Flame retardant material for new energy vehicles and preparation method thereof

Abstract

The invention discloses a flame retardant material for new energy vehicles and a preparation method thereof. Adipic acid, a modified monomer and hexamethylenediamine are reacted to form a nylon structure, and a modified filler is contained inside. When the flame retardant material is burned, organic phosphorus in the modified monomer and the modified filler will generate a large number of phosphorus-containing free radicals, which can capture free radicals with higher activity and prevent chain reactions, thereby playing a flame retardant role. The sulfur, nitrogen and boron elements in the modified monomer and the modified filler can be combined to generate a dense carbon layer on the surface of the material, thereby isolating oxygen, inhibiting heat transfer, and releasing non-flammable gas to dilute the oxygen concentration, thereby inhibiting combustion. At the same time, the modified filler has a good smoke suppression effect, reducing the smoke generated during combustion.

Description

Technical Field

[0001] The present invention relates to the technical field of flame retardant material preparation, and in particular to a flame retardant material for new energy vehicles and a preparation method thereof. Background Art

[0002] As an important representative of sustainable transportation in the future, new energy vehicles have the advantages of energy saving, environmental protection, pollution reduction, and greenhouse gas emission reduction, and are increasingly receiving widespread attention and praise around the world. With the increasing awareness of environmental protection and sustainable development, the market demand for new energy vehicles continues to rise, and higher requirements are also placed on the performance and safety of automotive materials. Among many synthetic polymer materials, nylon materials are favored due to their excellent physical properties, wear resistance and chemical corrosion resistance. They are widely used in the manufacture of automotive parts, such as engine hoods, exhaust pipes, cooling systems, wire and cable casings, etc., but their flame retardant effect is poor, and they will produce a lot of smoke when burning, which cannot meet the use requirements of new energy vehicles. Summary of the invention

[0003] The purpose of the present invention is to provide a flame retardant material for new energy vehicles and a preparation method thereof, which solves the problem that the flame retardant material for new energy vehicles at this stage has poor flame retardant effect and generates a large amount of smoke.

[0004] The purpose of the present invention can be achieved through the following technical solutions:

[0005] A method for preparing a flame retardant material for new energy vehicles, comprising the following steps:

[0006] Step A1: Glycidol, diphenylphosphinoyl chloride, triethylamine and DMF are mixed evenly, and reacted for 10-15 hours at a speed of 120-150 r / min and a temperature of 3-5° C. to obtain intermediate 1; intermediate 1, 4,4'-diaminodiphenyl sulfone and DMF are mixed evenly, and reacted for 8-10 hours at a speed of 150-200 r / min, a temperature of 60-70° C. and a pH value of 11-12 to obtain intermediate 2;

[0007] Step A2: The intermediate 2, 4-formylphenylboronic acid, 5A molecular sieve and DMF are mixed evenly, and the reaction is carried out for 10-15 hours at a speed of 60-80 r / min and a temperature of 60-65° C. to obtain the intermediate 3; the intermediate 3, melamine and DMF are mixed evenly, and nitrogen is introduced for protection, and the reaction is carried out for 5-7 hours at a speed of 150-200 r / min and a temperature of 60-65° C.; DOPO and glacial acetic acid are added, and the temperature is raised to 100-105° C., and the reaction is carried out for 10-15 hours to obtain the modified monomer;

[0008] Step A3: Evenly mix adipic acid, modified filler, deionized water and DMF, introduce nitrogen protection, stir and add modified monomer and hexamethylenediamine at a speed of 150-200 r / min and a temperature of 80-90° C., and react for 10-15 hours to obtain a flame retardant material for new energy vehicles.

[0009] Furthermore, the molar ratio of glycidol, diphenylphosphinoyl chloride and triethylamine in step A1 is 1:1:1.2, and the molar ratio of intermediate 1 and 4,4'-diaminodiphenyl sulfone is 4:1.

[0010] Furthermore, the usage ratio of the intermediate 2, 4-formylphenylboronic acid and 5A molecular sieve described in step A2 is 8mmol:16mmol:2g, the molar ratio of the intermediate 3, melamine and DOPO is 1:2:2, and the usage amount of glacial acetic acid is 5‰ of the mass of DOPO.

[0011] Furthermore, the usage ratio of adipic acid, modified filler, modified monomer and hexamethylenediamine in step A3 is 12 mmol:400 mg:1 mmol:12 mmol.

[0012] Further, the modified filler is prepared by the following steps:

[0013] Step B1: 2-nitroterephthalic acid, DMF and acetonitrile are mixed evenly, stirred at a speed of 120-150 r / min and a temperature of 20-25° C., and a copper acetate solution is added, stirred for 10-15 minutes, heated to 120-125° C., and reacted for 20-25 hours to obtain a copper organic framework, and the copper organic framework, stannous chloride and concentrated hydrochloric acid solution are mixed evenly, reacted at a speed of 150-200 r / min and a temperature of 65-70° C. for 1-2 hours, and the pH value is adjusted to be alkaline to obtain an amino framework;

[0014] Step B2: The amino framework, KH560, DMF and toluene are mixed evenly, nitrogen is introduced for protection, and the reaction is carried out for 6-8 hours at a speed of 120-150 r / min, a temperature of 40-50°C, and a pH value of 11-12 to obtain a functionalized framework. The functionalized framework, acrylic acid, p-toluenesulfonic acid and toluene are mixed evenly, nitrogen is introduced for protection, and the reaction is carried out for 5-7 hours at a speed of 60-80 r / min and a temperature of 110-120°C. The filtrate is removed by filtration. The substrate, DOPO, glacial acetic acid, DMF and toluene are mixed, nitrogen is introduced for protection, and the reaction is carried out for 6-8 hours at a speed of 200-300 r / min and a temperature of 30-40°C to obtain a precursor;

[0015] Step B3: The precursor, DMF, ethanol and deionized water are mixed evenly, stirred at a speed of 150-200r / min and a temperature of 25-30°C, and hydrochloric acid solution is added to a pH value of 2-5, and stirred for 20-30min to obtain a modified liquid, sodium montmorillonite, ethanol and deionized water are mixed evenly, stirred at a speed of 300-500r / min and a temperature of 80-85°C, and the modified liquid is added to react for 7-9h to obtain modified montmorillonite, and the modified montmorillonite, urea, diammonium phosphate and deionized water are mixed evenly, and stirred at a speed of 600-800r / min and a temperature of 20-25°C for 2-4h to obtain a modified filler.

[0016] Further, the amount ratio of 2-nitroterephthalic acid, DMF, acetonitrile and copper acetate solution in step B1 is 1.2mmol:20mL:20mL:14mL, the copper acetate solution is mixed with anhydrous copper acetate, DMF and acetonitrile in a ratio of 1.4mmol:10mL:10mL, the amount ratio of copper organic framework, stannous chloride and concentrated hydrochloric acid solution is 0.25g:1g:15mL, and the mass fraction of concentrated hydrochloric acid solution is 36%.

[0017] Furthermore, the molar ratio of the amino group on the amino framework described in step B2 to KH560 is 1:2, the molar ratio of the hydroxyl group, acrylic acid and DOPO on the functionalized framework is 1:1:1, the amount of p-toluenesulfonic acid used is 1% of the mass of acrylic acid, and the amount of glacial acetic acid used is 5‰ of the mass of DOPO.

[0018] Furthermore, the amount ratio of the precursor, DMF, ethanol and deionized water in step B3 is 2g:20mL:15mL:5mL, the amount ratio of sodium montmorillonite, ethanol, deionized water and modifying liquid is 1g:75mL:25mL:20mL, and the amount ratio of modified montmorillonite, urea, diammonium dihydrogen phosphate and deionized water is 3g:1g:1g:50mL.

[0019] Beneficial effects of the present invention: A flame retardant material for new energy vehicles prepared by the present invention is prepared by reacting adipic acid, a modified monomer and hexamethylenediamine to form a nylon structure, and at the same time contains a modified filler inside, wherein the modified monomer uses propylene oxide and diphenylphosphinoyl chloride as raw materials, so that the alcohol hydroxyl group on the propylene oxide reacts with the chlorine atom site on the diphenylphosphinoyl chloride to obtain an intermediate 1, and the intermediate 1 is reacted with 4,4'-diaminodiphenyl sulfone, so that the epoxy group on the intermediate 1 reacts with the amino group on the 4,4'-diaminodiphenyl sulfone to obtain an intermediate 2, and the intermediate 2 is reacted with 4-formylphenylboronic acid, so that two hydroxyl groups on one side of the intermediate 2 react with the boric acid group on the 4-formylphenylboronic acid to obtain an intermediate 3, and the intermediate 3 is reacted with melamine, so that the aldehyde group on the intermediate 3 reacts with the amino group on the melamine, and then DOPO is added, so that the generated carbon-nitrogen double bond is grafted with the PH bond on the DOPO to obtain a modified monomer.

[0020] The modified filler uses 2-nitroterephthalic acid and copper acetate solution as raw materials, copper ions react with carboxyl groups on 2-nitroterephthalic acid to form a copper organic framework, the copper organic framework is reduced to convert nitro groups into amino groups to obtain an amino framework, the amino framework is reacted with KH560 to react amino groups on the amino framework with epoxy groups of KH560 to obtain a functionalized framework, the functionalized framework is reacted with acrylic acid to esterify hydroxyl groups on the functionalized framework with carboxyl groups on acrylic acid, and then DOPO is added to graft carbon-carbon double bonds with PH bonds on DOPO to obtain a precursor, the precursor is hydrolyzed under acidic conditions to convert siloxane on the surface into silanol groups, the precursor is blended with sodium montmorillonite to combine silanol groups with hydroxyl groups on the sodium montmorillonite to obtain a modified montmorillonite, the modified montmorillonite, urea and diammonium phosphate are blended to allow the modified montmorillonite to adsorb urea and diammonium phosphate to obtain a modified filler.

[0021] When the flame retardant material burns, the organic phosphorus in the modified monomer and modified filler will produce a large number of phosphorus-containing free radicals, which can capture more active free radicals and prevent chain reactions, thereby playing a flame retardant role. The modified monomer and modified filler can cooperate with the sulfur, nitrogen and boron elements to produce a dense carbon layer on the surface of the material, thereby isolating oxygen, inhibiting heat transfer, and releasing non-combustible gas to dilute the oxygen concentration, thereby inhibiting combustion. At the same time, the modified filler has a good smoke suppression effect, reducing the smoke generated during combustion. DETAILED DESCRIPTION

[0022] The technical solutions in the embodiments of the present invention are described clearly and completely below. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention. Example 1

[0023] A method for preparing a flame retardant material for new energy vehicles, comprising the following steps:

[0024] Step A1: Glycidol, diphenylphosphinoyl chloride, triethylamine and DMF were mixed evenly, and the mixture was reacted at a speed of 120 r / min and a temperature of 3° C. for 10 h to obtain intermediate 1; intermediate 1, 4,4'-diaminodiphenyl sulfone and DMF were mixed evenly, and the mixture was reacted at a speed of 150 r / min, a temperature of 60° C. and a pH value of 11 for 8 h to obtain intermediate 2;

[0025] Step A2: The intermediate 2, 4-formylphenylboronic acid, 5A molecular sieve and DMF are mixed evenly, and the reaction is carried out at a speed of 60 r / min and a temperature of 60° C. for 10 hours to obtain the intermediate 3; the intermediate 3, melamine and DMF are mixed evenly, nitrogen is introduced for protection, and the reaction is carried out at a speed of 150 r / min and a temperature of 60° C. for 5 hours; DOPO and glacial acetic acid are added, the temperature is raised to 100° C., and the reaction is carried out for 10 hours to obtain the modified monomer;

[0026] Step A3: Adipic acid, modified filler, deionized water and DMF are mixed evenly, nitrogen is introduced for protection, and the modified monomer and hexamethylenediamine are added under stirring at a speed of 150 r / min and a temperature of 80° C. The mixture is reacted for 10 hours to obtain a flame retardant material for new energy vehicles.

[0027] The molar ratio of glycidol, diphenylphosphinoyl chloride and triethylamine in step A1 is 1:1:1.2, and the molar ratio of intermediate 1 and 4,4'-diaminodiphenyl sulfone is 4:1.

[0028] The usage ratio of the intermediate 2, 4-formylphenylboronic acid and 5A molecular sieve described in step A2 is 8mmol:16mmol:2g, the molar ratio of the intermediate 3, melamine and DOPO is 1:2:2, and the usage amount of glacial acetic acid is 5‰ of the mass of DOPO.

[0029] The usage ratio of adipic acid, modified filler, modified monomer and hexamethylenediamine described in step A3 is 12mmol:400mg:1mmol:12mmol.

[0030] The modified filler is prepared by the following steps:

[0031] Step B1: 2-nitroterephthalic acid, DMF and acetonitrile are mixed evenly, stirred at a speed of 120 r / min and a temperature of 20° C., and a copper acetate solution is added, stirred for 10 min, heated to 120° C., and reacted for 20 h to obtain a copper organic framework; the copper organic framework, stannous chloride and concentrated hydrochloric acid solution are mixed evenly, reacted at a speed of 150 r / min and a temperature of 65° C. for 1 h, and the pH value is adjusted to be alkaline to obtain an amino framework;

[0032] Step B2: The amino framework, KH560, DMF and toluene are mixed evenly, nitrogen is introduced for protection, and the reaction is carried out for 6 hours at a speed of 120 r / min, a temperature of 40°C and a pH value of 11 to obtain a functionalized framework. The functionalized framework, acrylic acid, p-toluenesulfonic acid and toluene are mixed evenly, nitrogen is introduced for protection, and the reaction is carried out for 5 hours at a speed of 60 r / min and a temperature of 110°C. The filtrate is removed by filtration. The substrate, DOPO, glacial acetic acid, DMF and toluene are mixed, nitrogen is introduced for protection, and the reaction is carried out for 6 hours at a speed of 200 r / min and a temperature of 30°C to obtain a precursor.

[0033] Step B3: The precursor, DMF, ethanol and deionized water are mixed evenly, stirred at a speed of 150r / min and a temperature of 25°C, and hydrochloric acid solution is added to a pH value of 2, and stirred for 20 minutes to obtain a modified liquid. The sodium montmorillonite, ethanol and deionized water are mixed evenly, stirred at a speed of 300r / min and a temperature of 80°C, and the modified liquid is added to react for 7 hours to obtain modified montmorillonite. The modified montmorillonite, urea, diammonium dihydrogen phosphate and deionized water are mixed evenly, and stirred at a speed of 600r / min and a temperature of 20°C for 2 hours to obtain a modified filler.

[0034] The amount ratio of 2-nitroterephthalic acid, DMF, acetonitrile and copper acetate solution described in step B1 is 1.2mmol:20mL:20mL:14mL, the copper acetate solution is mixed with anhydrous copper acetate, DMF and acetonitrile in a ratio of 1.4mmol:10mL:10mL, the amount ratio of copper organic framework, stannous chloride and concentrated hydrochloric acid solution is 0.25g:1g:15mL, and the mass fraction of concentrated hydrochloric acid solution is 36%.

[0035] The molar ratio of the amino group on the amino framework described in step B2 to KH560 is 1:2, the molar ratio of the hydroxyl group, acrylic acid and DOPO on the functionalized framework is 1:1:1, the amount of p-toluenesulfonic acid used is 1% of the mass of acrylic acid, and the amount of glacial acetic acid used is 5‰ of the mass of DOPO.

[0036] The amount ratio of the precursor, DMF, ethanol and deionized water in step B3 is 2g:20mL:15mL:5mL, the amount ratio of sodium montmorillonite, ethanol, deionized water and modifying liquid is 1g:75mL:25mL:20mL, and the amount ratio of modified montmorillonite, urea, diammonium dihydrogen phosphate and deionized water is 3g:1g:1g:50mL. Example 2

[0037] A method for preparing a flame retardant material for new energy vehicles, comprising the following steps:

[0038] Step A1: Glycidol, diphenylphosphinoyl chloride, triethylamine and DMF were mixed evenly, and the mixture was reacted at a speed of 120 r / min and a temperature of 4° C. for 15 h to obtain intermediate 1; intermediate 1, 4,4'-diaminodiphenyl sulfone and DMF were mixed evenly, and the mixture was reacted at a speed of 150 r / min, a temperature of 65° C. and a pH value of 12 for 9 h to obtain intermediate 2;

[0039] Step A2: The intermediate 2, 4-formylphenylboronic acid, 5A molecular sieve and DMF are mixed evenly, and the reaction is carried out at a speed of 60 r / min and a temperature of 65° C. for 10 hours to obtain the intermediate 3; the intermediate 3, melamine and DMF are mixed evenly, nitrogen is introduced for protection, and the reaction is carried out at a speed of 200 r / min and a temperature of 60° C. for 6 hours; DOPO and glacial acetic acid are added, the temperature is raised to 100° C., and the reaction is carried out for 15 hours to obtain the modified monomer;

[0040] Step A3: Adipic acid, modified filler, deionized water and DMF are mixed evenly, nitrogen is introduced for protection, and the modified monomer and hexamethylenediamine are added under stirring at a speed of 150 r / min and a temperature of 85° C. The mixture is reacted for 15 hours to obtain a flame retardant material for new energy vehicles.

[0041] The molar ratio of glycidol, diphenylphosphinoyl chloride and triethylamine in step A1 is 1:1:1.2, and the molar ratio of intermediate 1 and 4,4'-diaminodiphenyl sulfone is 4:1.

[0042] The usage ratio of the intermediate 2, 4-formylphenylboronic acid and 5A molecular sieve described in step A2 is 8mmol:16mmol:2g, the molar ratio of the intermediate 3, melamine and DOPO is 1:2:2, and the usage amount of glacial acetic acid is 5‰ of the mass of DOPO.

[0043] The usage ratio of adipic acid, modified filler, modified monomer and hexamethylenediamine described in step A3 is 12mmol:400mg:1mmol:12mmol.

[0044] The modified filler is prepared by the following steps:

[0045] Step B1: 2-nitroterephthalic acid, DMF and acetonitrile are mixed evenly, stirred at a speed of 120 r / min and a temperature of 25° C., and a copper acetate solution is added, stirred for 10 min, heated to 125° C., and reacted for 23 h to obtain a copper organic framework; the copper organic framework, stannous chloride and concentrated hydrochloric acid solution are mixed evenly, reacted at a speed of 150 r / min and a temperature of 68° C. for 1.5 h, and the pH value is adjusted to be alkaline to obtain an amino framework;

[0046] Step B2: The amino framework, KH560, DMF and toluene are mixed evenly, nitrogen is introduced for protection, and the reaction is carried out for 7 hours at a speed of 120 r / min, a temperature of 45°C and a pH value of 12 to obtain a functionalized framework. The functionalized framework, acrylic acid, p-toluenesulfonic acid and toluene are mixed evenly, nitrogen is introduced for protection, and the reaction is carried out for 6 hours at a speed of 60 r / min and a temperature of 115°C. The filtrate is removed by filtration. The substrate, DOPO, glacial acetic acid, DMF and toluene are mixed, nitrogen is introduced for protection, and the reaction is carried out for 7 hours at a speed of 200 r / min and a temperature of 35°C to obtain a precursor.

[0047] Step B3: The precursor, DMF, ethanol and deionized water are mixed evenly, stirred at a speed of 150 r / min and a temperature of 25°C, and hydrochloric acid solution is added to a pH value of 5, and stirred for 25 minutes to obtain a modified liquid. The sodium montmorillonite, ethanol and deionized water are mixed evenly, stirred at a speed of 300 r / min and a temperature of 85°C, and the modified liquid is added to react for 8 hours to obtain modified montmorillonite. The modified montmorillonite, urea, diammonium dihydrogen phosphate and deionized water are mixed evenly, and stirred at a speed of 600 r / min and a temperature of 25°C for 3 hours to obtain a modified filler.

[0048] The amount ratio of 2-nitroterephthalic acid, DMF, acetonitrile and copper acetate solution described in step B1 is 1.2mmol:20mL:20mL:14mL, the copper acetate solution is mixed with anhydrous copper acetate, DMF and acetonitrile in a ratio of 1.4mmol:10mL:10mL, the amount ratio of copper organic framework, stannous chloride and concentrated hydrochloric acid solution is 0.25g:1g:15mL, and the mass fraction of concentrated hydrochloric acid solution is 36%.

[0049] The molar ratio of the amino group on the amino framework described in step B2 to KH560 is 1:2, the molar ratio of the hydroxyl group, acrylic acid and DOPO on the functionalized framework is 1:1:1, the amount of p-toluenesulfonic acid used is 1% of the mass of acrylic acid, and the amount of glacial acetic acid used is 5‰ of the mass of DOPO.

[0050] The amount ratio of the precursor, DMF, ethanol and deionized water in step B3 is 2g:20mL:15mL:5mL, the amount ratio of sodium montmorillonite, ethanol, deionized water and modifying liquid is 1g:75mL:25mL:20mL, and the amount ratio of modified montmorillonite, urea, diammonium dihydrogen phosphate and deionized water is 3g:1g:1g:50mL. Example 3

[0051] A method for preparing a flame retardant material for new energy vehicles, comprising the following steps:

[0052] Step A1: Glycidol, diphenylphosphinoyl chloride, triethylamine and DMF were mixed evenly, and the mixture was reacted at a speed of 150 r / min and a temperature of 5° C. for 15 h to obtain intermediate 1; intermediate 1, 4,4'-diaminodiphenyl sulfone and DMF were mixed evenly, and the mixture was reacted at a speed of 200 r / min, a temperature of 70° C. and a pH value of 12 for 10 h to obtain intermediate 2;

[0053] Step A2: The intermediate 2, 4-formylphenylboronic acid, 5A molecular sieve and DMF are mixed evenly, and the reaction is carried out for 15 hours at a speed of 80 r / min and a temperature of 65° C. to obtain the intermediate 3; the intermediate 3, melamine and DMF are mixed evenly, nitrogen is introduced for protection, and the reaction is carried out for 7 hours at a speed of 200 r / min and a temperature of 65° C.; DOPO and glacial acetic acid are added, the temperature is raised to 105° C., and the reaction is carried out for 15 hours to obtain the modified monomer;

[0054] Step A3: Adipic acid, modified filler, deionized water and DMF are mixed evenly, nitrogen is introduced for protection, and the modified monomer and hexamethylenediamine are added under stirring at a speed of 200 r / min and a temperature of 90° C., and the reaction is carried out for 10-15 hours to obtain a flame retardant material for new energy vehicles.

[0055] The molar ratio of glycidol, diphenylphosphinoyl chloride and triethylamine in step A1 is 1:1:1.2, and the molar ratio of intermediate 1 and 4,4'-diaminodiphenyl sulfone is 4:1.

[0056] The usage ratio of the intermediate 2, 4-formylphenylboronic acid and 5A molecular sieve described in step A2 is 8mmol:16mmol:2g, the molar ratio of the intermediate 3, melamine and DOPO is 1:2:2, and the usage amount of glacial acetic acid is 5‰ of the mass of DOPO.

[0057] The usage ratio of adipic acid, modified filler, modified monomer and hexamethylenediamine described in step A3 is 12mmol:400mg:1mmol:12mmol.

[0058] The modified filler is prepared by the following steps:

[0059] Step B1: 2-nitroterephthalic acid, DMF and acetonitrile are mixed evenly, stirred at a speed of 150 r / min and a temperature of 25° C., and a copper acetate solution is added, stirred for 15 min, heated to 125° C., and reacted for 25 h to obtain a copper organic framework; the copper organic framework, stannous chloride and concentrated hydrochloric acid solution are mixed evenly, reacted at a speed of 200 r / min and a temperature of 70° C. for 2 h, and the pH value is adjusted to be alkaline to obtain an amino framework;

[0060] Step B2: The amino framework, KH560, DMF and toluene are mixed evenly, nitrogen is introduced for protection, and the reaction is carried out for 8 hours at a speed of 150 r / min, a temperature of 50°C and a pH value of 12 to obtain a functionalized framework. The functionalized framework, acrylic acid, p-toluenesulfonic acid and toluene are mixed evenly, nitrogen is introduced for protection, and the reaction is carried out for 7 hours at a speed of 80 r / min and a temperature of 120°C. The filtrate is removed by filtration. The substrate, DOPO, glacial acetic acid, DMF and toluene are mixed, nitrogen is introduced for protection, and the reaction is carried out for 8 hours at a speed of 300 r / min and a temperature of 40°C to obtain a precursor.

[0061] Step B3: The precursor, DMF, ethanol and deionized water are mixed evenly, stirred at a speed of 200 r / min and a temperature of 30°C, and hydrochloric acid solution is added to a pH value of 5, and stirred for 30 minutes to obtain a modified liquid. The sodium montmorillonite, ethanol and deionized water are mixed evenly, stirred at a speed of 500 r / min and a temperature of 85°C, and the modified liquid is added to react for 9 hours to obtain modified montmorillonite. The modified montmorillonite, urea, diammonium dihydrogen phosphate and deionized water are mixed evenly, and stirred at a speed of 800 r / min and a temperature of 25°C for 4 hours to obtain a modified filler.

[0062] The amount ratio of 2-nitroterephthalic acid, DMF, acetonitrile and copper acetate solution described in step B1 is 1.2mmol:20mL:20mL:14mL, the copper acetate solution is mixed with anhydrous copper acetate, DMF and acetonitrile in a ratio of 1.4mmol:10mL:10mL, the amount ratio of copper organic framework, stannous chloride and concentrated hydrochloric acid solution is 0.25g:1g:15mL, and the mass fraction of concentrated hydrochloric acid solution is 36%.

[0063] The molar ratio of the amino group on the amino framework described in step B2 to KH560 is 1:2, the molar ratio of the hydroxyl group, acrylic acid and DOPO on the functionalized framework is 1:1:1, the amount of p-toluenesulfonic acid used is 1% of the mass of acrylic acid, and the amount of glacial acetic acid used is 5‰ of the mass of DOPO.

[0064] The amount ratio of the precursor, DMF, ethanol and deionized water in step B3 is 2g:20mL:15mL:5mL, the amount ratio of sodium montmorillonite, ethanol, deionized water and modifying liquid is 1g:75mL:25mL:20mL, and the amount ratio of modified montmorillonite, urea, diammonium dihydrogen phosphate and deionized water is 3g:1g:1g:50mL.

[0065] Comparative Example 1

[0066] Compared with Example 1, this comparative example uses ethylenediamine instead of 4,4'-diaminodiphenyl sulfone, and the remaining steps are the same.

[0067] Comparative Example 2

[0068] Compared with Example 1, this comparative example uses an amino framework to replace the modified filler, and the remaining steps are the same.

[0069] Comparative Example 3

[0070] Compared with Example 1, this comparative example uses a precursor instead of a modified filler, and the remaining steps are the same.

[0071] Comparative Example 4

[0072] Compared with Example 1, this comparative example uses modified montmorillonite instead of modified filler, and the remaining steps are the same.

[0073] Comparative Example 5

[0074] Compared with Example 1, this comparative example uses propyltriethoxysilane instead of the modifying liquid, and the other steps are the same.

[0075] The flame retardant materials obtained in Examples 1-3 and Comparative Examples 1-4 were made into 125mm×13mm×10mm samples according to the standard of GB / T2408-2008 to detect the vertical combustion level, and 130mm×10mm×10mm samples were made according to the standard of GB / T2406.2-2009 to detect the limiting oxygen index, and 75mm×75mm×5mm samples were made according to the standard of ISO5659-2 to detect the limiting oxygen index. 2 Under the conditions, the maximum smoke release rate and smoke release amount were tested, and the test results are shown in the following table.

[0076] Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Vertical burning level V0 V0 V0 V1 V1 V1 V1 V2 Limiting oxygen index% 35.4 36.1 36.8 31.2 26.6 27.5 25.1 25.1 <![CDATA[Smoke release rate m 2 / s]]> 0.021 0.017 0.014 0.025 0.037 0.029 0.023 0.114 <![CDATA[Smoke release amount m 2 > 11.2 10.5 9.8 12.3 17.7 15.9 11.8 26.3

[0077] It can be seen from the above table that the present invention has a good flame retardant and smoke suppression effect.

[0078] The above contents are merely examples and explanations of the concept of the present invention. The technicians in this technical field may make various modifications or additions to the specific embodiments described or replace them in a similar manner. As long as they do not deviate from the concept of the invention or exceed the scope defined by the claims, they should all fall within the protection scope of the present invention.

Claims

1. A method for preparing a flame retardant material for new energy vehicles, characterized in that: The specific steps include: Step A1: glycidol, diphenylphosphinoyl chloride, triethylamine and DMF are mixed to react to obtain intermediate 1, and intermediate 1, 4,4'-diaminodiphenyl sulfone and DMF are mixed to react to obtain intermediate 2; Step A2: intermediate 2, 4-formylphenylboronic acid, 5A molecular sieve and DMF are mixed for reaction to obtain intermediate 3, intermediate 3, melamine and DMF are uniformly mixed, nitrogen is introduced for protection, DOPO and glacial acetic acid are added, and the temperature is raised for reaction to obtain a modified monomer; Step A3: uniformly mixing adipic acid, modified filler, deionized water and DMF, introducing nitrogen protection, stirring and adding modified monomer and hexamethylenediamine to react, thereby preparing a flame retardant material for new energy vehicles; The modified filler is prepared by the following steps: Step B1: 2-nitroterephthalic acid, DMF and acetonitrile are mixed and stirred, and a copper acetate solution is added to react to obtain a copper organic framework, and the copper organic framework, stannous chloride and concentrated hydrochloric acid solution are mixed to react, and the pH value is adjusted to be alkaline to obtain an amino framework; Step B2: The amino framework, KH560, DMF and toluene are mixed evenly, nitrogen is introduced for protection, and a reaction is carried out to obtain a functionalized framework; the functionalized framework, acrylic acid, p-toluenesulfonic acid and toluene are mixed evenly, nitrogen is introduced for protection, and a reaction is carried out, and the filtrate is removed by filtering; the substrate, DOPO, glacial acetic acid, DMF and toluene are mixed, nitrogen is introduced for protection, and a reaction is carried out to obtain a precursor; Step B3: The precursor, DMF, ethanol and deionized water are mixed and stirred, and hydrochloric acid solution is added, and stirred to obtain a modified liquid. Sodium montmorillonite, ethanol and deionized water are mixed and stirred, and the modified liquid is added to react to obtain modified montmorillonite. The modified montmorillonite, urea, diammonium dihydrogen phosphate and deionized water are mixed and stirred to obtain a modified filler.

2. The method for preparing a flame retardant material for new energy vehicles according to claim 1, characterized in that: The molar ratio of glycidol, diphenylphosphinoyl chloride and triethylamine in step A1 is 1:1:1.2, and the molar ratio of intermediate 1 and 4,4'-diaminodiphenyl sulfone is 4:

1.

3. The method for preparing a flame retardant material for new energy vehicles according to claim 1, characterized in that: The usage ratio of the intermediate 2, 4-formylphenylboronic acid and 5A molecular sieve described in step A2 is 8 mmol:16 mmol:2 g, and the molar ratio of the intermediate 3, melamine and DOPO is 1:2:

2.

4. The method for preparing a flame retardant material for new energy vehicles according to claim 1, characterized in that: The usage ratio of adipic acid, modified filler, modified monomer and hexamethylenediamine described in step A3 is 12mmol:400mg:1mmol:12mmol.

5. The method for preparing a flame retardant material for new energy vehicles according to claim 1, characterized in that: The amount ratio of 2-nitroterephthalic acid, DMF, acetonitrile and copper acetate solution in step B1 is 1.2mmol:20mL:20mL:14mL, and the amount ratio of copper organic framework, stannous chloride and concentrated hydrochloric acid solution is 0.25g:1g:15mL.

6. The method for preparing a flame retardant material for new energy vehicles according to claim 1, characterized in that: The molar ratio of the amino group on the amino framework described in step B2 to KH560 is 1:2, and the molar ratio of the hydroxyl group, acrylic acid and DOPO on the functionalized framework is 1:1:

1.

7. The method for preparing a flame retardant material for new energy vehicles according to claim 1, characterized in that: The amount ratio of the precursor, DMF, ethanol and deionized water in step B3 is 2g:20mL:15mL:5mL, the amount ratio of sodium montmorillonite, ethanol, deionized water and modifying liquid is 1g:75mL:25mL:20mL, and the amount ratio of modified montmorillonite, urea, diammonium dihydrogen phosphate and deionized water is 3g:1g:1g:50mL.

8. A flame retardant material for new energy vehicles, characterized in that: Prepared according to any one of claims 1 to 7.