CN110835395A - Flame-retardant ablation-resistant filler and preparation method and application thereof - Google Patents
Flame-retardant ablation-resistant filler and preparation method and application thereof Download PDFInfo
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- C08G14/00—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00
- C08G14/02—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes
- C08G14/04—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols
- C08G14/06—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols and monomers containing hydrogen attached to nitrogen
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- C08G14/00—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00
- C08G14/02—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes
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Abstract
The invention relates to a flame-retardant ablation-resistant filler, a preparation method and application thereof, wherein the raw materials of the filler comprise a phenolic compound, an aldehyde compound and an amine compound, and the molar ratio of amino groups on the phenolic compound, the aldehyde compound and the amine compound is (X): y: z, wherein Y is (1-3) X X + (0.5-2) X Z, the average particle size of the filler is 120-5000nm, the nitrogen content is 5-35 w t%, and the filler is prepared by (1) mixing a phenolic compound and an aldehyde compound in a solvent to obtain a solution A; (2) mixing an amine compound and an aldehyde compound in a solvent to obtain a solution B; (3) mixing the solution A and the solution B to obtain a solution C; (4) heating, washing, drying and grinding the solution C to obtain the compound. Compared with the prior art, the invention has the advantages of simple preparation method, good sphericity, uniform granularity, excellent flame retardant property and the like, and can be used as a filler of flame-retardant, ablative and other heat-proof composite materials and coatings.
Description
Technical Field
The invention relates to the technical field of flame-retardant materials, in particular to a flame-retardant ablation-resistant filler and a preparation method and application thereof.
Background
The phenolic resin is found in synthetic resins firstly and is a resin variety which realizes industrial production at the earliest time, and is widely applied to the field of aerospace, especially ablation-resistant materials due to the characteristics of cheap raw materials, easy synthesis, excellent ablation resistance, high carbon forming rate after high-temperature pyrolysis and the like. In recent years, different types and forms of modified phenolic resins have been developed, and the application range has been greatly widened.
Patent CN 108840981A discloses a method for synthesizing flame-retardant phenolic resin, which takes acetaminophen and formaldehyde as raw materials to synthesize nitrogenous phenolic resin under the action of an alkaline catalyst; patent CN104448175A discloses a method for synthesizing melamine phenolic resin, which takes formaldehyde, melamine and phenol as raw materials, takes p-toluenesulfonic acid as a curing agent, adjusts the pH value through triethylamine and phosphoric acid, and synthesizes melamine phenolic resin in a three-neck flask. The synthesis method disclosed in the above patent requires the participation of a catalyst and the adjustment of pH, which is difficult to expand the production, and the form of the product cannot be effectively controlled and adjusted, resulting in a limited application range.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide the flame-retardant ablation-resistant filler which is simple in preparation method, good in sphericity, uniform in granularity and high in nitrogen content, and the preparation method and the application thereof.
The purpose of the invention can be realized by the following technical scheme:
a flame-retardant ablation-resistant filler is prepared from the following raw materials of a phenolic compound, an aldehyde compound and an amine compound, wherein the molar ratio of amino groups on the phenolic compound to the aldehyde compound to the amine compound is X: y: and Z, wherein Y is (1-3). times.X + (0.5-2). times.Z.
Further, the phenolic compound comprises one or more of phenol, resorcinol or hydroquinone; the aldehyde compound comprises one or more of formaldehyde, furfural or terephthalaldehyde; the amine compound comprises one or more of melamine, ethylenediamine, diethylenetriamine, tetraethylenepentamine, hexamethylenediamine, piperazine or polyethyleneimine.
The filler has an average particle diameter of 120-5000nm and a nitrogen content of 5-35 wt%, preferably 10-35 wt%, more preferably 20-35 wt%.
A preparation method of a flame-retardant ablation-resistant filler comprises the following steps:
(1) mixing a phenolic compound and an aldehyde compound in a solvent, and stirring for reaction until the mixture is clear to obtain a solution A;
(2) mixing an amine compound and an aldehyde compound in a solvent, and stirring for reaction until the mixture is clear to obtain a solution B;
(3) mixing the solution A and the solution B, stirring, and supplementing a solvent to adjust the concentration of the solution A and the solution B if necessary to obtain a solution C;
(4) and heating the solution C, reacting until a solid is separated out from the solution, pouring out supernatant liquor, washing, drying and grinding the separated solid to obtain the flame-retardant ablation-resistant filler.
Further, the phenolic compound comprises one or more of phenol, resorcinol or hydroquinone, preferably resorcinol; the aldehyde compound comprises one or more of formaldehyde, furfural or terephthalaldehyde, preferably formaldehyde; the amine compound comprises one or more of melamine, ethylenediamine, diethylenetriamine, tetraethylenepentamine, hexamethylenediamine, piperazine or polyethyleneimine, preferably melamine; the solvent comprises one or more of water, ethanol or dimethyl sulfoxide.
Further, the molar ratio of the phenolic compound to the aldehyde compound in the step (1) is 1 (1-3); the total concentration of the phenolic compound and the aldehyde compound is 3-40 omega t%, the reaction temperature is 20-35 ℃, and the stirring speed is 150-250 rpm.
Further, the molar ratio of the amino group on the amine compound to the aldehyde compound in the step (2) is 1 (0.5-2); the total concentration of the amine compound and the aldehyde compound is 5-30 omega t%; the reaction temperature is 20-90 ℃, and the stirring speed is 150-250 rpm.
Further, the volume ratio of the solution A to the solution B in the step (3) is (0.5-2.5):1, the rotation speed of the stirring is 150-250rpm, the time is 1-10min, and the total concentration of the phenolic compound, the aldehyde compound and the amine compound is 0.02-0.2 g/mL.
Further, the reaction temperature in the step (4) is 80-180 ℃, the reaction time is 1-24h, the drying temperature is 50-90 ℃, and the reaction time is 12-36 h.
The application of the flame-retardant ablation-resistant filler in the thermal-protection composite material is characterized in that the flame-retardant ablation-resistant filler is used as a filler of a flame-retardant ablation-type thermal-protection composite material or a coating.
Further, the total heat release amount of the heat-proof composite material is reduced by 15-30MJ/m by the flame-retardant ablation-resistant filler2The peak value of the heat release rate is reduced by 10-30kW/m2。
Since phenolic aldehyde polymerizations generally require basic catalysts, amine aldehyde polymerizations generally require acidic catalysts. In the present invention, the phenolic compound which is acidic in the solution a serves as a catalyst for the amine aldehyde polymerization in the solution B, and the amine compound which is basic in the solution B serves as a catalyst for the phenol aldehyde polymerization in the solution a, so that the solution a and the solution B can mutually catalyze the polymerization reaction with each other. Specifically, the phenolic compound donates a proton to promote the dehydration condensation of an amine aldehyde, while the deprotonated phenolic compound, that is, a phenoxide, can undergo a substitution reaction with the aldehyde compound at the ortho-para position.
The invention aims to prepare a copolymer of phenol, aldehyde and amine, wherein the phenol and the aldehyde mainly provide ablation resistance, the amine provides high flame retardance, and the preparation is seemingly the simplest by a one-pot method, but some amine compounds such as melamine react with aldehyde compounds slower than the phenol and the aldehyde, and sometimes the amine aldehyde reaction speed needs to be increased by heating. The dissolving process of the solution A and the solution B is actually the prepolymerization process of phenolic aldehyde and amine aldehyde, and the respective reaction is favorable for the controllability of the prepolymerization process.
Compared with the prior art, the invention has the following advantages:
(1) the invention has simple production process and mild reaction condition, does not need to add a catalyst independently, does not need to adjust the pH, and can be pelletized only by simply mixing and heating the reaction raw materials;
(2) prepolymerizing phenol, aldehyde and amine respectively, and mixing; the method has controllability compared with a one-pot method, and can adjust the proportion of phenol, aldehyde and amine in the product microspheres to be consistent with the feeding ratio;
(3) the filler prepared by the invention combines the flame retardance of amine compounds and the ablation resistance of phenolic resin; on one hand, the amine compound containing nitrogen in the filler can release inert gases such as nitrogen and the like at high temperature, dilute oxygen and combustible gas and slow down the combustion of a matrix; on the other hand, phenolic aldehyde components in the filler form a carbon layer at high temperature, so that the ablation resistance of the matrix is improved, and the structure of the material is kept complete; in addition, the flame retardance and the ablation resistance of the filler can be flexibly adjusted by changing the type and the proportion of raw materials according to specific requirements, and the nitrogen content can reach 35 omega t at most, namely the filler is a new material fusing three elements of ablation resistance, flame retardance and filler;
(4) the flame-retardant ablation-resistant filler prepared by the invention has good sphericity, uniform granularity and good ablation resistance and flame retardance, so that the flame-retardant ablation-resistant filler can be used as a powder filler to be applied to various composite material systems, and has a good effect particularly in an organic silicon system.
Drawings
FIG. 1 is a photograph of the appearance of the flame-retardant ablation-resistant filler of example 1;
FIG. 2 is an SEM photograph of the flame retardant ablation resistant filler of example 1;
FIG. 3 is a graph of the heat release rate in a cone calorimeter test for silicone rubber before and after the addition of the flame-retardant ablation-resistant filler of example 1;
FIG. 4 is a graph of the total heat release in a cone calorimeter test for silicone rubbers before and after the addition of the flame-retardant ablation-resistant filler of example 1;
FIG. 5 is a top view of the silicone rubber of example 1 after cone calorimeter testing before and after the addition of the flame-retardant, ablation-resistant filler.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments.
Example 1
12.81g resorcinol and 18.96g formaldehyde solution (37 t% strength) were added to 50mL deionized water and stirred at 200rpm at ambient temperature until the solution was clear to give solution A.
14.70g of melamine and 28.38g of formaldehyde solution (37 w/t%) were added to 100mL of deionized water and stirred at 85 ℃ at 200rpm until the solution was clear, giving solution B.
And after the solution B is cooled to the normal temperature, pouring the solution A into the solution B, continuously stirring for 5min, and diluting the solution to 300mL by using deionized water to obtain a solution C.
And heating the solution C to 85 ℃, keeping the temperature and standing for 2h, cooling to room temperature, pouring out supernatant, washing with deionized water for 3 times, filtering, and drying in an electric heating air blast drying oven at 85 ℃ for 24h to obtain the flame-retardant ablation-resistant filler.
As shown in FIG. 1-2, the flame-retardant ablation-resistant filler obtained in this example had good sphericity and uniform particle size, and had an average particle diameter of about 2.5 μm and a nitrogen content of 26 ω t%.
The flame-retardant ablation-resistant filler obtained in example 1 was added to the silicone rubber in a ratio of 20 parts per hundred parts of the silicone rubber to prepare a sample of 100mm × 100mm × 3mm for cone calorimeter testing, the heat radiation power was 50kW/m2And compared with the sample without the flame-retardant and ablation-resistant filler, and the results are shown in FIGS. 3-5;
the flame-retardant ablation-resistant filler can increase the peak value of the heat release rate of the silicone rubber from 150kW/m2Down to 140kW/m2The total heat release amount is 85MJ/m2Reduced to 70MJ/m2After the test of the cone calorimeter, the silicon rubber without the flame-retardant and ablation-resistant filler is burnt through and burnt off, and the silicon rubber with the flame-retardant and ablation-resistant filler maintains a relatively complete form. The above results show that the flame-retardant ablation-resistant filler synthesized in example 1 can significantly improve the flame-retardant and ablation-resistant properties of the matrix.
Example 2
Solution A was obtained by adding 17.82g of resorcinol and 26.28g of formaldehyde solution (37 ω t% concentration) to 50mL of deionized water and stirring at 200rpm at normal temperature until the solution was clear.
10.20g of melamine and 19.62g of formaldehyde solution (37 w/t%) were added to 100mL of deionized water and stirred at 85 ℃ at 200rpm until the solution was clear, giving solution B.
And after the solution B is cooled to the normal temperature, pouring the solution A into the solution B, continuously stirring for 5min, and diluting the solution to 300mL by using deionized water to obtain a solution C.
And heating the solution C to 85 ℃, keeping the temperature and standing for 2h, cooling to room temperature, pouring out supernatant, washing with deionized water for 3 times, filtering, and drying in an electric heating air blast drying oven at 85 ℃ for 24h to obtain the flame-retardant ablation-resistant filler.
The flame-retardant ablation-resistant filler obtained in the embodiment has good sphericity and uniform particle size, the average particle size is about 4 mu m, and the nitrogen content is 17 omega t%.
Example 3
8.22g resorcinol and 12.18g formaldehyde solution (37 t% strength) were added to 50mL deionized water and stirred at 200rpm at ambient temperature until the solution was clear to give solution A.
18.84g of melamine and 36.30g of formaldehyde solution (37 w/t%) were added to 100mL of deionized water and stirred at 85 ℃ at 200rpm until the solution was clear, giving solution B.
And after the solution B is cooled to the normal temperature, pouring the solution A into the solution B, continuously stirring for 5min, and diluting the solution to 300mL by using deionized water to obtain a solution C.
And heating the solution C to 85 ℃, keeping the temperature and standing for 2h, cooling to room temperature, pouring out supernatant, washing with deionized water for 3 times, filtering, and drying in an electric heating air blast drying oven at 85 ℃ for 24h to obtain the flame-retardant ablation-resistant filler.
The flame-retardant ablation-resistant filler obtained in the embodiment has good sphericity and uniform particle size, the average particle size is about 1.7 mu m, and the nitrogen content is 31 omega t%.
Example 4
4.8g resorcinol and 3.6g formaldehyde solution (37 w.t%) were added to 160mL deionized water and stirred until the solution was clear to give solution A.
1.8g of ethylenediamine and 3.6g of formaldehyde solution (37. omega. t%) were added to 64mL of ethanol and stirred until the solution was clear to give solution B.
And pouring the solution A into the solution B, and stirring for 5min to obtain a solution C.
And heating the solution C to 80 ℃, keeping the temperature, standing for 24 hours, cooling to room temperature, pouring out supernatant, and drying the precipitate in an electrothermal blowing drying oven at 50 ℃ for 24 hours to obtain the flame-retardant ablation-resistant filler.
The flame-retardant ablation-resistant filler obtained in the embodiment has good sphericity and uniform particle size, the average particle size is about 2 mu m, and the nitrogen content is 7.3 omega t%.
Example 5
4.8g resorcinol and 3.6g formaldehyde solution (37 w.t%) were added to 160mL deionized water and stirred until the solution was clear to give solution A.
2.1g of diethylenetriamine and 3.6g of formaldehyde solution (. omega.t%) were added to 64mL of ethanol and stirred until the solution became clear, giving solution B.
And pouring the solution A into the solution B, and stirring for 5min to obtain a solution C.
And heating the solution C to 80 ℃, keeping the temperature, standing for 24 hours, cooling to room temperature, pouring out supernatant, and drying the precipitate in an electrothermal blowing drying oven at 50 ℃ for 24 hours to obtain the flame-retardant ablation-resistant filler.
The flame-retardant ablation-resistant filler obtained in the embodiment has good sphericity and uniform particle size, the average particle size is about 1.3 mu m, and the nitrogen content is 8.1 omega t%.
Example 6
4.8g resorcinol and 3.6g formaldehyde solution (37 w.t%) were added to 160mL deionized water and stirred until the solution was clear to give solution A.
2.3g tetraethylenepentamine and 3.6g formaldehyde solution (37 w t%) were added to 64mL ethanol and stirred until the solution was clear to give solution B.
And pouring the solution A into the solution B, and stirring for 5min to obtain a solution C.
And heating the solution C to 80 ℃, keeping the temperature, standing for 24 hours, cooling to room temperature, pouring out supernatant, and drying the precipitate in an electrothermal blowing drying oven at 50 ℃ for 24 hours to obtain the flame-retardant ablation-resistant filler.
The flame-retardant ablation-resistant filler obtained in the embodiment has good sphericity and uniform particle size, the average particle size is about 2 mu m, and the nitrogen content is 9.2 omega t%.
Example 7
4.8g resorcinol and 3.6g formaldehyde solution (37 w.t%) were added to 160mL deionized water and stirred until the solution was clear to give solution A.
3.5g of hexamethylenediamine and 3.6g of formaldehyde solution (37. omega. t%) were added to 64mL of ethanol and stirred until the solution was clear, giving solution B.
And pouring the solution A into the solution B, and stirring for 5min to obtain a solution C.
And heating the solution C to 80 ℃, keeping the temperature, standing for 24 hours, cooling to room temperature, pouring out supernatant, and drying the precipitate in an electrothermal blowing drying oven at 50 ℃ for 24 hours to obtain the flame-retardant ablation-resistant filler.
The flame-retardant ablation-resistant filler obtained in the embodiment has good sphericity and uniform particle size, the average particle size is about 1.5 mu m, and the nitrogen content is 7.1 omega t%.
Example 8
4.8g resorcinol and 3.6g formaldehyde solution (37 w.t%) were added to 160mL deionized water and stirred until the solution was clear to give solution A.
2.6g piperazine and 3.6g formaldehyde solution (37 ω t% concentration) were added to 64mL ethanol and stirred until the solution was clear to give solution B.
And pouring the solution A into the solution B, and stirring for 5min to obtain a solution C.
And heating the solution C to 80 ℃, keeping the temperature, standing for 24 hours, cooling to room temperature, pouring out supernatant, and drying the precipitate in an electrothermal blowing drying oven at 50 ℃ for 24 hours to obtain the flame-retardant ablation-resistant filler.
The flame-retardant ablation-resistant filler obtained in the embodiment has good sphericity and uniform particle size, the average particle size is about 1.5 mu m, and the nitrogen content is 8.7 omega t%.
Example 9
4.8g resorcinol and 3.6g formaldehyde solution (37 w.t%) were added to 160mL deionized water and stirred until the solution was clear to give solution A.
2.6g of polyethyleneimine (MW 1800g/mol) and 3.6g of formaldehyde solution (concentration 37. omega. t%) were added to 64mL of ethanol and stirred until the solution was clear, giving solution B.
And pouring the solution A into the solution B, and stirring for 5min to obtain a solution C.
And heating the solution C to 80 ℃, keeping the temperature, standing for 24 hours, cooling to room temperature, pouring out supernatant, and drying the precipitate in an electrothermal blowing drying oven at 50 ℃ for 24 hours to obtain the flame-retardant ablation-resistant filler.
The flame-retardant ablation-resistant filler obtained in the embodiment has good sphericity and uniform granularity, the average particle size is about 120nm, and the nitrogen content is 8.7 omega t%.
Example 10
(1) Mixing hydroquinone and furfural in ethanol solvent, stirring at room temperature for reaction until the mixture is clear, wherein the stirring speed is 150-250rpm, and obtaining a solution A; wherein the molar ratio of the benzenediol to the furfural is 1: 1; the total concentration of benzenediol and furfural was 3 ω t%.
(2) Mixing hexamethylenediamine and furfural in ethanol, stirring at 90 ℃ for reaction until the mixture is clear, wherein the stirring speed is 150-250rpm, and obtaining a solution B; wherein the molar ratio of hexamethylene diamine to furfural is 1: 1; the total concentration of hexamethylenediamine and furfural was 30 ω t%;
(3) mixing the solution A and the solution B according to the volume ratio of 0.5:1, and stirring to obtain a solution C; the stirring speed is 150-250rpm, the time is 1-10min, and if necessary, a solvent is added to ensure that the total concentration of the hexamethylene diamine, the hydroquinone and the furfural is 0.02 g/mL.
(4) And heating the solution C, reacting for 1-4h at 80 ℃ until a solid is separated out of the solution, pouring out supernatant, washing the separated solid, drying for 12-24h at 50-60 ℃, and grinding to obtain the flame-retardant ablation-resistant filler.
The flame-retardant ablation-resistant filler obtained in the embodiment has good sphericity, uniform granularity, average particle size of about 120nm and nitrogen content of about 35 omega t percent, the flame-retardant ablation-resistant filler obtained in the embodiment is added into organic silicon rubber according to the proportion of 20 parts/hundred parts of organic silicon rubber to prepare a sample of 100mm multiplied by 3mm, and the sample is subjected to cone calorimeter test, and the heat radiation power is 50kW/m2After testing, the total heat release amount of the heat-proof composite material can be reduced by 30MJ/m2The peak value of the heat release rate is reduced by 30kW/m2。
Example 11
(1) Mixing resorcinol and furfural in a solvent dimethyl sulfoxide, stirring at room temperature for reaction until the mixture is clear, wherein the stirring speed is 150-250rpm, and obtaining a solution A; wherein the molar ratio of the resorcinol to the furfural is 1: 3; the total concentration of resorcinol and furfural was 40 wt%.
(2) Mixing ethylenediamine and furfural in dimethyl sulfoxide, stirring at 90 ℃ for reaction until the mixture is clear, wherein the stirring speed is 150-250rpm, and obtaining a solution B; wherein the molar ratio of the ethylenediamine to the furfural is 1: 1; the total concentration of ethylenediamine and furfural was 5 ω t%;
(3) mixing the solution A and the solution B according to the volume ratio of 2.5:1, and stirring to obtain a solution C; stirring at 150-250rpm for 1-10min, and adding dimethyl sulfoxide as solvent if necessary to make total concentration of ethylenediamine, resorcinol and furfural 0.2 g/mL.
(4) And heating the solution C, reacting for 4-24h at 180 ℃ until a solid is separated out of the solution, pouring out supernatant, washing the separated solid, drying for 24-36h at 60-90 ℃, and grinding to obtain the flame-retardant ablation-resistant filler.
The flame-retardant ablation-resistant filler obtained in the embodiment has good sphericity, uniform granularity, average particle size of about 5000nm and nitrogen content of about 5 omega t percent, and the flame-retardant ablation-resistant filler obtained in the embodimentThe burning and burning-resistant filler is added into the organic silicon rubber in the proportion of 20 parts per hundred parts of the organic silicon rubber to prepare a sample of 100mm multiplied by 3mm for cone calorimeter test, and the heat radiation power is 50kW/m2After testing, the total heat release amount of the heat-proof composite material can be reduced by 15MJ/m2The peak value of the heat release rate is reduced by 10kW/m2。
Claims (9)
1. The flame-retardant and ablation-resistant filler is characterized in that raw materials of the filler comprise phenolic compounds, aldehyde compounds and amine compounds, wherein the molar ratio of amino groups on the phenolic compounds, the aldehyde compounds and the amine compounds is (X: y: and Z, wherein Y is (1-3). times.X + (0.5-2). times.Z.
2. The flame retardant ablation-resistant filler of claim 1 wherein the phenolic compound comprises one or more of phenol, resorcinol or hydroquinone; the aldehyde compound comprises one or more of formaldehyde, furfural or terephthalaldehyde; the amine compound comprises one or more of melamine, ethylenediamine, diethylenetriamine, tetraethylenepentamine, hexamethylenediamine, piperazine or polyethyleneimine.
3. A method of preparing a flame retardant, ablation resistant filler according to claim 1, comprising the steps of:
(1) mixing a phenolic compound and an aldehyde compound in a solvent, and stirring for reaction until the mixture is clear to obtain a solution A;
(2) mixing an amine compound and an aldehyde compound in a solvent, and stirring for reaction until the mixture is clear to obtain a solution B;
(3) mixing the solution A and the solution B, and stirring to obtain a solution C;
(4) and heating the solution C, reacting until a solid is separated out from the solution, pouring out a supernatant, washing, drying and grinding the separated solid to obtain the flame-retardant ablation-resistant filler.
4. The method for preparing the flame-retardant and ablation-resistant filler according to the claim 3, wherein the solvent in the step (1) comprises one or more of water, ethanol or dimethyl sulfoxide, and the molar ratio of the phenolic compound to the aldehyde compound is 1 (1-3); the total concentration of the phenolic compound and the aldehyde compound is 3-40 omega t%, the reaction temperature is 20-35 ℃, and the stirring speed is 150-250 rpm.
5. The method for preparing the flame-retardant and ablation-resistant filler according to claim 3, wherein the solvent in the step (2) comprises one or more of water, ethanol or dimethyl sulfoxide, and the molar ratio of the amino group on the amine compound to the aldehyde compound is 1 (0.5-2); the total concentration of the amine compound and the aldehyde compound is 5-30 omega t%; the reaction temperature is 20-90 ℃, and the stirring speed is 150-250 rpm.
6. The method for preparing the flame-retardant and ablation-resistant filler as claimed in claim 3, wherein the volume ratio of the solution A to the solution B in the step (3) is (0.5-2.5):1, the stirring speed is 150-250rpm, the time is 1-10min, and the total concentration of the phenolic compound, the aldehyde compound and the amine compound is 0.02-0.2 g/mL.
7. The method for preparing the flame-retardant and ablation-resistant filler according to claim 3, wherein the reaction temperature in the step (4) is 80-180 ℃ and the reaction time is 1-24 hours, and the drying temperature is 50-90 ℃ and the reaction time is 12-36 hours.
8. Use of a flame-retardant ablation-resistant filler according to claim 1 as a filler for flame-retardant, ablative-type heat-protective composites or coatings.
9. Use of a flame retardant ablation-resistant filler according to claim 8, wherein the flame retardant ablation-resistant filler reduces the total heat release of the heat-protective composite by 15-30MJ/m2。
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5270434A (en) * | 1990-10-12 | 1993-12-14 | Isover Saint-Gobain | Phenolic resin, procedure for preparation of the resin, and sizing composition for mineral fibers containing this resin |
| JP2019167427A (en) * | 2018-03-22 | 2019-10-03 | 積水化学工業株式会社 | Manufacturing method of oxazine resin particle |
-
2019
- 2019-12-14 CN CN201911286946.8A patent/CN110835395A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5270434A (en) * | 1990-10-12 | 1993-12-14 | Isover Saint-Gobain | Phenolic resin, procedure for preparation of the resin, and sizing composition for mineral fibers containing this resin |
| JP2019167427A (en) * | 2018-03-22 | 2019-10-03 | 積水化学工業株式会社 | Manufacturing method of oxazine resin particle |
Non-Patent Citations (2)
| Title |
|---|
| HUANHUAN ZHOU ET AL: "Facile preparation and ultra-microporous structure of melamine–resorcinol–formaldehyde polymeric microspheres", 《CHEMICAL COMMUNICATIONS》 * |
| 唐磊等: "《耐高温隔热材料技术》", 31 July 2013, 国防工业出版社 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112724346A (en) * | 2020-02-28 | 2021-04-30 | 杭摩新材料(嘉兴)有限公司 | Flame-retardant phenolic resin and preparation method and application thereof |
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