-modified aggregation-induced luminescence urea-formaldehyde microcapsule suspension. After cooling to room temperature, washing, and filtration, the suspension was dried in a vacuum drying oven at 40℃ for 48 hours. The resulting phosphazene-modified aggregation-induced luminescence urea-formaldehyde microcapsules CN-BIVB were then prepared. 16 Store in a desiccator for later use.

[0094] The coating preparation method includes the following steps: Polyurethane resin, acrylic resin, barium sulfate, kaolin, quartz powder, potassium salt of polyacrylic acid copolymer, polyether defoamer, polyether siloxane, organobentonite, sulfur-containing organic compounds, zinc phosphate, cyclohexanone, and propylene glycol methyl ether are mixed according to weight parts and placed in a disperser, and stirred thoroughly at 1000-2000 rpm for 40-60 minutes. After uniform mixing, phosphazene-modified aggregation-induced luminescence urea-formaldehyde microcapsules CN-BIVB are added. 16 Stir for another 30 minutes at 400-600 rpm. After thorough stirring, filter, package, and store in the finished product warehouse, labeling as described.

[0095] Comparative Example 3

[0096] The formulation of the environmentally friendly aggregation-induced light-emitting flame-retardant coating in this embodiment is as follows, all by weight:

[0097] 70 parts polyurethane resin, 60 parts acrylic resin, 22 parts barium sulfate, 11 parts kaolin, 17 parts quartz powder, modified aggregation-induced light-emitting urea-formaldehyde microcapsules CN-BIVB 16 3 parts, potassium salt of polyacrylic acid copolymer 2 parts, polyether defoamer 2 parts, polyether siloxane 1.5 parts, organobentonite 1.5 parts, sulfur-containing organic compound 1 part, zinc phosphate 2 parts, cyclohexanone 25 parts, propylene glycol methyl ether 25 parts.

[0098] Modified aggregation-induced luminescence urea-formaldehyde microcapsules CN-BIVB 16 The preparation method includes the following steps:

[0099] (1) Add a certain amount of sodium dodecylbenzenesulfonate, sodium lignosulfonate, polypropylene glycol and deionized water to a 250mL three-necked flask, and stir for 0.5h to ensure thorough mixing and dissolution. Slowly add a certain amount of urea, phenoxycyclophosphonitrile and a small amount of melamine to the above mixed solution, adjust the pH to 3-6 with dilute hydrochloric acid, stir for 2 hours and set aside for use.

[0100] (2) CN-BIVB 16 Dissolve in a small amount of toluene and disperse at high speed to ensure complete dissolution, forming a core material dispersion;

[0101] (3) Add CN-BIVB to the mixed solution in step 1 16 The core material dispersion was stirred for 20-30 minutes using a high-speed shear emulsifier at 10000-15000 r / min. The emulsified mixture was transferred to a three-necked flask, and a certain amount of 37% formaldehyde solution was added dropwise. The mixture was reacted at 50-100℃ for 4-8 hours. After cooling to room temperature, the solution was adjusted to neutral with sodium hydroxide solution to obtain a suspension of modified aggregation-induced emission urea-formaldehyde microcapsules. After cooling to room temperature, washing, and filtration, the suspension was dried in a vacuum drying oven at 40℃ for 48 hours. The resulting modified aggregation-induced emission urea-formaldehyde microcapsules CN-BIVB were then prepared. 16 Store in a desiccator for later use.

[0102] The coating preparation method includes the following steps: Polyurethane resin, acrylic resin, barium sulfate, kaolin, quartz powder, potassium salt of polyacrylic acid copolymer, polyether defoamer, polyether siloxane, organobentonite, sulfur-containing organic compounds, zinc phosphate, cyclohexanone, and propylene glycol methyl ether are mixed according to weight parts and placed in a disperser, and stirred thoroughly at 1000-2000 rpm for 40-60 minutes. After uniform mixing, modified aggregation-induced luminescence urea-formaldehyde microcapsules CN-BIVB are added. 16 Stir for another 30 minutes at 400-600 rpm. After thorough stirring, filter, package, and store in the finished product warehouse, labeling as described.

[0103] The coatings obtained in Examples 1 to 3 were subjected to performance testing, and the results are as follows:

[0104]

[0105]

[0106] This invention utilizes fire-resistant modified urea-formaldehyde resin microcapsules to encapsulate AIE fluorescent materials, preparing a series of environmentally friendly aggregation-induced emission (AIE) flame-retardant coatings. Compared to ordinary urea-formaldehyde resin microcapsules, the modified urea-formaldehyde resin microcapsules prepared with polyol ethers, sodium lignosulfonate, and reactive phosphazenes exhibit stronger anti-aging properties, flexibility, environmental friendliness, mechanical properties, and flame retardancy. Simultaneously, phosphazene compounds possess excellent flame-retardant properties, and the functional groups in the reactive phosphazenes can chemically bond with the groups in the modified urea-formaldehyde resin, thereby introducing phosphazene fragments into the microcapsule shell. These phosphazene fragments, combined with heat-resistant lignin groups, synergistically exhibit superior flame-retardant and fire-resistant effects, effectively preventing AIE fluorescent agent leakage due to high-temperature shell rupture and reduced indication performance. In terms of technical effects, the coatings of this invention exhibit excellent temperature resistance, hardness, adhesion, corrosion resistance, and flame-retardant properties. Under different temperatures, the addition of CN-BIVB... 14 CN-BIVB 16 Both coatings containing TPI microcapsules and coatings with these materials exhibit color changes at high temperatures, demonstrating excellent flame retardant and early warning properties. In particular, coatings with added TPI microcapsules can even show a gradual linear color change effect at different temperatures. These environmentally friendly, aggregation-induced light-emitting flame-retardant coatings integrate aesthetic appeal, flame retardancy, and temperature warning, providing timely alerts for changes in external temperature.

[0107] The specific embodiments of the present invention have been described above. It should be understood that the present invention is not limited to the specific embodiments described above, and those skilled in the art can make various modifications and variations within the scope of the claims, which do not affect the essence of the present invention.

Claims

1. An environmentally friendly aggregation-induced luminescence flame-retardant coating, characterized in that, All components are expressed in parts by weight and include the following: 100-130 parts film-forming resin, 30-50 parts filler, 1-3 parts refractory modified aggregation-induced light-emitting urea-formaldehyde microcapsules, 1-2 parts wetting agent, 1-2 parts defoamer, 1-1.5 parts leveling agent, 0.5-1.5 parts anti-settling agent, 0.8-1 part mildew inhibitor, 1-2 parts rust inhibitor, and 40-50 parts diluent. The refractory-modified aggregation-induced emission urea-formaldehyde microcapsules comprise an aggregation-induced emission fluorescent material as the core structure and a refractory-modified urea-formaldehyde resin as the shell structure. The preparation method of the refractory-modified aggregation-induced emission urea-formaldehyde microcapsules includes the following steps: (1) Add a certain amount of sodium dodecylbenzenesulfonate, sodium lignosulfonate, polyol ether and deionized water to a 250mL three-necked flask, stir for 0.5h to make it fully mixed and dissolved, slowly add a certain amount of urea, reactive phosphazene and a small amount of melamine to the above mixed solution, adjust the pH to 3-6 with dilute hydrochloric acid, stir for 2 hours and set aside for use. (2) Dissolve the aggregation-induced emission fluorescent material in a small amount of toluene and disperse it at high speed to ensure complete dissolution, forming a core material dispersion; (3) Add the core material dispersion to the mixed solution obtained in step (1), and stir for 20-30 min at 10000-15000 r / min using a high-speed shear emulsifier; transfer the emulsified mixture to a three-necked flask, add a certain amount of formaldehyde solution with a mass fraction of 37% dropwise, react at 50-100℃ for 4-8 hours, cool to room temperature and adjust to neutral with sodium hydroxide solution to obtain a suspension of refractory modified aggregation-induced luminescence urea-formaldehyde microcapsules; cool to room temperature, wash, filter, and place in a vacuum drying oven to dry at 40℃ for 48 h, and place the obtained refractory modified aggregation-induced luminescence urea-formaldehyde microcapsules in a desiccator for later use; The polyol ether is polyvinyl alcohol, polyether polyol, and amine-terminated polyether; The structure of the aggregation-induced emission fluorescent material includes: The structure of the reactive phosphazene includes:

2. The environmentally friendly aggregation-induced light-emitting flame-retardant coating according to claim 1, characterized in that, Film-forming resins include two or more of the following: fluorocarbon resins, silicone resins, polyurethane resins, polyester resins, and acrylic resins.

3. The environmentally friendly aggregation-induced light-emitting flame-retardant coating according to claim 1, characterized in that, The filler includes two or more of the following: mica powder, barium sulfate, calcium carbonate, talc powder, attapulgite, kaolin, quartz powder, aluminum hydroxide, diatomaceous earth, and montmorillonite.

4. The environmentally friendly aggregation-induced light-emitting flame-retardant coating according to claim 1, characterized in that, The wetting agent is a potassium salt of polyacrylic acid copolymer; the defoamer is one or more of organosilicon defoamer, polyether defoamer, or polyether-modified silicone defoamer; the leveling agent is one or more of organosilicon-modified polysiloxane or polyether-modified siloxane; and the anti-settling agent is organobentonite.

5. The environmentally friendly aggregation-induced light-emitting flame-retardant coating according to claim 1, characterized in that, The mildew inhibitor is one or more of phenolic compounds, sulfur-containing organic compounds, or nitrogen-containing organic compounds; the rust inhibitor 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.

6. A method for preparing an environmentally friendly aggregation-induced light-emitting flame-retardant coating as described in any one of claims 1-5, comprising the following steps: mixing film-forming resin, filler, wetting agent, defoamer, leveling agent, anti-settling agent, mildew inhibitor, rust inhibitor, and diluent in parts by weight and placing them in a disperser, and stirring thoroughly at 1000-2000 rpm for 40-60 minutes; after uniform mixing, adding refractory-modified aggregation-induced light-emitting urea-formaldehyde microcapsules, and stirring again at 500-800 rpm for 30 minutes; after thorough mixing, filtering, packaging, and placing in the finished product warehouse, and labeling.

7. The application of an environmentally friendly aggregation-induced light-emitting flame-retardant coating as described in any one of claims 1-5 in fire-resistant materials.

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