CN111363380B - Nano zirconium phosphate coated modified ammonium polyphosphate and intumescent fire retardant coating prepared from same - Google Patents
Nano zirconium phosphate coated modified ammonium polyphosphate and intumescent fire retardant coating prepared from same Download PDFInfo
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Abstract
The invention discloses a nano zirconium phosphate coated modified ammonium polyphosphate flame retardant, which is characterized in that a zirconium phosphate nanosheet is coated on polyethyleneimine PEI modified ammonium polyphosphate, so that a P-O-C-N flame retardant synergistic effect is exerted, and a flame retardant effect is exerted in a gas phase and a solid phase; the modified ammonium polyphosphate flame-retardant coating is applied to preparation of an intumescent fire-retardant coating, has the advantages of high carbon layer strength, compact intumescent carbon layer, high-efficiency flame retardance and smoke suppression, can effectively solve the problems that ammonium polyphosphate is easy to migrate and hydrolyze in a humid environment, and improves the weather resistance and durability of the coating; the obtained intumescent fire-retardant coating integrates the functions of flame retardance, smoke suppression and enhancement, has excellent halogen-free char formation property, environmental protection and wide applicability, and the related preparation method has simple process and mild reaction conditions, and is suitable for popularization and application.
Description
Technical Field
The invention belongs to the technical field of flame-retardant materials, and particularly relates to nano-zirconium phosphate coated modified ammonium polyphosphate and an intumescent fire-retardant coating prepared by using the same.
Background
The intumescent fire-retardant coating is prepared by taking macromolecular aqueous emulsion, macromolecular resin and the like as a matrix, adding an intumescent fire-retardant system consisting of an acid source, a gas source, a carbon source and the like, and a filler and an auxiliary agent. The components react at high temperature, are dehydrated and carbonized to form a uniform and compact cellular expanded carbon layer, and isolate the air and heat transfer, thereby achieving excellent fireproof and heat-insulating effects.
Ammonium polyphosphate is a novel high-efficiency non-halogen intumescent flame retardant, and has a phosphorus content of 30-32% and a nitrogen content of 14-16%. The ammonium polyphosphate fire retardant is characterized by extremely low smoke generation amount during combustion, no toxicity, no odor, good fire resistance, small relative density and the like, is used as an acid source of the intumescent fire retardant coating, has the effects of the acid source and a gas source, can form a high-efficiency intumescent fire retardant system by combining a carbon source, can form a porous carbon layer on the surface when being heated, effectively blocks heat and oxygen, can inhibit smoke and prevent molten drops, and has great effect in the intumescent fire retardant coating. However, ammonium polyphosphate which is an inorganic polymer has poor thermal stability, poor compatibility with a high molecular base material and easy moisture absorption in a humid environment, and has a plurality of defects when being directly added into a fireproof coating. The hygroscopic nature of APP makes it susceptible to migration from the interior of the coating to the surface and fading, resulting in a decrease in the durability and weatherability of the coating.
In order to solve the above technical problems, surface modification of APP by a surface coating technique is a common and effective method. In chinese patent CN108219233A, APP is coated with magnesium hydroxide by electrostatic adsorption force, and magnesium hydroxide is adsorbed on the APP surface, but there are problems of weak binding force, low surface coating degree, and the like; patent CN101503591B mainly forms an expansion layer through the physical expansion of low-sulfur expandable graphite, which reduces the smoke amount of the coating, but the synergistic flame retardant effect is not good, resulting in poor flame retardant and heat insulation effect of the coating. Therefore, a modification means for further optimizing APP functional components is urgently needed, and the APP functional components are applied to the development of a new-generation fireproof coating which is environment-friendly, efficient, durable, stable and attractive.
Disclosure of Invention
The invention mainly aims to solve the problems that ammonium polyphosphate is easy to migrate and hydrolyze in a humid environment, has poor compatibility with a base material, has a loose expanded carbon layer in an intumescent fire-retardant coating, has low strength and the like, and provides a nano zirconium phosphate coated modified ammonium polyphosphate flame retardant which has a P-O-C-N flame-retardant synergistic effect and has a flame-retardant effect in a gas phase and a solid phase by coating a zirconium phosphate nanosheet on polyethyleneimine modified ammonium polyphosphate; the obtained flame retardant is applied to the preparation of the intumescent fire-retardant coating, has the advantages of low cost, good halogen-free char formation, environmental protection, wide applicability and the like, and the related preparation method has simple process and mild reaction conditions, and is suitable for popularization and application.
In order to achieve the purpose, the invention adopts the technical scheme that:
a preparation method of nano zirconium phosphate coated modified ammonium polyphosphate comprises the following steps:
1) TBA-debonded zirconium phosphate (ZrP): ultrasonically dispersing zirconium phosphate in water under a stirring condition, then dropwise adding tetrabutylammonium hydroxide solution, carrying out ultrasonic stirring reaction after dropwise adding, then dropwise adding concentrated acid to carry out secondary reaction, and then carrying out solid-liquid separation to obtain semitransparent gel precipitate;
2) coating APP with PEI: ultrasonically dispersing ammonium polyphosphate in water under the stirring condition to form a suspension, adding Polyethyleneimine (PEI), and performing adsorption treatment under the stirring condition to obtain a mixed solution containing modified ammonium polyphosphate;
3) nano zirconium phosphate coating modified ammonium polyphosphate: and (3) mechanically stirring the semitransparent gel precipitate obtained in the step 1) to uniformly disperse the semitransparent gel precipitate in water, then dropwise adding the mixed solution obtained in the step 2), stirring for reaction, centrifuging, and drying to obtain the nano zirconium phosphate coated modified ammonium polyphosphate (powder).
In the above scheme, the zirconium phosphate is alpha-zirconium phosphate.
In the scheme, the molar ratio of zirconium phosphate to tetrabutylammonium hydroxide in the step 1) is 3: 2-1: 6.
In the scheme, the reaction temperature in the step 1) is 0-5 ℃.
In the scheme, the concentration of the tetrabutylammonium hydroxide solution in the step 1) is 0.05-5mol/L, and the dripping time is 30-90 min; the concentration of the concentrated acid is 3-18mol/L, and the dripping time is 30-90 min.
In the scheme, the concentrated acid is one or more of concentrated phosphoric acid, concentrated hydrochloric acid and concentrated nitric acid; concentrated phosphoric acid is preferred.
In the scheme, the molar ratio of the acid introduced in the step 1) to the tetrabutylammonium hydroxide is 50: 1-1: 10.
In the scheme, the mass ratio of the polyethyleneimine to the ammonium polyphosphate in the step 2) is 1 (0.1-5).
In the scheme, the action time of the mechanical stirring and ultrasonic treatment in the step 2) is 0.5-2 h; the adsorption treatment time is 2-12 h.
In the scheme, the dropping time of the mixed solution in the step 3) is 30-90 min.
In the scheme, the stirring reaction time in the step 3) is 12-48 h.
In the scheme, the mass ratio of the ammonium polyphosphate to the zirconium phosphate is 5: 1-1: 10.
The nanometer zirconium phosphate coated modified ammonium polyphosphate obtained by the scheme is applied to preparation of an intumescent fire retardant coating, and comprises the following components in percentage by mass: 20-30% of methacrylic acid modified acrylate core-shell emulsion, 30-36% of nano zirconium phosphate coated modified ammonium polyphosphate, 10-20% of pentaerythritol, 10-15% of melamine, 1-5% of titanium dioxide, 0.5-1% of hydroxyethyl cellulose, 0.5-1% of dispersing agent, 0.5-1% of defoaming agent, 0.5-1% of n-octanol and the balance of water.
In the scheme, the dispersant is wetting dispersant 5040 and the like.
In the scheme, the defoaming agent is an organic silicon defoaming agent 470 and the like.
The intumescent fire-retardant coating prepared according to the scheme integrates the functions of flame retardance, smoke suppression and enhancement, and has the advantages of low cost, good durability and weather resistance, good char formation, environmental protection and wide applicability.
The principle of the invention is as follows:
1) firstly, inserting TBA between zirconium phosphate layers, weakening the acting force between the zirconium phosphate layers, peeling the zirconium phosphate layers, and exposing-OH rich in the zirconium phosphate layers to obtain zirconium phosphate nano-sheets; then, adsorbing polyethyleneimine PEI with a surface rich in cations on the surface of APP by using the adsorption effect of positive electricity and negative electricity; and finally, adsorbing the nano-sheet zirconium phosphate on the surface of the PEI, thereby preparing the ammonium polyphosphate coated and modified by the nano-sheet zirconium phosphate, effectively improving the problems of migration, precipitation and cracking, poor compatibility with a substrate and the like of the ammonium polyphosphate APP molecule, and improving the stability of the ammonium polyphosphate.
2) The PEI can absorb a large amount of carbon dioxide in humid air, when the PEI is adsorbed on the surface of APP (PEI-APP), the APP which is used as an acid source and an air source in a coating system can improve the release amount of non-combustible gas, and the PEI also has larger carbon content and can further enhance the carbon content of an expanded carbon layer; the zirconium phosphate nanosheets are adsorbed on the obtained PEI-APP, and due to the solid acid effect of zirconium phosphate, the catalytic carbonization effect of the APP can be improved, the strength and compactness of a carbon layer are enhanced, meanwhile, the flame-retardant synergistic effect of P-O-C-N can be exerted, a free radical trapping agent can be generated in a gas phase, and free radicals playing a role in chain growth in a combustion reaction are inhibited, so that the flame-retardant effect is exerted, and the flame-retardant and smoke-suppression properties are efficiently improved.
Compared with the prior art, the invention has the beneficial effects that:
1) by adding the nano zirconium phosphate coated and modified ammonium polyphosphate to replace ammonium polyphosphate, the high-efficiency flame retardance and excellent char forming property of the ammonium polyphosphate are utilized to play a high-efficiency synergistic flame-retardant role with an expansion system consisting of pentaerythritol and melamine in the fireproof coating, so that the fireproof coating has a carbon layer with higher quality strength, and further has high-efficiency flame retardance.
2) The modified ammonium polyphosphate can act on a gas phase and a condensed phase together, play a free radical quenching effect and a flame-retardant gas dilution effect in the gas phase, play a covering effect in the condensed phase, and effectively catalyze a char-forming agent in a coating to generate a char reaction, and a carbonized product can improve the strength, thermal stability and barrier property of an expanded char layer so as to improve the fire resistance of the coating.
3) The expanded fireproof coating has the advantages that the carbon layer is high in strength, the expanded carbon layer is compact, the flame retardance and smoke suppression are high in efficiency, the problems that ammonium polyphosphate is easy to migrate and hydrolyze in a humid environment are solved, and the weather resistance and durability of the coating are improved; the obtained intumescent fire-retardant coating integrates the functions of flame retardance, smoke suppression and reinforcement, has excellent halogen-free char formation property, environmental protection and wide applicability, and the related preparation method has simple process and is suitable for popularization and application.
Detailed Description
In order to better understand the present invention, the following examples are further provided to illustrate the present invention, but the present invention is not limited to the following examples.
In the following examples, the preparation of zirconium phosphate (α -zirconium phosphate) used comprises the following steps: 100mL of concentrated phosphoric acid with a molar concentration of 3mo1/L was prepared, and added to a 250mL three-necked flask, 10.00g of zirconium oxychloride (ZrOCl) was added2-8H20) Heating to 95 ℃, mechanically stirring for 20min to fully disperse zirconium oxychloride, stopping stirring, reacting at a reflux temperature for 24h, standing the obtained mixed solution after the reaction is finished, naturally cooling to normal temperature, pouring out the supernatant, performing centrifugal treatment (10000r/min, 10min) on the milky precipitate at the lower layer for solid-liquid separation, washing the obtained solid product with a proper amount of deionized water, performing centrifugal treatment again, and repeating the steps until the centrifugal clear liquid meets the pH requirement>And 5, drying the washed solid product in an oven at the temperature of 80 ℃ for 12 hours, and grinding to obtain white zirconium phosphate powder.
In the following examples, the dispersant used was wetting dispersant 5040 and the defoamer was silicone defoamer 470.
In the following examples, the preparation method of the methacrylic acid modified acrylate emulsion used comprises the following steps:
1) 1.0g of alkylphenol polyoxyethylene and 2.0g of lauryl sodium sulfate are dissolved in 90ml of deionized water to prepare an emulsifier aqueous solution, and the emulsifier aqueous solution is divided into three parts of 35ml, 30ml and 25 ml; ultrasonically dispersing 35ml of emulsifier aqueous solution for 40min, adding 50g of n-butyl acrylate and 10g of methyl methacrylate, stirring and mixing at room temperature, and pre-emulsifying for 1h to prepare a nuclear pre-emulsion; adding 10g of n-butyl acrylate, 30g of methyl methacrylate and 2.4g of methacrylic acid into 30ml of an emulsifier aqueous solution, stirring and mixing at room temperature, and pre-emulsifying for 2 hours to prepare a shell pre-emulsion; dissolving 0.3g of sodium bicarbonate in 25ml of emulsifier water solution, stirring and dissolving to prepare a buffer water solution; adding 0.5g of potassium persulfate into 30ml of deionized water, stirring and dissolving to prepare an initiator aqueous solution;
2) preparing a seed emulsion: sequentially adding a buffer aqueous solution, an initiator aqueous solution with the volume of 1/3 and a nuclear pre-emulsion with the volume of 1/2 in a reaction vessel while stirring, heating to 70 ℃, and preserving heat for 0.5h when a large amount of blue light appears in the emulsion to obtain a seed emulsion;
3) polymerization of the core layer: slowly dripping the rest nuclear pre-emulsion and 1/3 initiator aqueous solution into the seed emulsion after the heat preservation of the seed emulsion is finished, controlling the temperature to 80 ℃ and preserving the heat for 0.5h after finishing dripping within 1h to obtain nuclear layer emulsion;
4) shell polymerization: and (3) when the heat preservation of the core emulsion is finished, dropwise adding the rest initiator aqueous solution and the shell pre-emulsion, finishing dropping within 1.5h, then heating to 85 ℃, preserving the heat for 0.5h, then naturally cooling to 40 ℃, adjusting the pH value to 8, and sieving by using a 200-mesh sieve to obtain the methacrylic acid modified acrylate core-shell emulsion.
Example 1
A preparation method of nano zirconium phosphate coated modified ammonium polyphosphate comprises the following steps:
1) TBA stripping zirconium phosphate: in a 500ml four-mouth flask, 0.01mol of zirconium phosphate and 300ml of deionized water are fully dispersed by mechanical stirring and ultrasonic action, the process lasts for 30min, the temperature is kept at 5 ℃, then 100ml of tetrabutyl ammonium hydroxide solution (the TBA concentration is 0.1mol/L) is dripped into the four-mouth flask at a constant speed within 30min, the reaction is continued for 2h after dripping, 20ml of 4mol/L concentrated phosphoric acid is dripped into the flask at a constant speed within 30min, and after the reaction is finished (2h), the obtained mixed solution is centrifuged to carry out solid-liquid separation, so that semitransparent gel precipitate is obtained and is washed by distilled water;
2) coating APP with PEI: dispersing 3g of ammonium polyphosphate in deionized water through mechanical stirring and ultrasonic action to form a suspension, adding 6g of Polyethyleneimine (PEI) into the suspension, and adsorbing for 2 hours under the stirring condition to form a mixed solution containing modified ammonium polyphosphate;
3) nano zirconium phosphate coating modified ammonium polyphosphate: uniformly dispersing the nano-sheet zirconium phosphate (semitransparent gel precipitate) obtained in the step 1) through mechanical stirring, slowly dropwise adding the mixed solution obtained in the step 2) into the nano-sheet zirconium phosphate within 1h, mechanically stirring for 24h, centrifuging, and vacuum drying at 50 ℃ for 24h to obtain the nano-zirconium phosphate coated modified ammonium polyphosphate.
Example 2
A preparation method of nano zirconium phosphate coated modified ammonium polyphosphate comprises the following steps:
1) TBA stripping zirconium phosphate: in a 500ml four-mouth flask, 0.01mol of zirconium phosphate and 300ml of deionized water are fully dispersed by mechanical stirring and ultrasonic action, the process lasts for 30min, the temperature is kept at 5 ℃, then 100ml of tetrabutyl ammonium hydroxide solution (the TBA concentration is 0.1mol/L) is dripped into the four-mouth flask at a constant speed within 30min, the reaction is continued for 2h after dripping, 20ml of 4mol/L concentrated phosphoric acid is dripped into the flask at a constant speed within 30min, and after the reaction is finished (2h), the obtained mixed solution is centrifuged to carry out solid-liquid separation, so that semitransparent gel precipitate is obtained and is washed by distilled water;
2) coating APP with PEI: dispersing 2g of ammonium polyphosphate in deionized water through mechanical stirring and ultrasonic action to form a suspension, adding 4g of polyethyleneimine PEI into the suspension, and adsorbing for 2 hours under the stirring condition to form a mixed solution containing modified ammonium polyphosphate.
3) Nano zirconium phosphate coating modified ammonium polyphosphate: uniformly dispersing the nano-sheet zirconium phosphate (semitransparent gel precipitate) obtained in the step 1) through mechanical stirring, slowly dropwise adding the mixed solution obtained in the step 2) into the nano-sheet zirconium phosphate within 1h, mechanically stirring for 24h, centrifuging, and vacuum drying at 50 ℃ for 24h to obtain the nano-zirconium phosphate coated modified ammonium polyphosphate.
Application example 1
The nanometer zirconium phosphate coated modified ammonium polyphosphate obtained in the example 1 is applied to the preparation of the intumescent fire retardant coating, and comprises the following components in percentage by mass: 20% of methacrylic acid modified acrylate emulsion, 36% of nano zirconium phosphate coated modified ammonium polyphosphate, 12% of pentaerythritol, 12% of melamine, 3% of titanium dioxide, 0.5% of hydroxyethyl cellulose, 0.5% of dispersing agent, 0.5% of defoaming agent, 0.5% of n-octanol and 15% of water, wherein the specific preparation method comprises the following steps: grinding the weighed nano zirconium phosphate coated modified ammonium polyphosphate, pentaerythritol, melamine, titanium dioxide and hydroxyethyl cellulose into powder, and then adding water to fully grind and uniformly mix; adding the defoaming agent and the dispersing agent, and continuously and fully grinding; and finally, adding methacrylic acid modified acrylate emulsion and n-octanol, fully grinding and uniformly mixing to obtain the fireproof coating.
Application example 2
The preparation method of the fireproof coating in application example 2 is substantially the same as that in application example 1, except that the fireproof coating comprises the following components in percentage by mass: 20% of methacrylic acid modified acrylate emulsion, 32% of nano zirconium phosphate coated modified ammonium polyphosphate, 12% of pentaerythritol, 12% of melamine, 3% of titanium dioxide, 0.5% of hydroxyethyl cellulose, 0.5% of dispersing agent, 0.5% of defoaming agent, 0.5% of n-octanol and 19% of water.
Application example 3
The preparation method of the fireproof coating in application example 3 is substantially the same as that in application example 1, except that the fireproof coating comprises the following components in percentage by mass: 20% of methacrylic acid modified acrylate emulsion, 30% of nano zirconium phosphate coated modified ammonium polyphosphate, 12% of pentaerythritol, 12% of melamine, 3% of titanium dioxide, 0.5% of hydroxyethyl cellulose, 0.5% of dispersing agent, 0.5% of defoaming agent, 0.5% of n-octanol and 21% of water.
Comparative example 1
The preparation method of the fireproof coating in the comparative example 1 is substantially the same as that in the application example 1, except that the fireproof coating comprises the following components in percentage by mass: 20% of methacrylic acid modified acrylate emulsion, 36% of ammonium polyphosphate, 12% of pentaerythritol, 12% of melamine, 3% of titanium dioxide, 0.5% of hydroxyethyl cellulose, 0.5% of dispersing agent, 0.5% of defoaming agent, 0.5% of n-octyl alcohol and 15% of water.
Comparative example 2
The preparation method of the fireproof coating in the comparative example 2 is substantially the same as that in the application example 1, except that the fireproof coating comprises the following components in percentage by mass: 20% of methacrylic acid modified acrylate emulsion, 31% of ammonium polyphosphate, 12% of pentaerythritol, 12% of melamine, 3% of titanium dioxide, 0.5% of hydroxyethyl cellulose, 0.5% of dispersing agent, 0.5% of defoaming agent, 0.5% of n-octyl alcohol, 15% of water and 5% of zirconium phosphate.
Comparative example 3
The preparation method of the fireproof coating in the comparative example 3 is substantially the same as that in the application example 1, except that the fireproof coating comprises the following components in percentage by mass: 20% of methacrylic acid modified acrylate emulsion, 31% of ammonium polyphosphate, 12% of pentaerythritol, 12% of melamine, 3% of titanium dioxide, 0.5% of hydroxyethyl cellulose, 0.5% of dispersant, 0.5% of defoamer, 0.5% of n-octanol, 15% of water and 5% of mixture of zirconium phosphate and polyethyleneimine (3% of zirconium phosphate and 2% of PEI).
The intumescent fire-retardant coatings obtained in application examples 1-3 and comparative examples 1-3 were respectively subjected to fire resistance tests, and the results are shown in table 1.
TABLE 1 relevant Performance test of the intumescent coatings obtained in application examples 1-3 and comparative examples 1-3
The above results show that: the nano zirconium phosphate coated modified ammonium polyphosphate has high flame retardant efficiency, is environment-friendly and pollution-free, has good compatibility with resin, base materials and the like, effectively solves the problems of easy migration and easy hydrolysis of APP and the like, and can further effectively improve the fire resistance, durability and weather resistance of the obtained intumescent fire-retardant coating.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the present invention. The invention can be realized by all the raw materials listed in the invention, and the invention can be realized by the upper and lower limit values and interval values of all the raw materials, and the examples are not listed. Further, the applicant intends to point out that modifications and variations may be made in accordance with the above teachings while remaining within the spirit and principles of the present invention, and all such modifications and variations are intended to fall within the scope of the appended claims.
Claims (10)
1. A nanometer zirconium phosphate coated modified ammonium polyphosphate for an intumescent fire retardant coating, the preparation method comprises the following steps:
1) TBA-debonded zirconium phosphate (ZrP): ultrasonically dispersing zirconium phosphate in water under a stirring condition, then dropwise adding tetrabutylammonium hydroxide solution, carrying out ultrasonic stirring reaction after dropwise adding, then dropwise adding concentrated acid to carry out secondary reaction, and then carrying out solid-liquid separation to obtain semitransparent gel precipitate;
2) coating APP with PEI: ultrasonically dispersing ammonium polyphosphate in water under the stirring condition to form a suspension, adding Polyethyleneimine (PEI), and performing adsorption treatment under the stirring condition to obtain a mixed solution containing modified ammonium polyphosphate;
3) nano zirconium phosphate coating modified ammonium polyphosphate: and (2) mechanically stirring the semitransparent gel precipitate obtained in the step 1) to uniformly disperse the semitransparent gel precipitate in water, then dropwise adding the mixed solution obtained in the step 2), stirring for reaction, centrifuging, and drying to obtain the nano zirconium phosphate coated modified ammonium polyphosphate.
2. The nano zirconium phosphate coated modified ammonium polyphosphate according to claim 1, wherein the molar ratio of the zirconium phosphate to the tetrabutylammonium hydroxide in the step 1) is 3:2 to 1: 6.
3. The nano zirconium phosphate coated modified ammonium polyphosphate according to claim 1, wherein the reaction temperature in step 1) is 0-5 ℃.
4. The nano zirconium phosphate coated modified ammonium polyphosphate according to claim 1, wherein the concentration of the tetrabutyl ammonium hydroxide solution in the step 1) is 0.05-5mol/L, and the dropping time is 30-90 min; the concentration of the concentrated acid is 3-18mol/L, and the dripping time is 30-90 min.
5. The nano zirconium phosphate coated modified ammonium polyphosphate according to claim 1, wherein the mass ratio of the polyethyleneimine to the ammonium polyphosphate in the step 2) is 1 (0.1-5).
6. The nano zirconium phosphate coated modified ammonium polyphosphate according to claim 1, wherein the adsorption treatment time in the step 2) is 2-12 h.
7. The nano zirconium phosphate coated modified ammonium polyphosphate according to claim 1, wherein the dropping time of the mixed solution in the step 3) is 30-90 min.
8. The nano zirconium phosphate coated modified ammonium polyphosphate according to claim 1, wherein the stirring reaction time in the step 3) is 12-48 h.
9. The nano zirconium phosphate coated modified ammonium polyphosphate according to claim 1, wherein the mass ratio of the ammonium polyphosphate to the zirconium phosphate is 5: 1-1: 10.
10. The intumescent fire retardant coating prepared by using the nano zirconium phosphate coated and modified ammonium polyphosphate according to any one of claims 1 to 9 is characterized by comprising the following components in percentage by mass: 20-30% of methacrylic acid modified acrylate core-shell emulsion, 30-36% of nano zirconium phosphate coated modified ammonium polyphosphate, 10-20% of pentaerythritol, 10-15% of melamine, 1-5% of titanium dioxide, 0.5-1% of hydroxyethyl cellulose, 0.5-1% of dispersing agent, 0.5-1% of defoaming agent, 0.5-1% of n-octanol and the balance of water.
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