Fireproof flame-retardant coating and preparation method thereof

Abstract

The invention relates to a fireproof flame-retardant coating and a preparation method thereof. The coating comprises the following components in parts by weight: 50-70 parts of water-based hydroxy acrylic latex, 4-10 parts of a flame-retardant functional component, 1-5 parts of a coalescing agent, 0.1-2 parts of a defoaming agent, 10-20 parts of filler, 0.1-2 parts of a dispersing agent, 0.1-2 parts of a preservative, 0.1-2 parts of a flatting agent and 10-30 parts of deionized water. Compared with the prior art, the coating obtained by the invention has excellent fire resistance, water resistance, acid resistance, alkali resistance and good adhesive force during use.

Description

Technical Field

[0001] The invention relates to the technical field of coatings, and in particular to a fire-resistant flame-retardant coating and a preparation method thereof. Background Art

[0002] Waterborne paint, also known as water-based paint or water-based paint, is a paint with water as the main solvent. It is a green and environmentally friendly paint. Waterborne paint includes three types: water-dilutable, water-dispersible (latex paint) and water-soluble. Compared with solvent-based paint, it uses water as the main volatile component, and has the advantages of being non-toxic, environmentally friendly, odorless, having very few volatiles, and being non-flammable and non-explosive. Waterborne acrylic resin paint is the main variety with the highest market share. It has the advantages of good light resistance, weather resistance, heat resistance, light color, and good construction performance. It has been used in the automotive, furniture, and construction industries. However, waterborne acrylic paint also has the disadvantages of long drying time, easy to become sticky at high temperatures, easy to become brittle at low temperatures, and flammable itself. In particular, the flammable disadvantage of waterborne acrylic paint itself can easily lead to fires, resulting in a large number of casualties and significant property losses, which seriously restricts the widespread promotion and application of waterborne acrylic paint.

[0003] For example, CN112281236A discloses a triazine flame retardant modified ultra-high molecular weight polyethylene fiber and a preparation method thereof, comprising the following component raw materials, ultra-high molecular weight polyethylene fiber and triazine flame retardant, wherein the weight ratio of the ultra-high molecular weight polyethylene fiber to the triazine flame retardant is 1:(0.1-0.5); the triazine flame retardant comprises the following component raw materials, intermediate I, diaminodiphenylmethane, dioxane and dibutyltin dilaurate, wherein the weight ratio of the intermediate I, diaminodiphenylmethane, dioxane and dibutyltin dilaurate is (4-6):(6-10):(40-60):(0.5-2); the intermediate I comprises the following component raw materials by weight, cyanuric chloride, acetone solution and diphenylamine, wherein the weight ratio of cyanuric chloride, acetone solution and diphenylamine is (5-10):(20-30):(2-5).

[0004] For example, CN118530641A discloses a method for preparing a modified polyacrylic acid fire retardant coating. The present invention uses (2-carboxylethyl)phenylphosphonic acid and methylvinyldichlorosilane as raw materials to prepare intermediate 1, which is then reacted with thionyl chloride and PEPA to prepare phosphorus-containing modified vinyl silane. Nano silicon dioxide and trimethoxy (4-vinylphenyl) silane are used as raw materials to obtain vinyl nano silicon dioxide. Butyl acrylate and phosphorus-containing modified vinyl silane and vinyl nano silicon dioxide are subjected to emulsion polymerization to obtain a modified polyacrylic acid emulsion, and finally a dispersant is added thereto to mix uniformly to obtain a modified polyacrylic acid fire retardant coating.

[0005] For example, CN118271885B discloses a fire retardant coating and a preparation method thereof, which is made of the following raw materials in parts by weight: 50-60 parts of hyperbranched perfluoropolyether polyurethane acrylate polymer, 6-8 parts of flame retardant functional components containing unsaturated olefinic bonds, 3-5 parts of 2,4,6-trivinyl cycloboroxine, 1-3 parts of 3,9-divinyl-2,4,8,10-tetraoxaspiro[5.5]undecane, 3-5 parts of 3-[N,N-dimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]ammonium]propane-1-sulfonic acid inner salt, 1-3 parts of 10-(4-vinylphenyl)-10H-phenoxazine, 2-4 parts of 2-vinylpyrimidine, 10-20 parts of inorganic filler, 1-3 parts of coupling agent, 1-3 parts of defoaming agent, 1-3 parts of dispersant, 0.8-1.2 parts of leveling agent, and 3-5 parts of photoinitiator.

[0006] However, the flame retardant effect of the above coatings is single, and most of them use organic phosphorus to generate a carbon layer for flame retardancy, and the flame retardant performance is still to be improved. Based on this, the present invention is specially proposed. Summary of the invention

[0007] The purpose of the present invention is to provide a fire-resistant flame-retardant coating and a preparation method thereof in order to overcome the poor flame retardant performance and single flame retardant effect of the above-mentioned prior art. The coating obtained by the present invention has excellent fire resistance, water resistance, acid resistance, alkali resistance, and good adhesion when used.

[0008] The purpose of the present invention can be achieved by the following technical solutions:

[0009] The invention provides a fire-resistant flame-retardant coating, comprising the following components by weight: 50-70 parts of water-based hydroxy acrylic latex, 4-10 parts of flame-retardant functional components, 1-5 parts of film-forming aids, 0.1-2 parts of defoaming agents, 10-20 parts of fillers, 0.1-2 parts of dispersants, 0.1-2 parts of preservatives, 0.1-2 parts of leveling agents, and 10-30 parts of deionized water.

[0010] Preferably, the water-based strong hydroxyl acrylic latex is prepared in the following manner:

[0011] Add emulsifier and deionized water into a flask, and then add methyl methacrylate, butyl acrylate, hydroxypropyl acrylate and styrene, pre-emulsify for 0.5-1.5 hours to obtain a liquid phase, then add initiator and deionized water into a four-necked flask, and then add the above liquid phase, react at 70-90°C for 4 hours, cool and filter to obtain water-based hydroxy acrylic latex.

[0012] Preferably, the emulsifier is sodium dodecylbenzene sulfonate as a film-forming aid, and the initiator is potassium persulfate;

[0013] And / or, the mass ratio of the emulsifier, methyl methacrylate, butyl acrylate, hydroxypropyl acrylate, styrene, and initiator is (3-6): (20-30): (30-40): (10-20): (1-5).

[0014] Preferably, the flame retardant functional component is prepared by the following method:

[0015] 4-chlorophenyl diphenyl phosphate, diboronic acid pinacol ester, Pd(dppf)Cl2, potassium acetate, and 1,4-dioxane were added to a flask in sequence, and the mixture was stirred at 80-120° C. for 1-3 hours. After the reaction was completed, it was purified by column chromatography to obtain intermediate 1;

[0016] Then add intermediate 1, cyanuric chloride, Pd(PPh3)4, and potassium carbonate into a flask, and then add toluene, ethanol, and water in sequence. Then stir the mixture at 80-120°C for 1-3 hours. After the reaction is completed, purify it by column chromatography to obtain a flame retardant functional component.

[0017] Preferably, the ratio of the amount of 4-chlorophenyl diphenyl phosphate, diboronic acid pinacol ester, Pd(dppf)Cl2, potassium acetate, and 1,4-dioxane is (50-70) mmol: (50-70) mmol: (1-2) mmol: (100-150) mmol: (150-300) ml;

[0018] And / or, the ratio of the intermediate 1, cyanuric chloride, Pd(PPh3)4, potassium carbonate, toluene, ethanol, and water is (150-180)mmol:(50-60)mmol:(0.5-2)mmol:(100-120)mmol:(100-200)ml:(50-100)ml:(50-100)ml.

[0019] Preferably, the film-forming aid is selected from one or more of ethylene glycol butyl ether, diethylene glycol butyl ether, triethylene glycol butyl ether, diethylene glycol ethyl ether, ethylene glycol hexyl ether, and ethylene glycol phenyl ether;

[0020] And / or, the defoamer is a higher alcohol defoamer or an organosilicon defoamer;

[0021] And / or, the filler is one or more of double fly ash, titanium dioxide, talcum powder, feldspar powder, and precipitated barium sulfate;

[0022] And / or, the dispersant is one or more of sodium hexametaphosphate, sodium salt of polycarboxylate, potassium salt of polyacrylate, sodium salt of polyacrylate;

[0023] And / or, the preservative is one or more of aluminum dihydrogen tripolyphosphate, zinc phosphate, and zinc hydroxyphosphite;

[0024] And / or, the leveling agent is German BYK leveling agent BYK-333 or silicone leveling agent HY-5030.

[0025] The present invention also provides a method for preparing a fire-resistant flame-retardant coating, comprising the following steps:

[0026] S1, add an emulsifier and deionized water into a flask, then add methyl methacrylate, butyl acrylate, hydroxypropyl acrylate, and styrene thereto, pre-emulsify for 0.5-1.5 hours to obtain a liquid phase, then add an initiator and deionized water into a four-necked flask, then add the above liquid phase, react at 70-90° C. for 4 hours, cool and filter to obtain a water-based hydroxy acrylic latex;

[0027] S2, 4-chlorophenyl diphenyl phosphate, diboronic acid pinacol ester, Pd(dppf)Cl2, potassium acetate are added to a flask in sequence, and then 1,4-dioxane is added, and then the mixture is stirred at 80-120° C. for 1-3 hours. After the reaction is completed, it is purified by column chromatography to obtain intermediate 1, and then intermediate 1, cyanuric chloride, Pd(PPh3)4, and potassium carbonate are added to a flask, and then toluene, ethanol, and water are added in sequence, and then the mixture is stirred at 80-120° C. for 1-3 hours. After the reaction is completed, it is purified by column chromatography to obtain a flame retardant functional component;

[0028] S3, mixing water-based hydroxy acrylic latex, flame retardant functional components, film-forming aids, defoaming agents, fillers, dispersants, preservatives, leveling agents, and deionized water, and stirring at 1800-2000 r / min for 5-15 minutes to obtain a fire-resistant flame retardant coating.

[0029] Preferably, in step S1, the emulsifier is sodium dodecylbenzene sulfonate film-forming aid, and the initiator is potassium persulfate;

[0030] And / or, in step S1, the mass ratio of the emulsifier, methyl methacrylate, butyl acrylate, hydroxypropyl acrylate, styrene, and initiator is (3-6): (20-30): (30-40): (10-20): (1-5);

[0031] And / or, in step S2, the ratio of the amount of 4-chlorophenyl diphenyl phosphate, diboronic acid pinacol ester, Pd(dppf)Cl2, potassium acetate, and 1,4-dioxane is (50-70) mmol: (50-70) mmol: (1-2) mmol: (100-150) mmol: (150-300) ml;

[0032] And / or, in step S2, the ratio of the intermediate 1, cyanuric chloride, Pd(PPh3)4, potassium carbonate, toluene, ethanol, and water is (150-180) mmol: (50-60) mmol: (0.5-2) mmol: (100-120) mmol: (100-200) ml: (50-100) ml: (50-100) ml.

[0033] Preferably, in step S3, the mass ratio of the water-based hydroxylated acrylic latex, the flame retardant functional component, the film-forming aid, the defoaming agent, the filler, the dispersant, the preservative, the leveling agent, and the deionized water is (50-70): (4-10): (1-5): (0.1-2): (10-20): (0.1-2): (0.1-2): (0.1-2): (10-30);

[0034] And / or, in step S3, the film-forming aid is selected from one or more of ethylene glycol butyl ether, diethylene glycol butyl ether, triethylene glycol butyl ether, diethylene glycol ethyl ether, ethylene glycol hexyl ether, and ethylene glycol phenyl ether;

[0035] And / or, in step S3, the defoamer is a higher alcohol defoamer or an organosilicon defoamer;

[0036] And / or, in step S3, the filler is one or more of double fly ash, titanium dioxide, talcum powder, feldspar powder, and precipitated barium sulfate;

[0037] And / or, in step S3, the dispersant is one or more of sodium hexametaphosphate, sodium salt of polycarboxylate, potassium salt of polyacrylate, and sodium salt of polyacrylate;

[0038] And / or, in step S3, the preservative is one or more of aluminum dihydrogen tripolyphosphate, zinc phosphate, and zinc hydroxyphosphite;

[0039] And / or, in step S3, the leveling agent is German BYK leveling agent BYK-333 or silicone leveling agent HY-5030.

[0040] The present invention further provides a fire-resistant flame-retardant coating obtained by the preparation method of the fire-resistant flame-retardant coating as described above.

[0041] Compared with the prior art, the present invention has the following beneficial effects:

[0042] The formula obtained by the present invention improves the compatibility with the flame retardant functional component by using a self-made water-based hydroxyl acrylic latex, and on the other hand, by synthesizing an organic phosphorus heterocyclic compound flame retardant, the phosphorus-nitrogen synergistic effect is concentrated in one functional component to achieve a synergistic flame retardant effect of gas phase flame retardancy and condensed phase flame retardancy. The flame retardant functional component in the present application contains a large amount of N and P elements. When the coating is heated, a dense carbon layer is first formed. When the phosphorus element is heated, it can produce strong dehydrating substances such as polyphosphoric acid and metaphosphoric acid, which promotes the coating. Dehydration into carbon forms a dense carbon layer. The carbon layer is non-combustible and can isolate oxygen, making combustion impossible. Its thermal conductivity is poor, which can effectively reduce the heat transferred from the flame zone to the substrate, thereby reducing the mass loss rate of the material and the amount of combustibles generated. Then, non-combustible gases are released, among which N element is easily heated to release non-combustible gases such as CO2, N2, NH3 and H2O. Through these non-combustible gases, the oxygen in the air and the concentration of combustibles produced by thermal decomposition of polymers can be diluted. At the same time, part of the heat can be taken away in thermal convection, so that N element and P element can achieve the synergistic flame retardant effect of gas phase flame retardant and condensed phase flame retardant. DETAILED DESCRIPTION

[0043] For ease of understanding of the present application, the present application will be described more fully below by way of embodiments. However, the present application can be implemented in many different forms and is not limited to the embodiments described herein. On the contrary, the purpose of providing these embodiments is to make the understanding of the disclosure of the present application more thorough and comprehensive.

[0044] For simplicity, the present application only explicitly discloses some numerical ranges. However, any lower limit can be combined with any upper limit to form an unclearly recorded range; and any lower limit can be combined with other lower limits to form an unclearly recorded range, and any upper limit can be combined with any other upper limit to form an unclearly recorded range. In addition, although not clearly recorded, each point or single value between the range endpoints is included in the range. Thus, each point or single value can be combined with any other point or single value as its own lower limit or upper limit or with other lower limits or upper limits to form an unclearly recorded range.

[0045] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those generally understood by those skilled in the art of the present application. The terms used herein in the specification of the present application are only for the purpose of describing specific embodiments and are not intended to limit the present application. It should be noted that, unless otherwise stated, the term "and / or" used herein includes any and all combinations of one or more related listed items, and "above", "below" include the number, and the meaning of "multiple" in "one or more" is more than two.

[0046] Water-based acrylic paint also has disadvantages such as long drying time, easy to become sticky at high temperature, easy to become brittle at low temperature, and flammable. In particular, the flammable disadvantage of water-based acrylic paint itself can easily lead to fires, resulting in a large number of casualties and significant property losses, which seriously restricts the widespread promotion and application of water-based acrylic paint. In the prior art, the flame retardant effect of water-based acrylic paint is single, and most of them are flame-retardant by generating a carbon layer with organic phosphorus, and the flame retardant effect still needs to be improved. Based on this, this application is specially proposed.

[0047] The first aspect of the embodiment of the present application provides a fire-resistant flame-retardant coating, comprising the following components by weight: 50-70 parts of water-based hydroxylated acrylic latex, 4-10 parts of flame-retardant functional components, 1-5 parts of film-forming aids, 0.1-2 parts of defoaming agents, 10-20 parts of fillers, 0.1-2 parts of dispersants, 0.1-2 parts of preservatives, 0.1-2 parts of leveling agents, and 10-30 parts of deionized water.

[0048] In an optional embodiment, the water-based strong hydroxyl acrylic latex is prepared by the following method:

[0049] Add emulsifier and deionized water into a flask, and then add methyl methacrylate, butyl acrylate, hydroxypropyl acrylate and styrene. First, pre-emulsify for 0.5-1.5 hours to obtain a liquid phase. Then, add initiator and deionized water into a four-necked flask, and then add the above liquid phase. React at 70-90°C for 4 hours, cool and filter to obtain water-based hydroxy acrylic latex.

[0050] In an optional embodiment, the emulsifier is sodium dodecylbenzene sulfonate film-forming aid, and the initiator is potassium persulfate.

[0051] In an optional embodiment, the mass ratio of the emulsifier, methyl methacrylate, butyl acrylate, hydroxypropyl acrylate, styrene, and initiator is (3-6): (20-30): (30-40): (10-20): (1-5).

[0052] In an optional embodiment, the flame retardant functional component is prepared by the following method:

[0053] 4-chlorophenyl diphenyl phosphate, diboronic acid pinacol ester, Pd(dppf)Cl2, potassium acetate, and 1,4-dioxane were added to a flask in sequence, and the mixture was stirred at 80-120° C. for 1-3 hours. After the reaction was completed, it was purified by column chromatography to obtain intermediate 1;

[0054] Then add intermediate 1, cyanuric chloride, Pd(PPh3)4, and potassium carbonate into a flask, and then add toluene, ethanol, and water in sequence. Then stir the mixture at 80-120°C for 1-3 hours. After the reaction is completed, purify it by column chromatography to obtain a flame retardant functional component.

[0055] The specific synthesis route is as follows:

[0056]

[0057] The flame retardant functional components in the present application contain a large amount of N and P elements. When the phosphorus element is heated, it can produce strong dehydrating substances such as polyphosphoric acid and metaphosphoric acid, which promote the dehydration of the coating into carbon and form a dense carbon layer. The carbon layer is non-flammable and can isolate oxygen, which can prevent combustion. Its thermal conductivity is poor, which can effectively reduce the heat transferred from the flame zone to the substrate, thereby reducing the mass loss rate of the material and the amount of combustibles generated. In addition, the N element is easily heated to release non-combustible gases such as CO2, N2, NH3 and H2O. These non-combustible gases can dilute the oxygen in the air and the concentration of combustibles generated by the thermal decomposition of the polymer. At the same time, part of the heat can be taken away in the heat convection, so that the N element and the P element can achieve the synergistic flame retardant effect of gas phase flame retardancy and condensed phase flame retardancy.

[0058] It contains a lot of phosphorus and silicon. The silicon contained in it can form a glass-like substance when heated, covering the surface of the material, hindering the transport of materials and energy transfer, thereby improving the fire retardant performance of the coating.

[0059] In an optional embodiment, the usage ratio of the diphenyl 4-chlorophenylphosphate, pinacol borate, Pd(dppf)Cl2, potassium acetate, and 1,4-dioxane is (50-70) mmol: (50-70) mmol: (1-2) mmol: (100-150) mmol: (150-300) ml.

[0060] In an optional embodiment, the ratio of the intermediate 1, cyanuric chloride, Pd(PPh3)4, potassium carbonate, toluene, ethanol, and water is (150-180)mmol:(50-60)mmol:(0.5-2)mmol:(100-120)mmol:(100-200)ml:(50-100)ml:(50-100)ml.

[0061] In an optional embodiment, the film-forming aid is selected from one or more of ethylene glycol butyl ether, diethylene glycol butyl ether, triethylene glycol butyl ether, diethylene glycol ethyl ether, ethylene glycol hexyl ether, and ethylene glycol phenyl ether.

[0062] In an optional embodiment, the defoaming agent is a high-carbon alcohol defoaming agent or a silicone defoaming agent.

[0063] In an optional embodiment, the filler is one or more of double fly ash, titanium dioxide, talcum powder, feldspar powder, and precipitated barium sulfate.

[0064] In an optional embodiment, the dispersant is one or more of sodium hexametaphosphate, sodium salt of polycarboxylate, potassium salt of polyacrylate, and sodium salt of polyacrylate.

[0065] In an optional embodiment, the preservative is one or more of aluminum dihydrogen tripolyphosphate, zinc phosphate, and zinc hydroxyphosphite.

[0066] In an optional embodiment, the leveling agent is at least one of German BYK leveling agent BYK-333 and silicone leveling agent HY-5030.

[0067] The present application provides a method for preparing a fire-resistant flame-retardant coating, comprising the following steps:

[0068] S1, add an emulsifier and deionized water into a flask, then add methyl methacrylate, butyl acrylate, hydroxypropyl acrylate, and styrene thereto, first pre-emulsify for 0.5-1.5 hours to obtain a liquid phase, then add an initiator and deionized water into a four-necked flask, then add the above liquid phase, react at 70-90° C. for 4 hours, cool and filter to obtain a water-based hydroxy acrylic latex;

[0069] S2, 4-chlorophenyl diphenyl phosphate, diboronic acid pinacol ester, Pd(dppf)Cl2, potassium acetate are added to a flask in sequence, and then 1,4-dioxane is added, and then the mixture is stirred at 80-120° C. for 1-3 hours. After the reaction is completed, it is purified by column chromatography to obtain intermediate 1, and then intermediate 1, cyanuric chloride, Pd(PPh3)4, and potassium carbonate are added to a flask, and then toluene, ethanol, and water are added in sequence, and then the mixture is stirred at 80-120° C. for 1-3 hours. After the reaction is completed, it is purified by column chromatography to obtain a flame retardant functional component;

[0070] S3, mixing water-based hydroxy acrylic latex, flame retardant functional components, film-forming aids, defoaming agents, fillers, dispersants, preservatives, leveling agents, and water, and stirring at 1800-2000 r / min for 5-15 minutes to obtain a fire-resistant flame retardant coating.

[0071] In an optional embodiment, in step S1, the emulsifier is sodium dodecylbenzene sulfonate film-forming aid, and the initiator is potassium persulfate.

[0072] In an optional embodiment, in step S1, the mass ratio of the emulsifier, methyl methacrylate, butyl acrylate, hydroxypropyl acrylate, styrene, and initiator is (3-6): (20-30): (30-40): (10-20): (1-5).

[0073] In an optional embodiment, in step S2, the ratio of the amount of 4-chlorophenyl diphenyl phosphate, diboronic acid pinacol ester, Pd(dppf)Cl2, potassium acetate, and 1,4-dioxane is (50-70) mmol: (50-70) mmol: (1-2) mmol: (100-150) mmol: (150-300) ml.

[0074] In an optional embodiment, in step S2, the ratio of the amount of the intermediate 1, cyanuric chloride, Pd(PPh3)4, potassium carbonate, toluene, ethanol, and water is (150-180) mmol: (50-60) mmol: (0.5-2) mmol: (100-120) mmol: (100-200) ml: (50-100) ml: (50-100) ml.

[0075] In an optional embodiment, in step S3, the mass ratio of the aqueous hydroxylated acrylic latex, flame retardant functional component, film-forming aid, defoaming agent, filler, dispersant, preservative, leveling agent, and water is (50-70): (4-10): (1-5): (0.1-2): (10-20): (0.1-2): (0.1-2): (0.1-2): (10-30).

[0076] In an optional embodiment, in step S3, the film-forming aid is selected from one or more of ethylene glycol butyl ether, diethylene glycol butyl ether, triethylene glycol butyl ether, diethylene glycol ethyl ether, ethylene glycol hexyl ether, and ethylene glycol phenyl ether.

[0077] In an optional embodiment, in step S3, the defoaming agent is a high-carbon alcohol defoaming agent or a silicone defoaming agent.

[0078] In an optional embodiment, in step S3, the filler is one or more of double fly ash, titanium dioxide, talcum powder, feldspar powder, and precipitated barium sulfate.

[0079] In an optional embodiment, in step S3, the dispersant is one or more of sodium hexametaphosphate, sodium salt of polycarboxylate, potassium salt of polyacrylate, and sodium salt of polyacrylate.

[0080] In an optional embodiment, in step S3, the preservative is one or more of aluminum dihydrogen tripolyphosphate, zinc phosphate, and zinc hydroxyphosphite.

[0081] In an optional embodiment, in step S3, the leveling agent is at least one of German BYK leveling agent BYK-333 and silicone leveling agent HY-5030.

[0082] The third aspect of the embodiment of the present application provides a corrosion-resistant coating obtained by the preparation method of the fire-resistant and flame-retardant coating as described above.

[0083] The above implementation is described in more detail below in conjunction with specific examples.

[0084] Example 1

[0085] The corrosion-resistant coating in this example was prepared according to the formulation in Table 1 below.

[0086] Table 1

[0087]

[0088] The specific preparation method of the coating is as follows:

[0089] S1, preparation of water-based hydroxylated acrylic latex

[0090] Sodium dodecylbenzene sulfonate film-forming aid and deionized water are added to a flask, and then methyl methacrylate, butyl acrylate, hydroxypropyl acrylate and styrene are added thereto. First, pre-emulsify for 0.5 hours to obtain a liquid phase. Then, potassium persulfate and deionized water are added to a four-necked flask, and then the above liquid phase is added. The reaction is carried out at 80°C for 4 hours, and the temperature is cooled and filtered to obtain a water-based hydroxy acrylic latex, wherein the mass ratio of sodium dodecylbenzene sulfonate film-forming aid, methyl methacrylate, butyl acrylate, hydroxypropyl acrylate, styrene and potassium persulfate is 4:25:35:15:3.

[0091] S2, preparation of flame retardant functional components

[0092]

[0093] Take a four-necked round-bottom flask and put in a stirring bar and a reflux tube. After drying, fill it with nitrogen. Take 56.02mmol 4-chlorophenylphosphodiphenyl ester (CAS: 917028-00-3), 67.48mmol boric acid pinacol ester (CAS: 73183-34-3), 1.12mmol Pd(dppf)Cl2 (CAS: 72287-26-4), and 123.04mmol potassium acetate into the round-bottom flask. Measure 200mL of 1,4-dioxane and add it to the round-bottom flask, and stir the mixture at 100℃ for 2 hours. After the reaction is completed, the intermediate 1 is purified by column chromatography; a four-necked round-bottom flask is placed in a stirring rod and a reflux tube, and nitrogen is filled in after drying. 158.34mmol of intermediate 1, 51.85mmol of cyanuric chloride, 0.51mmol of Pd(PPh3)4, 101.47mmol of potassium carbonate, 140mL of toluene, 60mL of ethanol, and 60mL of water are added to the flask, and the mixture is stirred at 80°C for 2 hours. After the reaction is completed, the flame retardant functional component is purified by column chromatography, with a yield of 78%, and elemental analysis: C57H42N3O9P3, theoretical value C, 68.06; H, 4.21; N, 4.18; O, 14.31; P, 9.24; measured value C, 68.08; H, 4.22; N, 4.13; P, 9.26;. HRMS (ESI) m / z (Μ+H)+: theoretical value: 1005.21; found value: 1006.34.

[0094] S3, coating preparation

[0095] Aqueous hydroxylated acrylic latex, flame retardant functional components, film-forming aids, defoamers, fillers, dispersants, preservatives, leveling agents, and water were mixed in the weight portions shown in Table 1 above, and stirred at 2000 r / min for 10 min to obtain a fire-resistant flame retardant coating.

[0096] Example 2

[0097] Compared with Example 1, most of them are the same, except for the replacement of the target component, as shown in Table 2 below.

[0098] Table 2

[0099]

[0100] Example 3

[0101] Compared with Example 1, most of them are the same, except for the replacement of the target component, as shown in Table 3 below.

[0102] Table 3

[0103]

[0104] Example 4

[0105] Compared with Example 1, most of them are the same, except for the replacement of the target component, as shown in Table 4 below.

[0106] Table 4

[0107]

[0108] Comparative Example 1

[0109] Compared with Example 1, most of them are the same, except for the replacement of the target component, the flame retardant functional component is changed to resorcinol bis(diphenyl) phosphate, as shown in the following Table 5 for details.

[0110] Table 5

[0111]

[0112] Comparative Example 2

[0113] Compared with Example 1, most of them are the same, except for the replacement of the target component, the flame retardant functional component is changed to melamine, as shown in the following Table 6 for details.

[0114] Table 6

[0115]

[0116] Comparative Example 3

[0117] Compared with Example 1, most of them are the same, except for the replacement of the target component, as shown in Table 7 below.

[0118] Table 7

[0119]

[0120] Comparative Example 4

[0121] Compared with Example 1, most of them are the same, except for the replacement of the target component, as shown in Table 8 below.

[0122] Table 8

[0123]

[0124] Test Case

[0125] 1. The coatings prepared in Examples 1-5 and Comparative Examples 1-3 were applied on a clean steel plate of 80 mm×80 mm×0.8 mm and dried at 40° C. for 12 h to obtain a coating.

[0126] 2. Test the fire resistance performance in accordance with GB / T14907-2002.

[0127] 3. Test adhesion grade according to GB / T 9286-1998.

[0128] 4. Test water resistance according to GB / T 4893.1-2005.

[0129] 5. Test acid resistance according to GB / T4893.1-2005.

[0130] 6. Test alkali resistance according to GB / T 4893.1-2005.

[0131] The test results are shown in Table 9 below.

[0132] Table 9

[0133]

[0134]

[0135] As can be seen from the above table, the performance of the coatings obtained in Examples 1 to 4 of the present application is significantly better than that of Comparative Examples 1 to 3. Furthermore, the coatings obtained in the present application have excellent fire resistance, water resistance, acid resistance, alkali resistance, and good adhesion when used.

[0136] Compared with Comparative Example 1, Example 1 uses a common organophosphorus flame retardant to form a dense carbon layer, which has a certain flame retardant effect, but there is still a certain gap compared with the NP synergistic flame retardancy in Comparative Example 1.

[0137] Compared with Example 2, Example 1 uses a common nitrogen-based flame retardant, which only performs flame retardancy in the gas phase, and the flame retardancy effect still needs to be improved.

[0138] Compared with Example 3, Example 1 directly adds organic phosphorus flame retardant and organic nitrogen flame retardant. On the one hand, their compatibility with latex is poor. On the other hand, when the formed coating is heated, the organic phosphorus flame retardant and the organic nitrogen flame retardant act simultaneously. The organic phosphorus flame retardant generates a char layer, and the organic nitrogen flame retardant forms a non-combustible gas. However, there is no sequence in the formation of the non-combustible gas and the char layer. The non-combustible gas will form a variety of small holes in the char layer, resulting in poor density of the char layer, which leads to a decrease in flame retardant properties.

[0139] Compared with Comparative Example 4, in which no flame retardant was added, Example 1 had poor flame retardant performance.

[0140] The formula obtained in the present application improves the compatibility with the flame retardant functional component through the homemade water-based hydroxyl acrylic latex. On the other hand, by synthesizing the organic phosphorus heterocyclic compound flame retardant, the phosphorus-nitrogen synergistic effect is concentrated in one functional component to achieve the synergistic flame retardant effect of gas phase flame retardancy and condensed phase flame retardancy. The flame retardant functional component in the present application contains a large amount of N and P elements. When the coating is heated, a dense carbon layer is first formed. When the phosphorus element is heated, it can produce strong dehydrating substances such as polyphosphoric acid and metaphosphoric acid, which promotes the dehydration of the coating into carbon and forms a dense carbon layer. The carbon layer cannot be It can burn and isolate oxygen, making combustion impossible. Its poor thermal conductivity can effectively reduce the heat transferred from the flame zone to the substrate, thereby reducing the mass loss rate of the material and the amount of combustibles generated, and then release non-combustible gases. Among them, the N element is easily heated to release non-combustible gases such as CO2, N2, NH3 and H2O. Through these non-combustible gases, the oxygen in the air and the concentration of combustibles produced by thermal decomposition of polymers can be diluted. At the same time, part of the heat can be taken away in the heat convection, so that the N element and the P element can achieve the synergistic flame retardant effect of gas phase flame retardancy and condensed phase flame retardancy.

[0141] The above description of the embodiments is to facilitate the understanding and use of the invention by those skilled in the art. It is obvious that those skilled in the art can easily make various modifications to these embodiments and apply the general principles described herein to other embodiments without creative work. Therefore, the present invention is not limited to the above embodiments, and improvements and modifications made by those skilled in the art based on the disclosure of the present invention without departing from the scope of the present invention should be within the scope of protection of the present invention.

Claims

1. A fire-resistant flame retardant coating, characterized in that The invention comprises the following components by weight: 50-70 parts of water-based hydroxy acrylic latex, 4-10 parts of flame retardant functional components, 1-5 parts of film-forming aids, 0.1-2 parts of defoaming agents, 10-20 parts of fillers, 0.1-2 parts of dispersants, 0.1-2 parts of preservatives, 0.1-2 parts of leveling agents and 10-30 parts of deionized water.

2. A fire-resistant flame-retardant coating according to claim 1, characterized in that: The water-based strong hydroxyl acrylic latex is prepared in the following manner: Add emulsifier and deionized water into a flask, then add methyl methacrylate, butyl acrylate, hydroxypropyl acrylate and styrene, pre-emulsify for 0.5-1.5 hours to obtain a liquid phase, then add initiator and deionized water into a four-necked flask, then add the above liquid phase, react at 70-90°C for 4 hours, cool and filter to obtain water-based hydroxy acrylic latex.

3. A fire-resistant flame-retardant coating according to claim 2, characterized in that: The emulsifier is sodium dodecylbenzene sulfonate film-forming aid, and the initiator is potassium persulfate; And / or, the mass ratio of the emulsifier, methyl methacrylate, butyl acrylate, hydroxypropyl acrylate, styrene, and initiator is (3-6): (20-30): (30-40): (10-20): (1-5).

4. A fire-resistant flame-retardant coating according to claim 1, characterized in that: The flame retardant functional component is prepared in the following manner: 4-chlorophenyl diphenyl phosphate, diboronic acid pinacol ester, Pd(dppf)Cl2, potassium acetate, and 1,4-dioxane were added to a flask in sequence, and the mixture was stirred at 80-120° C. for 1-3 hours. After the reaction was completed, it was purified by column chromatography to obtain intermediate 1; Then add intermediate 1, cyanuric chloride, Pd(PPh3)4, and potassium carbonate into a flask, and then add toluene, ethanol, and water in sequence. Then stir the mixture at 80-120°C for 1-3 hours. After the reaction is completed, purify it by column chromatography to obtain a flame retardant functional component.

5. A fire-resistant flame-retardant coating according to claim 4, characterized in that: The ratio of the amount of 4-chlorophenyl diphenyl phosphate, diboronic acid pinacol ester, Pd(dppf)Cl2, potassium acetate, and 1,4-dioxane is (50-70) mmol: (50-70) mmol: (1-2) mmol: (100-150) mmol: (150-300) ml; And / or, the ratio of the intermediate 1, cyanuric chloride, Pd(PPh3)4, potassium carbonate, toluene, ethanol, and water is (150-180)mmol:(50-60)mmol:(0.5-2)mmol:(100-120)mmol:(100-200)ml:(50-100)ml:(50-100)ml.

6. The fire-resistant flame-retardant coating according to claim 1, characterized in that: The film-forming aid is selected from one or more of ethylene glycol butyl ether, diethylene glycol butyl ether, triethylene glycol butyl ether, diethylene glycol ethyl ether, ethylene glycol hexyl ether, and ethylene glycol phenyl ether; And / or, the defoamer is a higher alcohol defoamer or an organosilicon defoamer; And / or, the filler is one or more of double fly ash, titanium dioxide, talcum powder, feldspar powder, and precipitated barium sulfate; And / or, the dispersant is one or more of sodium hexametaphosphate, sodium salt of polycarboxylate, potassium salt of polyacrylate, sodium salt of polyacrylate; And / or, the preservative is one or more of aluminum dihydrogen tripolyphosphate, zinc phosphate, and zinc hydroxyphosphite; And / or, the leveling agent is German BYK leveling agent BYK-333 or silicone leveling agent HY-5030.

7. A method for preparing a fire-resistant flame-retardant coating, characterized in that: The following steps are involved: S1, add an emulsifier and deionized water into a flask, then add methyl methacrylate, butyl acrylate, hydroxypropyl acrylate, and styrene thereto, pre-emulsify for 0.5-1.5 hours to obtain a liquid phase, then add an initiator and deionized water into a four-necked flask, then add the above liquid phase, react at 70-90° C. for 4 hours, cool and filter to obtain a water-based hydroxy acrylic latex; S2, 4-chlorophenyl diphenyl phosphate, diboronic acid pinacol ester, Pd(dppf)Cl2, potassium acetate are added to a flask in sequence, and then 1,4-dioxane is added, and then the mixture is stirred at 80-120° C. for 1-3 hours. After the reaction is completed, it is purified by column chromatography to obtain intermediate 1, and then intermediate 1, cyanuric chloride, Pd(PPh3)4, and potassium carbonate are added to a flask, and then toluene, ethanol, and water are added in sequence, and then the mixture is stirred at 80-120° C. for 1-3 hours. After the reaction is completed, it is purified by column chromatography to obtain a flame retardant functional component; S3, mixing water-based hydroxy acrylic latex, flame retardant functional components, film-forming aids, defoaming agents, fillers, dispersants, preservatives, leveling agents, and deionized water, and stirring at 1800-2000 r / min for 5-15 minutes to obtain a fire-resistant flame retardant coating.

8. The method for preparing a fire-resistant flame-retardant coating according to claim 7, characterized in that: In step S1, the emulsifier is sodium dodecylbenzene sulfonate film-forming aid, and the initiator is potassium persulfate; And / or, in step S1, the mass ratio of the emulsifier, methyl methacrylate, butyl acrylate, hydroxypropyl acrylate, styrene, and initiator is (3-6): (20-30): (30-40): (10-20): (1-5); And / or, in step S2, the ratio of the amount of 4-chlorophenyl diphenyl phosphate, diboronic acid pinacol ester, Pd(dppf)Cl2, potassium acetate, and 1,4-dioxane is (50-70) mmol: (50-70) mmol: (1-2) mmol: (100-150) mmol: (150-300) ml; And / or, in step S2, the ratio of the intermediate 1, cyanuric chloride, Pd(PPh3)4, potassium carbonate, toluene, ethanol, and water is (150-180) mmol: (50-60) mmol: (0.5-2) mmol: (100-120) mmol: (100-200) ml: (50-100) ml: (50-100) ml.

9. The method for preparing a fire-resistant flame-retardant coating according to claim 7 or 8, characterized in that: In step S3, the mass ratio of the water-based hydroxylated acrylic latex, the flame retardant functional component, the film-forming aid, the defoaming agent, the filler, the dispersant, the preservative, the leveling agent, and the deionized water is (50-70): (4-10): (1-5): (0.1-2): (10-20): (0.1-2): (0.1-2): (0.1-2): (10-30); And / or, in step S3, the film-forming aid is selected from one or more of ethylene glycol butyl ether, diethylene glycol butyl ether, triethylene glycol butyl ether, diethylene glycol ethyl ether, ethylene glycol hexyl ether, and ethylene glycol phenyl ether; And / or, in step S3, the defoamer is a higher alcohol defoamer or an organosilicon defoamer; And / or, in step S3, the filler is one or more of double fly ash, titanium dioxide, talcum powder, feldspar powder, and precipitated barium sulfate; And / or, in step S3, the dispersant is one or more of sodium hexametaphosphate, sodium salt of polycarboxylate, potassium salt of polyacrylate, and sodium salt of polyacrylate; And / or, in step S3, the preservative is one or more of aluminum dihydrogen tripolyphosphate, zinc phosphate, and zinc hydroxyphosphite; And / or, in step S3, the leveling agent is German BYK leveling agent BYK-333 or silicone leveling agent HY-5030.

10. A fire-resistant flame-retardant coating obtained by the method for preparing a fire-resistant flame-retardant coating according to any one of claims 7 to 9.

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