CN111234564A - Environment-friendly flame retardant and intumescent fire-retardant coating prepared from same - Google Patents

Environment-friendly flame retardant and intumescent fire-retardant coating prepared from same Download PDF

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CN111234564A
CN111234564A CN202010161219.5A CN202010161219A CN111234564A CN 111234564 A CN111234564 A CN 111234564A CN 202010161219 A CN202010161219 A CN 202010161219A CN 111234564 A CN111234564 A CN 111234564A
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flame retardant
environment
friendly flame
zirconium phosphate
retardant
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CN111234564B (en
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刘治田
王成
霍思奇
张旗
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Wuhan Institute of Technology
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    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
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    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/04—Physical treatment, e.g. grinding, treatment with ultrasonic vibrations
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    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/08—Treatment with low-molecular-weight non-polymer organic compounds
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    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
    • C09D151/003—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
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    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/18—Fireproof paints including high temperature resistant paints
    • C09D5/185—Intumescent paints
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/32—Phosphorus-containing compounds
    • C08K2003/321—Phosphates
    • C08K2003/328—Phosphates of heavy metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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Abstract

The invention discloses an environment-friendly flame retardant, which is prepared by firstly utilizing tetrabutyl ammonium hydroxide and phosphoric acid to strip zirconium phosphate and then utilizing furfuryl amine to coat the zirconium phosphate. The flame retardant can effectively solve the problems of easy agglomeration and the like of zirconium phosphate, and can play a synergistic flame-retardant role with an intumescent flame-retardant system in the fireproof coating; the preparation method is applied to the preparation of the intumescent fire-retardant coating, and the film forming property, the fire resistance and the durability of the obtained fire-retardant coating can be obviously improved. The flame retardant provided by the invention integrates flame retardance, smoke suppression and enhancement functions, and has the advantages of low halogen-free cost, good char formation, high carbon layer strength, environmental friendliness, wide applicability, simple related preparation method process, mild reaction conditions and suitability for popularization and application.

Description

Environment-friendly flame retardant and intumescent fire-retardant coating prepared from same
Technical Field
The invention belongs to the technical field of flame retardant materials, and particularly relates to an environment-friendly flame retardant and an intumescent fire retardant coating prepared by using the same.
Background
A fire retardant coating is a substance that can act on the surface of a flammable material to increase its fire resistance, slow the rate of combustion, or prevent combustion for a certain period of time. The steel structure expansion type fireproof coating is prepared by taking high molecular water-based emulsion, high molecular resin and the like as a matrix, and adding an expansion fireproof system consisting of an acid source, a gas source, a carbon source and the like, a filler and an auxiliary agent. The components react at high temperature, and are dehydrated and carbonized to form a uniform and compact cellular expanded carbon layer to isolate air and heat transfer, thereby achieving the effects of fire prevention and heat insulation. However, the fireproof coating still has the defects that an expanded carbon layer formed at high temperature is not firm enough and is easy to be broken by flame, so that the fireproof performance of the coating is poor, and the like, and the defects can obviously reduce the fire resistance and the durability of the expanded fireproof coating.
ZrP is an artificially synthesized layered solid acid, has excellent thermal stability, chemical stability, strong acid and alkali resistance, has the characteristics of controllable length-diameter ratio, narrow particle size distribution and the like, and is one of excellent matrixes for preparing the polymer layered nano composite material. The ZrP layers are superposed through hydrogen bonding and Van der Waals force, and HP04 of the ZrP layers2-H in the radical+The interlayer space has large free activity, and the interlayer crystal water molecules can be replaced by polar organic molecules. Although ZrP has a layered barrier effect and a solid acid catalysis carbonization effect, the flame retardance of the flame retardant can be obviously improved, the carbon layer of the flame retardant system reported at present is loose, and zirconium phosphate is easy to agglomerate, so that the carbonization effect of a zirconium phosphate catalysis polymer is limited, and the problems of poor thermal stability, low flame retardant efficiency and the like of the flame retardant are caused.
In order to solve the problems that the flame retardant efficiency is low because zirconium phosphate can not efficiently catalyze polymers to form carbon, and an expanded carbon layer formed by the existing fireproof coating at high temperature is not firm enough; in patent CN109810545A, zirconium phosphate is stripped into nanosheets and added into a flame-retardant system, and the catalysis of the zirconium phosphate nanosheets is utilized to improve the carbonization effect of polymers, so that the flame-retardant efficiency is improved.
Therefore, the further optimization of the modification means and the performance of the zirconium phosphate compound has great research and application significance, and the development of a new-generation fireproof coating which is environment-friendly, efficient, durable, stable and attractive is greatly needed.
Disclosure of Invention
The invention mainly aims to solve the problems of poor char quality, low loose strength of a char layer, low flame retardant efficiency and the like of the conventional flame retardant coating system, the zirconium phosphate is stripped by tetrabutylammonium hydroxide and phosphoric acid to expose hydroxyl groups between zirconium phosphate layers, and then the zirconium phosphate is coated by furfurylamine to prepare the environment-friendly flame retardant.
In order to achieve the purpose, the invention adopts the technical scheme that:
an environment-friendly flame retardant is prepared by the following steps:
1) exfoliated zirconium phosphate (ZrP): ultrasonically dispersing zirconium phosphate in water under a stirring condition, then dropwise adding a tetrabutylammonium hydroxide solution (TBA can weaken the acting force between zirconium phosphate layers, peeling zirconium phosphate and exposing hydroxyl groups between the layers), ultrasonically stirring for reaction after the dropwise adding is finished, dropwise adding concentrated acid into the obtained reaction system for secondary reaction (removing the TBA solution), and then carrying out solid-liquid separation to obtain a semitransparent gel precipitate;
2) furfuryl amine coated zirconium phosphate: mechanically stirring the product obtained in the step 1) and furfuryl amine at a certain temperature, centrifugally washing, and drying to obtain the environment-friendly flame retardant.
In the scheme, the zirconium phosphate is α -zirconium phosphate.
In the above scheme, the concentrated acid is one or more of concentrated phosphoric acid, concentrated hydrochloric acid and concentrated nitric acid.
In the scheme, the molar ratio of the zirconium phosphate to the furfuryl amine is 1 (1-8).
In the scheme, the concentration of the tetrabutylammonium hydroxide solution is 0.05-5 mol/L; the dropping time is 30-90 min.
In the scheme, the molar ratio of zirconium phosphate to tetrabutylammonium hydroxide introduced in the step 1) is 5: 1-1: 6.
In the scheme, the concentration of the concentrated acid is 3-18 mol/L; the dropping time is 30-90 min.
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 temperature of the ultrasonic stirring reaction and the secondary reaction is 0-5 ℃.
In the scheme, the ultrasonic dispersion in the step 1) is carried out for 30-60 min; the ultrasonic stirring reaction time is 2-6 h; the secondary reaction time is 2-8 h.
In the scheme, the mechanical stirring temperature in the step 2) is 20-60 ℃, and the stirring time is 24-36 h.
The environment-friendly flame retardant obtained by the scheme is applied to preparation of the 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 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-octyl alcohol, 1-10% of environment-friendly flame retardant and the balance of water.
The intumescent fire-retardant coating prepared according to the scheme has the advantages of excellent fire resistance, low halogen-free cost, good char forming property, high carbon layer strength, environmental protection and wide applicability.
The principle of the invention is as follows:
according to the invention, tetrabutylammonium hydroxide is firstly used for stripping zirconium phosphate to expose hydroxyl groups among zirconium phosphate layers, and then furfuryl amine and the stripped zirconium phosphate are used for coating the zirconium phosphate to prepare the environment-friendly flame retardant, and the flame retardant is applied to an intumescent fire retardant coating system, so that the fire resistance and the durability of the intumescent fire retardant coating system can be remarkably improved: when a fire disaster happens, pentaerythritol reacts with ammonium polyphosphate at high temperature, dehydration and carbonization are carried out, melamine is heated and decomposed to release non-combustible gas, a honeycomb-shaped carbon layer is formed, and the flame retardant effect is played; the environment-friendly flame retardant disclosed by the invention can quickly form carbon on the surface of a base material while playing a flame retardant role, fills gaps between sheet layers to form a plurality of dense micro-nano carbon cages, blocks oxygen in air, seals a large amount of degradation products, simultaneously introduces furfuryl amine to act in the micro carbon cages, and zirconium phosphate and the furfuryl amine react and can be crosslinked to generate a high-thermal-stability crosslinked net structure, so that the graphitization degree of a combustion carbon layer is further improved, a P-N synergistic effect can be realized, the carbon layer strength of the carbon cages can be effectively improved, a flame retardant role is further played on the microstructure level, and the flame retardant role and an expansion flame retardant system in the fireproof coating play a synergistic flame retardant role and improve the durability of the flame retardant.
Compared with the prior art, the invention has the beneficial effects that:
1) by adding the environment-friendly flame retardant component, the high-efficiency flame retardance and excellent char forming property of the environment-friendly flame retardant are utilized to play a synergistic flame retardant role with an expansion system consisting of ammonium polyphosphate, pentaerythritol and melamine in the fireproof coating, so that the fireproof coating has a carbon layer with higher quality strength, and therefore, the fireproof coating has high-efficiency flame retardance.
2) The furfuryl amine is used for carrying out reaction coating on the zirconium phosphate sheet layer, so that the surface polarity of zirconium phosphate can be effectively reduced, the uniformity of the surfaces of the zirconium phosphate and the zirconium phosphate can be ensured, the components of the fireproof coating can be effectively simplified, the compatibility and the dispersibility among the components of the coating are better, the film forming property and the practicability of the coating can be improved, and the fireproof performance of the obtained fireproof coating can be further effectively improved.
3) The furan ring in the furfuryl amine can be used as a charring agent when a polymer matrix is burnt or degraded, and can play the roles of delaying the thermal decomposition of the polymer, the combined action of phosphorus and nitrogen, synergistic charring and flame retardance and the like, so that the flame retardant has better thermal stability, and the flame retardant property of the intumescent fire-retardant coating is effectively improved.
4) The flame retardant provided by the invention integrates flame retardant and enhancement functions, and has the advantages of low halogen-free cost, good char forming property, high carbon layer strength, environmental friendliness, wide applicability, simple related preparation method process, mild reaction conditions and suitability 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 zirconium phosphate (α -zirconium phosphate) used was prepared by preparing 100mL of concentrated phosphoric acid having a molar concentration of 3mo1/L, charging into a 250mL three-necked flask, and adding 10.00g of zirconium oxychloride (ZrOCl)2-8H20) 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
An environment-friendly flame retardant is prepared by the following steps:
1) 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 (TBA concentration is 0.1mol/L) is dripped into the four-mouth flask at a constant speed within 30min, ultrasonic stirring reaction is continued for 2h after dripping, 20ml of concentrated phosphoric acid with the concentration of 14.5mol/L is dripped into the flask at a constant speed within 30min, and after the reaction is finished (2h), the mixed solution is centrifuged to carry out solid-liquid separation, so as to obtain semitransparent gel precipitate and is washed by distilled water;
2) furfuryl amine coated zirconium phosphate: and (2) mechanically stirring the product obtained in the step 1) and 0.06mol of furfuryl amine at 40 ℃ for 24h, centrifugally washing, and vacuum drying at 80 ℃ to obtain the environment-friendly flame retardant.
The application of the environment-friendly flame retardant obtained in the embodiment to the preparation of the intumescent fire retardant coating comprises the following steps: grinding the weighed environment-friendly flame retardant, 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.
Example 2
An environment-friendly flame retardant is prepared by the following steps:
1) 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 (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 concentrated phosphoric acid with the concentration of 14.5mol/L is dripped into the flask at a constant speed within 30min, and after the reaction is finished (2h), the mixed solution is centrifuged to carry out solid-liquid separation, so as to obtain semitransparent gel precipitate and is washed by distilled water;
2) furfuryl amine coated zirconium phosphate: and (2) mechanically stirring the product obtained in the step 1) and 0.03mol of furfuryl amine at 40 ℃ for 24 hours, centrifugally washing, and drying in vacuum at 80 ℃ to obtain the environment-friendly flame retardant.
The application of the environment-friendly flame retardant obtained in the embodiment to the preparation of the intumescent fire retardant coating comprises the following steps: grinding the weighed environment-friendly flame retardant, 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 1
The environment-friendly flame retardant obtained in the embodiment 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 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, 10% of water and 5% of environment-friendly flame retardant; grinding the weighed environment-friendly flame retardant, 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 environment-friendly flame retardant obtained in the embodiment 1 is applied to the preparation of the intumescent fire-retardant coating, and comprises the following components in percentage by mass: 20% of acrylate emulsion, 36% 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, 12% of water and 3% of environment-friendly flame retardant; grinding the weighed environment-friendly flame retardant, 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 3
The environment-friendly flame retardant obtained in the embodiment 1 is applied to the preparation of the intumescent fire-retardant coating, and comprises the following components in percentage by mass: 20% of acrylate emulsion, 36% 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, 13% of water and 2% of environment-friendly flame retardant; grinding the weighed environment-friendly flame retardant, 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.
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 acrylate emulsion, 36% 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 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 acrylate emulsion, 36% 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, 10% 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 acrylate emulsion, 36% 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, 10% of water and 5% of furfuryl amine.
Comparative example 4
The preparation method of the fireproof coating of comparative example 4 is substantially the same as that of application example 1, except that the components and the mass percentages thereof are as follows: 20% of acrylate emulsion, 36% 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, 10% of water, and 5% of mixture of zirconium phosphate and furfuryl amine (3% of zirconium phosphate and 2% of furfuryl amine).
The intumescent fire-retardant coatings obtained in application examples 1-3 and comparative examples 1-4 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 1-4
Figure BDA0002405864200000071
Figure BDA0002405864200000081
The above results show that: the environment-friendly flame retardant disclosed by the invention has the advantages of higher flame retardant efficiency, environmental friendliness, no pollution, good compatibility with resin, base materials and the like, and other properties of the material can be effectively considered, and the environment-friendly flame retardant can be applied to preparation of an intumescent fire-retardant coating, can show the advantages of excellent fire resistance, good char formation, high carbon layer strength, good stability and the like, and is simple in related preparation method and wide in application field.
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 (9)

1. An environment-friendly flame retardant is characterized in that the preparation method comprises the following steps:
1) stripping zirconium phosphate: 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) furfuryl amine coated zirconium phosphate: mechanically stirring the product obtained in the step 1) and furfuryl amine, centrifugally washing, and drying to obtain the environment-friendly flame retardant.
2. The environment-friendly flame retardant according to claim 1, wherein the molar ratio of the zirconium phosphate to the furfuryl amine is 1 (1-8).
3. The environment-friendly flame retardant according to claim 1, wherein the concentration of the tetrabutylammonium hydroxide solution is 0.05-5 mol/L; the dropping time is 30-90 min.
4. The environment-friendly flame retardant according to claim 1, wherein the molar ratio of zirconium phosphate to tetrabutylammonium hydroxide introduced in step 1) is 5:1 to 1: 6.
5. The environment-friendly flame retardant according to claim 1, wherein the concentrated acid is one or more of concentrated phosphoric acid, concentrated hydrochloric acid, and concentrated nitric acid; the concentration is 3-18 mol/L.
6. The environment-friendly flame retardant according to claim 1, wherein the ultrasonic stirring reaction and the secondary reaction temperature are 0-5 ℃.
7. The environment-friendly flame retardant according to claim 1, wherein the ultrasonic dispersion in step 1) is carried out for 30-60 min; the ultrasonic stirring reaction time is 2-6 h; the secondary reaction time is 2-8 h.
8. The environment-friendly flame retardant as defined in claim 1, wherein the mechanical stirring temperature in step 2) is 20-60 ℃ and the stirring time is 24-36 h.
9. An intumescent fire retardant coating prepared by using the environment-friendly fire retardant of any one of claims 1 to 8, which is characterized by comprising the following components in percentage by mass: 20-30% of methacrylic acid modified acrylate core-shell emulsion, 30-36% of 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-octyl alcohol, 1-10% of environment-friendly flame retardant and the balance of water.
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CN113831597A (en) * 2021-10-15 2021-12-24 武汉工程大学 Bio-based macromolecule modified nano zirconium phosphate flame retardant and fireproof coating prepared by using same
CN114958061A (en) * 2022-05-05 2022-08-30 北京建筑材料检验研究院有限公司 Multi-layer fireproof coating for high-rise building steel structure
CN115122454A (en) * 2022-07-19 2022-09-30 上海五岳木业有限公司 Fireproof furniture panel and preparation method thereof

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