CN112457525A - Graphene composite flame-retardant material and preparation method thereof - Google Patents
Graphene composite flame-retardant material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a graphene composite flame-retardant material and a preparation method thereof, wherein the graphene composite flame-retardant material comprises the following raw materials in parts by weight: 30-50 parts of modified graphene and 10-15 parts of flame retardant additive; the flame retardant additive and the modified graphene are condensed under the action of 1-hydroxy benzotriazole, amino groups on the flame retardant additive and carboxyl groups on the modified graphene are condensed, so that flame retardant additive molecules are fixed on the surface of the modified graphene to prepare the graphene composite flame retardant material, oxyacid of phosphorus of the graphene flame retardant material catalyzes a hydroxyl-containing compound to dehydrate into carbon, a coke layer is generated on the surface of the material, the coke layer can insulate oxygen and heat and further extinguish flame, meanwhile, smoke generated during material combustion is little, and the flame retardant property of the graphene composite flame retardant material cannot be reduced due to long-time use.
Description
Technical Field
The invention relates to the technical field of flame retardant material preparation, and particularly relates to a graphene composite flame retardant material and a preparation method thereof.
Background
Graphene is a new material with a single-layer sheet structure formed by carbon atoms, is a hexagonal honeycomb-lattice planar thin film formed by the carbon atoms through sp2 hybrid orbits, is a two-dimensional material with the thickness of only one carbon atom, and has the unique characteristics and excellent properties, such as quantum Hall effect, high modulus, strength and electron migration rate, huge specific surface area, excellent heat conduction and electric conduction performance and the like. Due to the characteristics and properties, the graphene has a very wide application prospect in the fields of energy, electrons, catalysis, biomedicine, composite materials and the like, and is widely applied to the preparation of flame retardant materials due to good flame retardance of the graphene.
The existing graphene composite flame-retardant material is mostly compounded by graphene and inorganic flame-retardant substances, so that the flame-retardant effect of the material is general, open fire on the surface of the material cannot be extinguished quickly, and a large amount of smoke can be generated when the material is combusted, and the environmental pollution is large.
Disclosure of Invention
The invention aims to provide a graphene composite flame-retardant material and a preparation method thereof.
The technical problems to be solved by the invention are as follows:
the existing graphene composite flame-retardant material is mostly compounded by graphene and inorganic flame-retardant substances, so that the flame-retardant effect of the material is general, open fire on the surface of the material cannot be extinguished quickly, and a large amount of smoke can be generated when the material is combusted, and the environmental pollution is large.
The purpose of the invention can be realized by the following technical scheme:
a graphene composite flame-retardant material comprises the following raw materials in parts by weight: 30-50 parts of modified graphene and 10-15 parts of flame retardant additive;
the graphene composite flame-retardant material is prepared by the following steps:
step S1: adding the modified graphene and deionized water into a reaction kettle, stirring at the rotation speed of 300-500r/min and the temperature of 35-40 ℃, adding the flame retardant additive and 1-hydroxybenzotriazole, and stirring for 2-3h to obtain a mixed solution;
step S2: and (4) carrying out ultrasonic treatment on the mixed solution prepared in the step (S1) for 10-15min under the condition that the frequency is 3-5MHz, filtering to remove filtrate, and drying the filter cake for 2-3h under the condition that the temperature is 80 ℃ to prepare the graphene composite flame-retardant material.
Further, the amount of the 1-hydroxybenzotriazole used in the step S1 is 25-30% of the modified graphene by mass.
Further, the modified graphene is prepared by the following steps:
step A1: adding concentrated sulfuric acid into a reaction kettle, stirring at the rotation speed of 150-200r/min, adding graphite and sodium nitrate at the temperature of 1-3 ℃, stirring for 10-15min, adding potassium permanganate, continuously stirring for 1-1.5h, heating to 35-40 ℃, reacting for 20-30min, adding deionized water, heating to 80-90 ℃, adding hydrogen peroxide, continuously reacting for 1-2h, filtering to remove filtrate, and drying a filter cake to obtain graphene oxide;
step A2: dissolving magnesium nitrate hexahydrate and aluminum nitrate nonahydrate in deionized water, adding urea, stirring at the rotation speed of 800-.
Further, the use amount ratio of the concentrated sulfuric acid, the graphite, the sodium nitrate, the potassium permanganate, the deionized water and the hydrogen peroxide in the step A1 is 22mL:1g:0.5g:3g:100mL:4mL, the mass number of the concentrated sulfuric acid is 70%, the mass fraction of the hydrogen peroxide is 10%, and the use amount ratio of the concentrated sulfuric acid, the graphite, the sodium nitrate, the potassium permanganate, the deionized water and the hydrogen peroxide in the step A1 in the step A2 is 22mL:1g:0.5g:3g:100mL:4 mL.
Further, the flame retardant additive is prepared by the following steps:
step B1: adding p-nitrophenol, p-methylaniline, cyclohexylamine and palladium carbon into a reaction kettle, introducing nitrogen to discharge air, reacting for 2-3h at the rotation speed of 120-250 ℃ and the temperature of 245-250 ℃ under the pressure of 1.0-1.3MPa, cooling to 60-70 ℃, standing for 10-15min, and taking an upper layer solution to prepare an intermediate 1;
the reaction process is as follows:
step B2: dissolving the intermediate 1 in tetrahydrofuran, reacting with chlorine gas under the condition of illumination for 1-1.5h to obtain an intermediate 2, adding the intermediate 2, potassium carbonate, deionized water and tetraethylammonium bromide into a reaction kettle, performing reflux reaction for 1-1.5h under the conditions of the rotating speed of 150-200r/min and the temperature of 110-120 ℃ to obtain an intermediate 3, adding cobalt acetate and acetic acid into the reaction kettle, stirring under the conditions of the rotating speed of 120-150r/min until the cobalt acetate is completely dissolved, adding the intermediate 3 and introducing oxygen at the oxygen introduction speed of 50-55mL/min, and reacting for 8-10h under the temperature of 95-100 ℃ to obtain an intermediate 4;
the reaction process is as follows:
step B3: adding the intermediate 4, melamine and tetrahydrofuran into a reaction kettle, introducing nitrogen for protection, stirring for 5-10min under the condition that the rotation speed is 200-;
the reaction process is as follows:
step B4: adding diphenyl chlorophosphate, dichloromethane and triethylamine into a reaction kettle, stirring for 5-10min at the rotation speed of 200-3 ℃ and at the temperature of 1-3 ℃, adding 4,4' -dihydroxy benzophenone, reacting for 1-1.5h, adding sodium borohydride, continuously stirring for 4-6h, adding deionized water, and standing for 10-15min to obtain an intermediate 7;
the reaction process is as follows:
step B5: adding the intermediate 6, iron powder and ethanol into a reaction kettle, carrying out reflux reaction for 3-5h at the temperature of 80-85 ℃, adding a hydrochloric acid solution for 20min, continuously reacting for 5-8h, adjusting the pH value of a reaction solution to 7-8 to obtain an intermediate 8, dissolving the intermediate 8 in tetrahydrofuran, introducing phosgene at the temperature of 25-30 ℃, continuously stirring for 30-50min, heating to the temperature of 120-150 ℃, continuously reacting for 2-3h, cooling to the temperature of 90-100 ℃, introducing nitrogen to remove phosgene, preserving heat for 10-15min to obtain an intermediate 9, adding the intermediate 9, the intermediate 7, triethylamine and toluene into the reaction kettle, carrying out reflux reaction for 4-6h at the temperature of 115-120 ℃, to obtain an intermediate 10;
the reaction process is as follows:
step B6: dissolving cyanuric chloride in acetone, adding the intermediate 10 and sodium acetate under the conditions of a rotation speed of 150-200r/min and a temperature of 40-50 ℃, reacting for 3-5h, adding ethylenediamine, performing reflux reaction at a temperature of 80-90 ℃ for 3-5h, and removing acetone to obtain the flame retardant additive.
The reaction process is as follows:
further, the dosage ratio of the p-nitrophenol, the p-methylaniline, the cyclohexylamine and the palladium carbon in the step B1 is 1mol:1mol:0.1mol:1g, the dosage molar ratio of the intermediate 1 and the chlorine gas in the step B2 is 2:1, the dosage ratio of the intermediate 2, the potassium carbonate, the deionized water and the tetraethylammonium bromide is 10g:9g:70mL:2mL, the dosage-mass ratio of the cobalt acetate to the intermediate 3 is 1:5, the dosage-mass ratio of the intermediate 4 and the melamine in the step B3 is 8:3, the dosage-mass ratio of the intermediate 5, the phosphorus pentachloride, the aluminum trichloride and the phenol is 1:3:0.1:7, the dosage-mass ratio of the diphenyl chlorophosphate, the dichloromethane, the triethylamine, the 4,4' -dihydroxy benzophenone and the sodium borohydride in the step B4 is 1mol:200mL:2mol:2mol:0.6mol, the intermediate 6, the iron powder, the ethanol and the chlorine hydride in the step B5, The using amount ratio of the hydrochloric acid solution is 4g:4.5g:55mL:10mL, the volume fraction of ethanol is 90%, the hydrochloric acid solution is formed by mixing concentrated hydrochloric acid with the mass fraction of 36% and ethanol with the volume fraction of 95% in a volume ratio of 1:9, the using amount molar ratio of the intermediate 8 to phosgene is 1:1, the using amount molar ratio of the intermediate 9, the intermediate 7 and triethylamine is 1:1:2, the using amount molar ratio of the cyanuric chloride, the intermediate 10 and the ethylenediamine in the step B6 is 1:1:1, and the using amount of sodium acetate is 30% of the mass of the cyanuric chloride.
A preparation method of a graphene composite flame-retardant material specifically comprises the following steps:
step S1: adding the modified graphene and deionized water into a reaction kettle, stirring at the rotation speed of 300-500r/min and the temperature of 35-40 ℃, adding the flame retardant additive and 1-hydroxybenzotriazole, and stirring for 2-3h to obtain a mixed solution;
step S2: and (4) carrying out ultrasonic treatment on the mixed solution prepared in the step (S1) for 10-15min under the condition that the frequency is 3-5MHz, filtering to remove filtrate, and drying the filter cake for 2-3h under the condition that the temperature is 80 ℃ to prepare the graphene composite flame-retardant material.
The invention has the beneficial effects that: the invention discloses a modified graphene prepared in the process of preparing a graphene composite flame-retardant material, wherein the modified graphene takes graphite as a raw material to be oxidized to prepare graphene oxide, magnesium nitrate hexahydrate and aluminum nitrate nonahydrate are taken as raw materials to prepare zinc-aluminum hydrotalcite, the zinc-aluminum hydrotalcite is embedded into the graphene oxide to prepare the modified graphene, a flame-retardant additive is prepared, p-nitrophenol and p-methylaniline are taken as raw materials to react to prepare an intermediate 1, the intermediate 1 and chlorine gas are subjected to substitution reaction under the illumination condition to prepare an intermediate 2, the intermediate 2 is further processed to prepare an intermediate 3, the intermediate 3 and oxygen are oxidized to prepare an intermediate 4, the intermediate 4 and melamine are reacted to prepare an intermediate 5, the intermediate 5 and phosphorus oxychloride are reacted and then are reacted with phenol, preparing an intermediate 6, reacting diphenyl chlorophosphate with 4,4' -dihydroxy benzophenone to prepare an intermediate 7, reducing the intermediate 6 with iron powder to convert nitro groups into amino groups to prepare an intermediate 8, reacting the intermediate 8 with phosgene to prepare an intermediate 9, further reacting the intermediate 9 with the intermediate 7 to prepare an intermediate 10, reacting the intermediate 10 with cyanuric chloride under temperature control to replace two chlorine atoms on the cyanuric chloride, reacting with ethylenediamine to replace the last chlorine atom to prepare a flame retardant additive, condensing the amino groups on the flame retardant additive and carboxyl groups on modified graphene under the action of 1-hydroxybenzotriazole to fix the flame retardant additive molecules on the surface of the modified graphene to prepare the graphene composite flame retardant material, the oxyacid of phosphorus of the graphene flame retardant material is dehydrated into carbon by catalyzing hydroxyl-containing compounds, so that a coke layer is generated on the surface of the material, the coke layer can isolate oxygen and heat, and further flame is extinguished, and meanwhile, smoke generated when the material is combusted is little, so that the flame retardant property of the material cannot be reduced due to long-time use.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
A graphene composite flame-retardant material comprises the following raw materials in parts by weight: 30 parts of modified graphene and 10 parts of flame retardant additive;
the graphene composite flame-retardant material is prepared by the following steps:
step S1: adding the modified graphene and deionized water into a reaction kettle, stirring at the rotating speed of 300r/min and the temperature of 35 ℃, adding the flame retardant additive and 1-hydroxybenzotriazole, and stirring for 2 hours to obtain a mixed solution;
step S2: and (4) carrying out ultrasonic treatment on the mixed solution prepared in the step (S1) for 10min under the condition that the frequency is 3MHz, filtering to remove filtrate, and drying the filter cake for 2h under the condition that the temperature is 80 ℃ to prepare the graphene composite flame-retardant material.
The modified graphene is prepared by the following steps:
step A1: adding concentrated sulfuric acid into a reaction kettle, stirring at the rotation speed of 150r/min, adding graphite and sodium nitrate at the temperature of 1 ℃, stirring for 10min, adding potassium permanganate, continuously stirring for 1h, heating to the temperature of 35 ℃, reacting for 20min, adding deionized water, heating to the temperature of 80 ℃, adding hydrogen peroxide, continuously reacting for 1h, filtering to remove filtrate, and drying a filter cake to obtain graphene oxide;
step A2: dissolving magnesium nitrate hexahydrate and aluminum nitrate nonahydrate in deionized water, adding urea, stirring for 8 hours at the rotation speed of 500r/min and the temperature of 90 ℃, cooling to 70 ℃, standing for 5 hours, adding ethanol and ethyl orthosilicate, reacting for 10 hours at the rotation speed of 200r/min and the temperature of 40 ℃, filtering to remove filtrate, washing a filter cake for 2 times by using deionized water, and drying for 2 hours at the temperature of 130 ℃ to obtain the modified graphene.
The flame retardant additive is prepared by the following steps:
step B1: adding p-nitrophenol, p-methylaniline, cyclohexylamine and palladium-carbon into a reaction kettle, introducing nitrogen to discharge air, reacting for 3 hours at the rotation speed of 150r/min, the temperature of 250 ℃ and the pressure of 1.3MPa, cooling to 70 ℃, standing for 15 minutes, and taking an upper layer solution to prepare an intermediate 1;
step B2: dissolving the intermediate 1 in tetrahydrofuran, reacting with chlorine gas for 1.5h under the illumination condition to obtain an intermediate 2, adding the intermediate 2, potassium carbonate, deionized water and tetraethylammonium bromide into a reaction kettle, performing reflux reaction for 1.5h at the rotation speed of 200r/min and the temperature of 120 ℃ to obtain an intermediate 3, adding cobalt acetate and acetic acid into the reaction kettle, stirring at the rotation speed of 150r/min until the cobalt acetate is completely dissolved, adding the intermediate 3 and introducing oxygen at the oxygen introduction speed of 55mL/min, and reacting for 8-10h at the temperature of 100 ℃ to obtain an intermediate 4;
step B3: adding the intermediate 4, melamine and tetrahydrofuran into a reaction kettle, introducing nitrogen for protection, stirring for 10min at the rotation speed of 300r/min, heating to 120 ℃ at the speed of 8 ℃/min, carrying out reflux reaction for 6h, distilling to remove tetrahydrofuran to obtain an intermediate 5, adding the intermediate 5, phosphorus pentachloride and toluene into the reaction kettle, carrying out reflux reaction for 5h at the rotation speed of 200r/min and the temperature of 120 ℃, adding aluminum trichloride and phenol, continuously refluxing for 16h, distilling to remove toluene, washing a substrate to be neutral, and preparing an intermediate 6;
step B4: adding diphenyl chlorophosphate, dichloromethane and triethylamine into a reaction kettle, stirring for 10min at the rotation speed of 300r/min and the temperature of 3 ℃, adding 4,4' -dihydroxy benzophenone, reacting for 1.5h, adding sodium borohydride, continuously stirring for 6h, adding deionized water, and standing for 15min to obtain an intermediate 7;
step B5: adding the intermediate 6, iron powder and ethanol into a reaction kettle, performing reflux reaction for 5 hours at the temperature of 85 ℃, adding a hydrochloric acid solution, adding for 20 minutes, continuously reacting for 8 hours, adjusting the pH value of a reaction solution to 8 to obtain an intermediate 8, dissolving the intermediate 8 in tetrahydrofuran, introducing phosgene at the temperature of 30 ℃, continuously stirring for 50 minutes, heating to the temperature of 150 ℃, continuously reacting for 3 hours, cooling to the temperature of 100 ℃, introducing nitrogen to remove phosgene, preserving heat for 15 minutes to obtain an intermediate 9, adding the intermediate 9, the intermediate 7, triethylamine and toluene into the reaction kettle, and performing reflux reaction for 6 hours at the temperature of 120 ℃ to obtain an intermediate 10;
step B6: dissolving cyanuric chloride in acetone, adding the intermediate 10 and sodium acetate under the conditions of a rotating speed of 200r/min and a temperature of 50 ℃, reacting for 5 hours, adding ethylenediamine, performing reflux reaction for 3 hours at a temperature of 90 ℃, and removing the acetone to obtain the flame retardant additive.
Example 2
A graphene composite flame-retardant material comprises the following raw materials in parts by weight: 40 parts of modified graphene and 13 parts of flame retardant additive;
the graphene composite flame-retardant material is prepared by the following steps:
step S1: adding the modified graphene and deionized water into a reaction kettle, stirring at the rotating speed of 300r/min and the temperature of 40 ℃, adding the flame retardant additive and 1-hydroxybenzotriazole, and stirring for 2 hours to obtain a mixed solution;
step S2: and (4) carrying out ultrasonic treatment on the mixed solution prepared in the step (S1) for 10min under the condition of the frequency of 5MHz, filtering to remove filtrate, and drying the filter cake for 3h under the condition of the temperature of 80 ℃ to prepare the graphene composite flame-retardant material.
The modified graphene is prepared by the following steps:
step A1: adding concentrated sulfuric acid into a reaction kettle, stirring at the rotation speed of 150r/min, adding graphite and sodium nitrate at the temperature of 3 ℃, stirring for 10min, adding potassium permanganate, continuously stirring for 1.5h, heating to the temperature of 35 ℃, reacting for 30min, adding deionized water, heating to the temperature of 80 ℃, adding hydrogen peroxide, continuously reacting for 2h, filtering to remove filtrate, and drying a filter cake to obtain graphene oxide;
step A2: dissolving magnesium nitrate hexahydrate and aluminum nitrate nonahydrate in deionized water, adding urea, stirring for 8 hours at the rotation speed of 500r/min and the temperature of 95 ℃, cooling to the temperature of 80 ℃, standing for 5 hours, adding ethanol and ethyl orthosilicate, reacting for 15 hours at the rotation speed of 300r/min and the temperature of 40 ℃, filtering to remove filtrate, washing a filter cake for 2 times by using deionized water, and drying for 3 hours at the temperature of 130 ℃ to obtain the modified graphene.
The flame retardant additive is prepared by the following steps:
step B1: adding p-nitrophenol, p-methylaniline, cyclohexylamine and palladium-carbon into a reaction kettle, introducing nitrogen to discharge air, reacting for 3 hours at the rotation speed of 120r/min, the temperature of 250 ℃ and the pressure of 1.0MPa, cooling to the temperature of 60 ℃, standing for 15 minutes, and taking an upper layer solution to prepare an intermediate 1;
step B2: dissolving the intermediate 1 in tetrahydrofuran, reacting with chlorine gas for 1h under the illumination condition to obtain an intermediate 2, adding the intermediate 2, potassium carbonate, deionized water and tetraethylammonium bromide into a reaction kettle, performing reflux reaction for 1.5h under the conditions of the rotating speed of 200r/min and the temperature of 110 ℃ to obtain an intermediate 3, adding cobalt acetate and acetic acid into the reaction kettle, stirring under the condition of the rotating speed of 120r/min until the cobalt acetate is completely dissolved, adding the intermediate 3 and introducing oxygen at the oxygen introduction speed of 55mL/min, and reacting for 10h under the condition of the temperature of 95 ℃ to obtain an intermediate 4;
step B3: adding the intermediate 4, melamine and tetrahydrofuran into a reaction kettle, introducing nitrogen for protection, stirring for 10min at the rotation speed of 200r/min, heating to 120 ℃ at the speed of 5 ℃/min, carrying out reflux reaction for 6h, distilling to remove tetrahydrofuran to obtain an intermediate 5, adding the intermediate 5, phosphorus pentachloride and toluene into the reaction kettle, carrying out reflux reaction for 3h at the rotation speed of 150r/min and the temperature of 120 ℃, adding aluminum trichloride and phenol, continuously refluxing for 16h, distilling to remove toluene, washing a substrate to be neutral, and preparing an intermediate 6;
step B4: adding diphenyl chlorophosphate, dichloromethane and triethylamine into a reaction kettle, stirring for 5min at the rotating speed of 200r/min and the temperature of 3 ℃, adding 4,4' -dihydroxy benzophenone, reacting for 1.5h, adding sodium borohydride, continuously stirring for 4h, adding deionized water, and standing for 15min to obtain an intermediate 7;
step B5: adding the intermediate 6, iron powder and ethanol into a reaction kettle, performing reflux reaction for 5 hours at the temperature of 80 ℃, adding a hydrochloric acid solution, adding for 20 minutes, continuously reacting for 5 hours, adjusting the pH value of a reaction solution to 8 to obtain an intermediate 8, dissolving the intermediate 8 in tetrahydrofuran, introducing phosgene at the temperature of 25 ℃, continuously stirring for 50 minutes, heating to the temperature of 120 ℃, continuously reacting for 3 hours, cooling to the temperature of 90 ℃, introducing nitrogen to remove phosgene, preserving heat for 15 minutes to obtain an intermediate 9, adding the intermediate 9, the intermediate 7, triethylamine and toluene into the reaction kettle, and performing reflux reaction for 6 hours at the temperature of 115 ℃ to obtain an intermediate 10;
step B6: dissolving cyanuric chloride in acetone, adding the intermediate 10 and sodium acetate under the conditions of the rotating speed of 150r/min and the temperature of 50 ℃, reacting for 3 hours, adding ethylenediamine, performing reflux reaction for 3 hours under the condition of the temperature of 90 ℃, removing acetone, and preparing the flame retardant additive.
Example 3
A graphene composite flame-retardant material comprises the following raw materials in parts by weight: 50 parts of modified graphene and 15 parts of flame retardant additive;
the graphene composite flame-retardant material is prepared by the following steps:
step S1: adding the modified graphene and deionized water into a reaction kettle, stirring at the rotating speed of 500r/min and the temperature of 40 ℃, adding the flame retardant additive and 1-hydroxybenzotriazole, and stirring for 3 hours to obtain a mixed solution;
step S2: and (4) carrying out ultrasonic treatment on the mixed solution prepared in the step (S1) for 15min under the condition of the frequency of 5MHz, filtering to remove filtrate, and drying the filter cake for 3h under the condition of the temperature of 80 ℃ to prepare the graphene composite flame-retardant material.
The modified graphene is prepared by the following steps:
step A1: adding concentrated sulfuric acid into a reaction kettle, stirring at the rotation speed of 200r/min, adding graphite and sodium nitrate at the temperature of 3 ℃, stirring for 15min, adding potassium permanganate, continuously stirring for 1.5h, heating to the temperature of 40 ℃, reacting for 30min, adding deionized water, heating to the temperature of 90 ℃, adding hydrogen peroxide, continuously reacting for 2h, filtering to remove filtrate, and drying a filter cake to obtain graphene oxide;
step A2: dissolving magnesium nitrate hexahydrate and aluminum nitrate nonahydrate in deionized water, adding urea, stirring for 10 hours at the rotation speed of 800r/min and the temperature of 95 ℃, cooling to the temperature of 80 ℃, standing for 6 hours, adding ethanol and ethyl orthosilicate, reacting for 15 hours at the rotation speed of 300r/min and the temperature of 50 ℃, filtering to remove filtrate, washing a filter cake for 3 times by using deionized water, and drying for 3 hours at the temperature of 130 ℃ to obtain the modified graphene.
The flame retardant additive is prepared by the following steps:
step B1: adding p-nitrophenol, p-methylaniline, cyclohexylamine and palladium-carbon into a reaction kettle, introducing nitrogen to discharge air, reacting for 3 hours at the rotation speed of 150r/min, the temperature of 250 ℃ and the pressure of 1.3MPa, cooling to 70 ℃, standing for 15 minutes, and taking an upper layer solution to prepare an intermediate 1;
step B2: dissolving the intermediate 1 in tetrahydrofuran, reacting with chlorine gas for 1.5h under the illumination condition to obtain an intermediate 2, adding the intermediate 2, potassium carbonate, deionized water and tetraethylammonium bromide into a reaction kettle, performing reflux reaction for 1.5h at the rotation speed of 200r/min and the temperature of 120 ℃ to obtain an intermediate 3, adding cobalt acetate and acetic acid into the reaction kettle, stirring at the rotation speed of 150r/min until the cobalt acetate is completely dissolved, adding the intermediate 3 and introducing oxygen at the oxygen introduction speed of 55mL/min, and reacting for 10h at the temperature of 100 ℃ to obtain an intermediate 4;
step B3: adding the intermediate 4, melamine and tetrahydrofuran into a reaction kettle, introducing nitrogen for protection, stirring for 10min at the rotation speed of 300r/min, heating to 120 ℃ at the speed of 8 ℃/min, carrying out reflux reaction for 6h, distilling to remove tetrahydrofuran to obtain an intermediate 5, adding the intermediate 5, phosphorus pentachloride and toluene into the reaction kettle, carrying out reflux reaction for 5h at the rotation speed of 200r/min and the temperature of 120 ℃, adding aluminum trichloride and phenol, continuously refluxing for 16h, distilling to remove toluene, washing a substrate to be neutral, and preparing an intermediate 6;
step B4: adding diphenyl chlorophosphate, dichloromethane and triethylamine into a reaction kettle, stirring for 10min at the rotation speed of 300r/min and the temperature of 3 ℃, adding 4,4' -dihydroxy benzophenone, reacting for 1.5h, adding sodium borohydride, continuously stirring for 6h, adding deionized water, and standing for 15min to obtain an intermediate 7;
step B5: adding the intermediate 6, iron powder and ethanol into a reaction kettle, performing reflux reaction for 5 hours at the temperature of 85 ℃, adding a hydrochloric acid solution, adding for 20 minutes, continuously reacting for 8 hours, adjusting the pH value of a reaction solution to 8 to obtain an intermediate 8, dissolving the intermediate 8 in tetrahydrofuran, introducing phosgene at the temperature of 30 ℃, continuously stirring for 50 minutes, heating to the temperature of 150 ℃, continuously reacting for 3 hours, cooling to the temperature of 100 ℃, introducing nitrogen to remove phosgene, preserving heat for 15 minutes to obtain an intermediate 9, adding the intermediate 9, the intermediate 7, triethylamine and toluene into the reaction kettle, and performing reflux reaction for 6 hours at the temperature of 120 ℃ to obtain an intermediate 10;
step B6: dissolving cyanuric chloride in acetone, adding the intermediate 10 and sodium acetate under the conditions of a rotating speed of 200r/min and a temperature of 50 ℃, reacting for 5 hours, adding ethylenediamine, performing reflux reaction at the temperature of 90 ℃ for 3-5 hours, and removing acetone to obtain the flame retardant additive.
Comparative example
The comparative example is a common graphene composite flame-retardant material in the market.
The graphene composite flame retardant materials prepared in examples 1 to 3 and the comparative example were added to a PVC material, and the PVC material was subjected to flame retardant testing, the test results of which are shown in table 1 below;
TABLE 1
As shown in the above Table 1, the flame retardancy of the PVC material reinforced by the graphene composite flame retardant materials prepared in the examples 1-3 is V0, and the smoke production rate is 0.085-0.091m2/s2The flame retardance of the PVC material reinforced by the graphene composite flame-retardant material prepared in the comparative example is V1, and the smoke production rate is 0.435m2/s2The invention has good flame retardant effect.
The foregoing is merely exemplary and illustrative of the principles of the present invention and various modifications, additions and substitutions of the specific embodiments described herein may be made by those skilled in the art without departing from the principles of the present invention or exceeding the scope of the claims set forth herein.
Claims (7)
1. A graphene composite flame-retardant material is characterized in that: the feed comprises the following raw materials in parts by weight: 30-50 parts of modified graphene and 10-15 parts of flame retardant additive;
the graphene composite flame-retardant material is prepared by the following steps:
step S1: adding the modified graphene and deionized water into a reaction kettle, stirring at the rotation speed of 300-500r/min and the temperature of 35-40 ℃, adding the flame retardant additive and 1-hydroxybenzotriazole, and stirring for 2-3h to obtain a mixed solution;
step S2: and (4) carrying out ultrasonic treatment on the mixed solution prepared in the step (S1) for 10-15min under the condition that the frequency is 3-5MHz, filtering to remove filtrate, and drying the filter cake for 2-3h under the condition that the temperature is 80 ℃ to prepare the graphene composite flame-retardant material.
2. The graphene composite flame retardant material according to claim 1, wherein: the dosage of the 1-hydroxybenzotriazole in the step S1 is 25-30% of the modified graphene by mass.
3. The graphene composite flame retardant material according to claim 1, wherein: the modified graphene is prepared by the following steps:
step A1: adding concentrated sulfuric acid into a reaction kettle, stirring at the rotation speed of 150-200r/min, adding graphite and sodium nitrate at the temperature of 1-3 ℃, stirring for 10-15min, adding potassium permanganate, continuously stirring for 1-1.5h, heating to 35-40 ℃, reacting for 20-30min, adding deionized water, heating to 80-90 ℃, adding hydrogen peroxide, continuously reacting for 1-2h, filtering to remove filtrate, and drying a filter cake to obtain graphene oxide;
step A2: dissolving magnesium nitrate hexahydrate and aluminum nitrate nonahydrate in deionized water, adding urea, stirring at the rotation speed of 800-.
4. The graphene composite flame retardant material according to claim 3, wherein: the using amount ratio of the concentrated sulfuric acid, the graphite, the sodium nitrate, the potassium permanganate, the deionized water and the hydrogen peroxide in the step A1 is 22mL:1g:0.5g:3g:100mL:4mL, the mass number of the concentrated sulfuric acid is 70%, the mass fraction of the hydrogen peroxide is 10%, and the using amount ratio of the concentrated sulfuric acid, the graphite, the sodium nitrate, the potassium permanganate, the deionized water and the hydrogen peroxide in the step A1 in the step A2 is 22mL:1g:0.5g:3g:100mL:4 mL.
5. The graphene composite flame retardant material according to claim 1, wherein: the flame retardant additive is prepared by the following steps:
step B1: adding p-nitrophenol, p-methylaniline, cyclohexylamine and palladium carbon into a reaction kettle, introducing nitrogen to discharge air, reacting for 2-3h at the rotation speed of 120-250 ℃ and the temperature of 245-250 ℃ under the pressure of 1.0-1.3MPa, cooling to 60-70 ℃, standing for 10-15min, and taking an upper layer solution to prepare an intermediate 1;
step B2: dissolving the intermediate 1 in tetrahydrofuran, reacting with chlorine gas under the condition of illumination for 1-1.5h to obtain an intermediate 2, adding the intermediate 2, potassium carbonate, deionized water and tetraethylammonium bromide into a reaction kettle, performing reflux reaction for 1-1.5h under the conditions of the rotating speed of 150-200r/min and the temperature of 110-120 ℃ to obtain an intermediate 3, adding cobalt acetate and acetic acid into the reaction kettle, stirring under the conditions of the rotating speed of 120-150r/min until the cobalt acetate is completely dissolved, adding the intermediate 3 and introducing oxygen at the oxygen introduction speed of 50-55mL/min, and reacting for 8-10h under the temperature of 95-100 ℃ to obtain an intermediate 4;
step B3: adding the intermediate 4, melamine and tetrahydrofuran into a reaction kettle, introducing nitrogen for protection, stirring for 5-10min under the condition that the rotation speed is 200-;
step B4: adding diphenyl chlorophosphate, dichloromethane and triethylamine into a reaction kettle, stirring for 5-10min at the rotation speed of 200-3 ℃ and at the temperature of 1-3 ℃, adding 4,4' -dihydroxy benzophenone, reacting for 1-1.5h, adding sodium borohydride, continuously stirring for 4-6h, adding deionized water, and standing for 10-15min to obtain an intermediate 7;
step B5: adding the intermediate 6, iron powder and ethanol into a reaction kettle, carrying out reflux reaction for 3-5h at the temperature of 80-85 ℃, adding a hydrochloric acid solution for 20min, continuously reacting for 5-8h, adjusting the pH value of a reaction solution to 7-8 to obtain an intermediate 8, dissolving the intermediate 8 in tetrahydrofuran, introducing phosgene at the temperature of 25-30 ℃, continuously stirring for 30-50min, heating to the temperature of 120-150 ℃, continuously reacting for 2-3h, cooling to the temperature of 90-100 ℃, introducing nitrogen to remove phosgene, preserving heat for 10-15min to obtain an intermediate 9, adding the intermediate 9, the intermediate 7, triethylamine and toluene into the reaction kettle, carrying out reflux reaction for 4-6h at the temperature of 115-120 ℃, to obtain an intermediate 10;
step B6: dissolving cyanuric chloride in acetone, adding the intermediate 10 and sodium acetate under the conditions of a rotation speed of 150-200r/min and a temperature of 40-50 ℃, reacting for 3-5h, adding ethylenediamine, performing reflux reaction at a temperature of 80-90 ℃ for 3-5h, and removing acetone to obtain the flame retardant additive.
6. The graphene composite flame retardant material according to claim 5, wherein: the dosage ratio of the p-nitrophenol, the p-methylaniline, the cyclohexylamine and the palladium carbon in the step B1 is 1mol:1mol:0.1mol:1g, the dosage molar ratio of the intermediate 1 and the chlorine gas in the step B2 is 2:1, the dosage ratio of the intermediate 2, the potassium carbonate, the deionized water and the tetraethylammonium bromide is 10g:9g:70mL:2mL, the dosage-mass ratio of the cobalt acetate to the intermediate 3 is 1:5, the dosage-mass ratio of the intermediate 4 to the melamine in the step B3 is 8:3, the dosage-mass ratio of the intermediate 5, the phosphorus pentachloride, the aluminum trichloride and the phenol is 1:3:0.1:7, the dosage-mass ratio of the diphenyl chlorophosphate, the dichloromethane, the triethylamine, the 4,4' -dihydroxybenzophenone and the sodium borohydride in the step B4 is 1mol:200mL:2mol:2mol:0.6mol, the dosage ratio of the intermediate 6, the iron powder, the ethanol and the hydrochloric acid solution in the step B5 is 4g:4.5g:55mL:10mL, the volume fraction of the ethanol is 90%, the hydrochloric acid solution is formed by mixing concentrated hydrochloric acid with the mass fraction of 36% and ethanol with the volume fraction of 95% in a volume ratio of 1:9, the using molar ratio of the intermediate 8 to phosgene is 1:1, the using molar ratio of the intermediate 9, the intermediate 7 and triethylamine is 1:1:2, the using molar ratio of the cyanuric chloride, the intermediate 10 and the ethylenediamine in the step B6 is 1:1:1, and the using amount of the sodium acetate is 30% of the mass of the cyanuric chloride.
7. The preparation method of the graphene composite flame-retardant material according to claim 1, characterized by comprising the following steps: the method specifically comprises the following steps:
step S1: adding the modified graphene and deionized water into a reaction kettle, stirring at the rotation speed of 300-500r/min and the temperature of 35-40 ℃, adding the flame retardant additive and 1-hydroxybenzotriazole, and stirring for 2-3h to obtain a mixed solution;
step S2: and (4) carrying out ultrasonic treatment on the mixed solution prepared in the step (S1) for 10-15min under the condition that the frequency is 3-5MHz, filtering to remove filtrate, and drying the filter cake for 2-3h under the condition that the temperature is 80 ℃ to prepare the graphene composite flame-retardant material.
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Effective date of registration: 20221024 Address after: No. 89, Gangqu Middle Road, Xinbei District, Changzhou City, Jiangsu Province, 213000 (in Binjiang Intelligent Equipment Enterprise Port) Patentee after: Xingtu (Changzhou) carbon materials Co.,Ltd. Address before: 224400 east 3, Sunxi Road, Funing high tech Industrial Development Zone, Yancheng City, Jiangsu Province (f) Patentee before: Jiangsu Xingtu New Material Technology Co.,Ltd. |