CN111849290A - High-thermal-conductivity flame-retardant acrylic resin coating and preparation method thereof - Google Patents
High-thermal-conductivity flame-retardant acrylic resin coating and preparation method thereof Download PDFInfo
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Abstract
The invention relates to the technical field of acrylic resin, and discloses a high-heat-conductivity flame-retardant acrylic resin coating which comprises the following formula raw materials and components: modified nano boron nitride-graphene composite material, condensing agent, methacrylic acid, styrene, methyl acrylate and initiator. The urea can promote the stripping of the boron nitride nanosheets, amino groups are modified into the lamellar structure of the boron nitride and are subjected to cross-linking reaction with the amino groups in the reduced graphene oxide, the boron nitride nanosheets are tightly combined with the graphene through the bonding effect of chemical bonds to form aerogel with a higher heat conductivity coefficient, the N- (beta-aminoethyl) -gamma-aminopropyltrimethoxysilane is reacted with the reduced graphene oxide, and the boron nitride-graphene composite material is grafted into the matrix of acrylic resin through the chemical bonds, so that the dispersibility and compatibility of the boron nitride-graphene aerogel with the three-dimensional lamellar structure and the acrylic resin are improved, and the acrylic resin coating film is endowed with excellent heat conductivity and flame retardance.
Description
Technical Field
The invention relates to the technical field of acrylic resin, in particular to a high-heat-conductivity flame-retardant acrylic resin coating and a preparation method thereof.
Background
The acrylic resin is a polymer of acrylic acid, methacrylic acid and derivatives thereof, the acrylic resin coating is a thermoplastic or thermosetting resin coating prepared by acrylic resin obtained by copolymerization of acrylic ester and styrene as main bodies and other acrylic ester, the thermoplastic acrylic resin does not generate further crosslinking in the film forming process, has relatively large molecular weight, good gloss and color retention, water and chemical resistance and quick drying, and is widely applied in the fields of buildings, automobiles, machinery, electric appliances and the like, the thermosetting acrylic resin has a certain functional group in the structure, forms a net structure by reacting with functional groups in added amino resin, epoxy resin, polyurethane and the like during paint making, and the thermosetting resin is generally relatively low in molecular weight and has excellent performances of fullness, hardness, solvent resistance, weather resistance and the like, the method is widely applied to products such as automobiles, motorcycles, coil steels and the like at present.
The high-temperature resistance and the flame retardance of the existing acrylic resin coating film are not high, nano boron nitride and nano graphene with high thermal conductivity coefficients can be used as fillers, the thermal conductivity of the acrylic resin coating film is utilized, and the graphene nano material also has wide application in the aspect of enhancing the flame retardance of the resin coating, but the nano boron nitride and graphene nano material have poor compatibility with acrylic resin, and the non-uniform dispersion of boron nitride and graphene can seriously affect the mechanical properties of the acrylic resin, such as tensile strength, toughness and the like.
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides a high-heat-conductivity flame-retardant acrylic resin coating and a preparation method thereof, solves the problems of poor heat conductivity and flame retardant property of acrylic resin, and simultaneously solves the problems of poor dispersibility and compatibility of graphene and boron nitride with acrylic resin.
(II) technical scheme
In order to achieve the purpose, the invention provides the following technical scheme: the high-heat-conductivity flame-retardant acrylic resin coating comprises the following formula raw materials in parts by weight: 2-6 parts of modified nano boron nitride-graphene composite material, 8-12 parts of condensing agent, 22-35 parts of methacrylic acid, 8-15 parts of styrene, 25-50 parts of methyl acrylate and 10-17 parts of initiator.
Preferably, the condensing agent is 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride.
Preferably, the initiator is ammonium persulfate.
Preferably, the preparation method of the modified nano boron nitride-graphene composite material comprises the following steps:
(1) adding a mixed solvent of distilled water and methanol into a reaction bottle, wherein the volume ratio of the distilled water to the mixed solvent of methanol is 1-2:1, adding boric acid and urea, stirring uniformly, freeze drying the solution to remove the solvent, placing the solid product in an atmosphere resistance furnace, introducing ammonia gas, heating at the rate of 2-5 ℃/min, calcining at 850-880 deg.C for 3-5h, washing the solid product with distilled water and ethanol, and fully drying to prepare the boron nitride nanosheet with the layered structure, adding ethanol solvent, the boron nitride nanosheet and urea into a planetary ball mill, carrying out ball milling for 25-30h at the revolution speed of 600-325 rpm and the rotation speed of 300-325rpm of the planetary ball mill, carrying out reduced pressure concentration on the solution to remove the solvent, placing the solid product into a dialysis bag, and adding distilled water to carry out a dialysis impurity removal process to prepare the aminated boron nitride nanosheet.
(2) Adding distilled water, aminated boron nitride nanosheets and reduced graphene oxide into a reaction bottle, after uniform ultrasonic dispersion, adding cross-linking agents of glutaraldehyde and resorcinol, continuing ultrasonic dispersion treatment for 1-2h, placing the reaction bottle into a constant-temperature water bath kettle, heating to 40-60 ℃, stirring at a constant speed for reaction for 5-8h, and performing freeze drying on the solution to prepare the nano boron nitride modified graphene aerogel.
(3) Introducing nitrogen into a reaction bottle to discharge air, adding a mixed solvent of distilled water and ethanol, wherein the volume ratio of the distilled water to the ethanol is 1:5-8, adding ground nano boron nitride modified graphene aerogel, uniformly dispersing by using ultrasonic waves, adding a silane coupling agent, placing the mixture in a constant-temperature water bath kettle, heating to 80-100 ℃, uniformly stirring for reaction for 15-20 hours, filtering the solution to remove the solvent, washing a solid product by using distilled water and ethanol, and fully drying to obtain the silane coupling agent grafted modified nano boron nitride-graphene composite material.
Preferably, the mass ratio of the boric acid to the nitrogen source urea in the step (1) is 1:22-28, and the mass ratio of the boron nitride nanosheet to the amino source urea is 1: 55-70.
Preferably, the mass ratio of the aminated boron nitride nanosheets, the reduced graphene oxide, the glutaraldehyde and the resorcinol in step (2) is 1:0.4-0.8:0.06-0.1: 0.2-0.4.
Preferably, the silane coupling agent in the step (3) is N- (beta-aminoethyl) -gamma-aminopropyltrimethoxysilane, and the mass ratio of the N- (beta-aminoethyl) -gamma-aminopropyltrimethoxysilane to the nano boron nitride modified graphene aerogel is 1: 1.2-2.
Preferably, the preparation method of the flame retardant acrylic resin coating with high thermal conductivity comprises the following steps:
(1) adding distilled water solvent, 2-6 parts of modified nano boron nitride-graphene composite material, 22-35 parts of methacrylic acid, 8-15 parts of styrene and 25-50 parts of methyl acrylate into a reaction bottle, stirring uniformly, adding 8-12 parts of condensing agent 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride, placing the reaction bottle into a constant-temperature water bath kettle, heating to 40-70 ℃, stirring at a constant speed for 10-15 hours, adding 8-15 parts of styrene and 10-17 parts of initiator ammonium persulfate, heating to 75-90 ℃, stirring at a constant speed for 3-6 hours, adding ammonia water to adjust the pH of the solution to be neutral, and carrying out a high-speed emulsification process on the solution to prepare the high-thermal-conductivity flame-retardant acrylic resin coating.
(III) advantageous technical effects
Compared with the prior art, the invention has the following beneficial technical effects:
the high-thermal-conductivity flame-retardant acrylic resin coating is prepared by taking distilled water and methanol as dispersion media, boric acid and urea as raw materials, preparing boron nitride nanosheets with huge specific surface areas by a freeze-drying method and an ammonia atmosphere high-temperature nitriding method, performing ball-milling blending modification on the boron nitride nanosheets by taking the urea as an ammonia source, promoting stripping of the boron nitride nanosheets by the urea, protecting boron nitride lamella from damaging the nanosheet shape in a high-speed ball-milling process, modifying amino into the lamella structure of the boron nitride nanosheets, performing cross-linking reaction by taking glutaraldehyde and resorcinol as cross-linking agents and reducing the amino in graphene oxide, preparing the nano boron nitride modified graphene aerogel by the freeze-drying method, enabling the boron nitride nanosheets to be tightly combined with graphene through the bonding effect of chemical bonds, enabling the boron nitride nanosheets to be difficult to fall off and separate from the graphene, the thermal conductivity coefficient of the nano boron nitride modified graphene aerogel is higher.
The high-thermal-conductivity flame-retardant acrylic resin coating is prepared by reacting silane coupling agent N- (beta-aminoethyl) -gamma-aminopropyltrimethoxysilane with hydroxyl in reduced graphene oxide to obtain a modified nano boron nitride-graphene composite material grafted with N- (beta-aminoethyl) -gamma-aminopropyltrimethoxysilane, and then taking 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride as a condensing agent to cause condensation reaction between amino in the N- (beta-aminoethyl) -gamma-aminopropyltrimethoxysilane and carboxyl in methacrylic acid and methyl acrylate, so that the boron nitride-graphene composite material is grafted into a substrate of acrylic resin through chemical bonds, the dispersibility and compatibility of the nano boron nitride and graphene with the acrylic resin are greatly improved, the heat-conducting property of the acrylic resin coating is obviously enhanced, the boron nitride and nanosheet-graphene aerogel material has a three-dimensional nano flaky structure, a flaky protective layer is formed in an acrylic resin matrix, when the acrylic resin coating burns, the three-dimensional flaky structure plays a role in uniformly transferring heat and reducing the phenomenon of heat concentration and aggregation, the three-dimensional flaky structure reduces the permeation of oxygen, and the acrylic coating is endowed with excellent flame retardant property under the synergistic effect.
Detailed Description
To achieve the above object, the present invention provides the following embodiments and examples: the high-heat-conductivity flame-retardant acrylic resin coating comprises the following formula raw materials in parts by weight: 2-6 parts of modified nano boron nitride-graphene composite material, 8-12 parts of condensing agent, 22-35 parts of methacrylic acid, 8-15 parts of styrene, 25-50 parts of methyl acrylate and 10-17 parts of initiator, wherein the condensing agent is 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride, and the initiator is ammonium persulfate.
The preparation method of the modified nano boron nitride-graphene composite material comprises the following steps:
(1) adding a mixed solvent of distilled water and methanol into a reaction bottle, wherein the volume ratio of the distilled water to the methanol is 1-2:1, adding boric acid and urea, the mass ratio of the boric acid to the urea is 1:22-28, stirring uniformly, freeze-drying the solution to remove the solvent, placing the solid product into an atmosphere resistance furnace, introducing ammonia gas, heating at the rate of 2-5 ℃/min, carrying out heat preservation and calcination at the temperature of 850 plus 880 ℃ for 3-5h, washing the solid product with distilled water and ethanol, fully drying to prepare the boron nitride nanosheet with the layered structure, adding ethanol solvent, the boron nitride nanosheet and urea into a planetary ball mill, wherein the mass ratio of the ethanol solvent to the boron nitride nanosheet to the urea is 1:55-70, the revolution speed of the planetary ball mill is 600 plus 650rpm, the rotation speed is 300 plus 325rpm, carrying out ball milling for 25-30h, carrying out reduced pressure concentration, and adding distilled water to perform a dialysis impurity removal process to prepare the aminated boron nitride nanosheet.
(2) Adding distilled water, aminated boron nitride nanosheets and reduced graphene oxide into a reaction bottle, after uniform ultrasonic dispersion, adding cross-linking agents of glutaraldehyde and resorcinol in a mass ratio of 1:0.4-0.8:0.06-0.1:0.2-0.4, continuing ultrasonic dispersion treatment for 1-2 hours, placing the reaction bottle into a constant-temperature water bath, heating to 40-60 ℃, stirring at a constant speed for reaction for 5-8 hours, and performing freeze drying on the solution to prepare the nano boron nitride modified graphene aerogel.
(3) Introducing nitrogen into a reaction bottle to discharge air, adding a mixed solvent of distilled water and ethanol, wherein the volume ratio of the distilled water to the ethanol is 1:5-8, adding ground nano boron nitride modified graphene aerogel, uniformly performing ultrasonic dispersion, adding a silane coupling agent N- (beta-aminoethyl) -gamma-aminopropyltrimethoxysilane, wherein the mass ratio of the silane coupling agent N- (beta-aminoethyl) -gamma-aminopropyltrimethoxysilane to the nano boron nitride modified graphene aerogel is 1:1.2-2, placing the mixture in a constant-temperature water bath, heating to 80-100 ℃, uniformly stirring for reaction for 15-20 hours, filtering the solution to remove the solvent, washing the solid product with distilled water and ethanol, and fully drying to obtain the silane coupling agent grafted modified nano boron nitride-graphene composite material.
The preparation method of the flame-retardant acrylic resin coating with high heat conductivity comprises the following steps:
(1) Adding distilled water solvent, 2-6 parts of modified nano boron nitride-graphene composite material, 22-35 parts of methacrylic acid, 8-15 parts of styrene and 25-50 parts of methyl acrylate into a reaction bottle, stirring uniformly, adding 8-12 parts of condensing agent 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride, placing the reaction bottle into a constant-temperature water bath kettle, heating to 40-70 ℃, stirring at a constant speed for 10-15 hours, adding 8-15 parts of styrene and 10-17 parts of initiator ammonium persulfate, heating to 75-90 ℃, stirring at a constant speed for 3-6 hours, adding ammonia water to adjust the pH of the solution to be neutral, and carrying out a high-speed emulsification process on the solution to prepare the high-thermal-conductivity flame-retardant acrylic resin coating.
Example 1
(1) Preparation of aminated boron nitride nanosheet component 1: adding a mixed solvent of distilled water and methanol into a reaction bottle, wherein the volume ratio of the distilled water to the mixed solvent of methanol is 1:1, adding boric acid and urea, the mass ratio of the boric acid to the urea is 1:22, stirring uniformly, freeze drying the solution to remove the solvent, placing the solid product in an atmosphere resistance furnace, introducing ammonia gas, heating at the rate of 2 ℃/min, calcining at 850 ℃ for 3h under heat preservation, washing the solid product with distilled water and ethanol, fully drying to prepare boron nitride nanosheets with layered structures, adding ethanol solvent, the boron nitride nanosheets and urea into a planetary ball mill at a mass ratio of 1:55, a revolution speed of the planetary ball mill of 600rpm and an autorotation speed of 300rpm, carrying out ball milling for 25h, concentrating the solution under reduced pressure to remove the solvent, placing the solid product in a dialysis bag, adding distilled water to perform dialysis impurity removal process, and preparing to obtain the aminated boron nitride nanosheet component 1.
(2) Preparing a nano boron nitride modified graphene aerogel component 1: adding distilled water, the aminated boron nitride nanosheet component 1 and reduced graphene oxide into a reaction bottle, after uniform ultrasonic dispersion, adding cross-linking agents of glutaraldehyde and resorcinol in a mass ratio of 1:0.4:0.06:0.2, continuing ultrasonic dispersion treatment for 1h, placing the reaction bottle into a constant-temperature water bath kettle, heating to 40 ℃, stirring at a constant speed for reaction for 5h, and carrying out freeze drying on the solution to prepare the nano boron nitride modified graphene aerogel component 1.
(3) Preparing a modified nano boron nitride-graphene composite material 1: introducing nitrogen into a reaction bottle to discharge air, adding a mixed solvent of distilled water and ethanol, wherein the volume ratio of the distilled water to the ethanol is 1:5, adding the ground nano boron nitride modified graphene aerogel component 1, uniformly performing ultrasonic dispersion, adding a silane coupling agent N- (beta-aminoethyl) -gamma-aminopropyltrimethoxysilane, wherein the mass ratio of the silane coupling agent N- (beta-aminoethyl) -gamma-aminopropyltrimethoxysilane to the nano boron nitride modified graphene aerogel is 1:1.2, placing the mixture in a constant-temperature water bath, heating to 80 ℃, uniformly stirring for reaction for 15 hours, filtering the solution to remove the solvent, washing the solid product by using distilled water and ethanol, and fully drying to obtain the silane coupling agent grafted modified nano boron nitride-graphene composite material 1.
(4) Preparing a high-thermal-conductivity flame-retardant acrylic resin coating 1: adding distilled water solvent, 2 parts of modified nano boron nitride-graphene composite material 1, 22 parts of methacrylic acid, 8 parts of styrene and 50 parts of methyl acrylate into a reaction bottle, stirring uniformly, adding 8 parts of condensing agent 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride, placing the reaction bottle into a constant-temperature water bath kettle, heating to 40 ℃, stirring at a constant speed for reaction for 10 hours, adding 8 parts of styrene and 10 parts of initiator ammonium persulfate, heating to 75 ℃, stirring at a constant speed for reaction for 3 hours, adding ammonia water to adjust the pH value of the solution to be neutral, and performing a high-speed emulsification process on the solution to prepare the high-thermal-conductivity flame-retardant acrylic resin coating 1.
Example 2
(1) Preparation of aminated boron nitride nanosheet component 2: adding a mixed solvent of distilled water and methanol into a reaction bottle, wherein the volume ratio of the distilled water to the mixed solvent of methanol is 1:1, adding boric acid and urea, the mass ratio of the boric acid to the urea is 1:22, stirring uniformly, freeze drying the solution to remove the solvent, placing the solid product in an atmosphere resistance furnace, introducing ammonia gas, heating at the rate of 2 ℃/min, calcining at 850 ℃ for 3h under heat preservation, washing the solid product with distilled water and ethanol, fully drying to prepare boron nitride nanosheets with layered structures, adding ethanol solvent, the boron nitride nanosheets and urea into a planetary ball mill at a mass ratio of 1:70, a revolution speed of the planetary ball mill of 600rpm and an autorotation speed of 300rpm, carrying out ball milling for 0h, concentrating the solution under reduced pressure to remove the solvent, placing the solid product in a dialysis bag, adding distilled water to perform dialysis impurity removal process, and preparing to obtain the aminated boron nitride nanosheet component 2.
(2) Preparing a nano boron nitride modified graphene aerogel component 2: adding distilled water, an aminated boron nitride nanosheet component 2 and reduced graphene oxide into a reaction bottle, after uniform ultrasonic dispersion, adding cross-linking agents of glutaraldehyde and resorcinol in a mass ratio of 1:0.8:0.1:0.2, continuing ultrasonic dispersion treatment for 2 hours, placing the reaction bottle into a constant-temperature water bath kettle, heating to 60 ℃, stirring at a constant speed for reaction for 5 hours, and carrying out freeze drying on the solution to prepare the nano boron nitride modified graphene aerogel component 2.
(3) Preparing a modified nano boron nitride-graphene composite material 2: introducing nitrogen into a reaction bottle to discharge air, adding a mixed solvent of distilled water and ethanol, wherein the volume ratio of the distilled water to the ethanol is 1:5, adding a ground nano boron nitride modified graphene aerogel component 2, uniformly performing ultrasonic dispersion, adding a silane coupling agent N- (beta-aminoethyl) -gamma-aminopropyltrimethoxysilane, wherein the mass ratio of the silane coupling agent N- (beta-aminoethyl) -gamma-aminopropyltrimethoxysilane to the nano boron nitride modified graphene aerogel is 1:1.2, placing the mixture into a constant-temperature water bath, heating to 80 ℃, uniformly stirring for reaction for 20 hours, filtering the solution to remove the solvent, washing a solid product by using distilled water and ethanol, and fully drying to obtain the silane coupling agent grafted modified nano boron nitride-graphene composite material 2.
(4) Preparing a high-thermal-conductivity flame-retardant acrylic resin coating 2: adding distilled water solvent, 3 parts of modified nano boron nitride-graphene composite material 2, 25 parts of methacrylic acid, 9.5 parts of styrene and 43 parts of methyl acrylate into a reaction bottle, stirring uniformly, adding 9 parts of condensing agent 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride, placing the reaction bottle into a constant-temperature water bath kettle, heating to 70 ℃, stirring at a constant speed for reaction for 10 hours, adding 9.5 parts of styrene and 12 parts of initiator ammonium persulfate, heating to 75 ℃, stirring at a constant speed for reaction for 6 hours, adding ammonia water to adjust the pH of the solution to be neutral, and performing a high-speed emulsification process on the solution to prepare the high-thermal-conductivity flame-retardant acrylic resin coating 2.
Example 3
(1) Preparation of aminated boron nitride nanosheet component 3: adding a mixed solvent of distilled water and methanol into a reaction bottle, wherein the volume ratio of the distilled water to the mixed solvent of methanol is 1.5:1, adding boric acid and urea, the mass ratio of the boric acid to the urea is 1:25, stirring uniformly, freeze drying the solution to remove the solvent, placing the solid product in an atmosphere resistance furnace, introducing ammonia gas, heating at a rate of 4 ℃/min, calcining at 870 ℃ for 4h under heat preservation, washing a solid product by using distilled water and ethanol, fully drying to prepare boron nitride nanosheets with a layered structure, adding ethanol solvent, the boron nitride nanosheets and urea into a planetary ball mill at a mass ratio of 1:65, a revolution speed of the planetary ball mill is 620rpm, an autorotation speed of the planetary ball mill is 310rpm, carrying out ball milling for 28h, concentrating the solution under reduced pressure to remove the solvent, placing the solid product in a dialysis bag, adding distilled water to perform dialysis impurity removal process, and preparing to obtain the aminated boron nitride nanosheet component 3.
(2) Preparing a nano boron nitride modified graphene aerogel component 3: adding distilled water, an aminated boron nitride nanosheet component 3 and reduced graphene oxide into a reaction bottle, after uniform ultrasonic dispersion, adding cross-linking agents of glutaraldehyde and resorcinol in a mass ratio of 1:0.6:0.08:0.3, continuing ultrasonic dispersion treatment for 1.5h, placing the reaction bottle into a constant-temperature water bath, heating to 50 ℃, stirring at a constant speed for reaction for 6h, and carrying out freeze drying on the solution to prepare the nano boron nitride modified graphene aerogel component 3.
(3) Preparing a modified nano boron nitride-graphene composite material 3: introducing nitrogen into a reaction bottle to discharge air, adding a mixed solvent of distilled water and ethanol, wherein the volume ratio of the distilled water to the ethanol is 1:6, adding a ground nano boron nitride modified graphene aerogel component 3, uniformly performing ultrasonic dispersion, adding a silane coupling agent N- (beta-aminoethyl) -gamma-aminopropyltrimethoxysilane, wherein the mass ratio of the silane coupling agent N- (beta-aminoethyl) -gamma-aminopropyltrimethoxysilane to the nano boron nitride modified graphene aerogel is 1:1.6, placing the mixture into a constant-temperature water bath, heating to 90 ℃, uniformly stirring for reaction for 18 hours, filtering the solution to remove the solvent, washing a solid product by using distilled water and ethanol, and fully drying to obtain the silane coupling agent grafted modified nano boron nitride-graphene composite material 3.
(4) Preparing a high-thermal-conductivity flame-retardant acrylic resin coating 3: adding distilled water solvent, 4 parts of modified nano boron nitride-graphene composite material 3, 28 parts of methacrylic acid, 11 parts of styrene and 38 parts of methyl acrylate into a reaction bottle, stirring uniformly, adding 10 parts of condensing agent 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride, placing the reaction bottle into a constant-temperature water bath kettle, heating to 55 ℃, stirring at a constant speed for reaction for 12 hours, adding 12 parts of styrene and 14 parts of initiator ammonium persulfate, heating to 80 ℃, stirring at a constant speed for reaction for 5 hours, adding ammonia water to adjust the pH of the solution to be neutral, and performing a high-speed emulsification process on the solution to prepare the high-thermal-conductivity flame-retardant acrylic resin coating 3.
Example 4
(1) Preparation of aminated boron nitride nanosheet component 4: adding a mixed solvent of distilled water and methanol into a reaction bottle, wherein the volume ratio of the distilled water to the mixed solvent of methanol is 1:1, adding boric acid and urea, the mass ratio of the boric acid to the urea is 1:22, stirring uniformly, freeze drying the solution to remove the solvent, placing the solid product in an atmosphere resistance furnace, introducing ammonia gas, heating at the rate of 2 ℃/min, calcining at 880 ℃ for 5h under heat preservation, washing the solid product with distilled water and ethanol, fully drying to obtain boron nitride nanosheets with layered structures, adding ethanol solvent, the boron nitride nanosheets and urea into a planetary ball mill at a mass ratio of 1:70, wherein the revolution speed of the planetary ball mill is 640rpm, the rotation speed of the planetary ball mill is 320rpm, carrying out ball milling for 30h, concentrating the solution under reduced pressure to remove the solvent, placing the solid product in a dialysis bag, adding distilled water to perform dialysis impurity removal process, and preparing to obtain the aminated boron nitride nanosheet component 4.
(2) Preparing a nano boron nitride modified graphene aerogel component 4: adding distilled water, an aminated boron nitride nanosheet component 4 and reduced graphene oxide into a reaction bottle, after uniform ultrasonic dispersion, adding cross-linking agents of glutaraldehyde and resorcinol in a mass ratio of 1:0.4:0.06:0.2, continuing ultrasonic dispersion treatment for 1h, placing the reaction bottle into a constant-temperature water bath kettle, heating to 40 ℃, stirring at a constant speed for reaction for 8h, and carrying out freeze drying on the solution to prepare a nano boron nitride modified graphene aerogel component 4.
(3) Preparing a modified nano boron nitride-graphene composite material 4: introducing nitrogen into a reaction bottle to discharge air, adding a mixed solvent of distilled water and ethanol, wherein the volume ratio of the distilled water to the ethanol is 1:8, adding a ground nano boron nitride modified graphene aerogel component 4, uniformly performing ultrasonic dispersion, adding a silane coupling agent N- (beta-aminoethyl) -gamma-aminopropyltrimethoxysilane, wherein the mass ratio of the silane coupling agent N- (beta-aminoethyl) -gamma-aminopropyltrimethoxysilane to the nano boron nitride modified graphene aerogel is 1:1.2, placing the mixture into a constant-temperature water bath, heating to 100 ℃, uniformly stirring for reaction for 15 hours, filtering the solution to remove the solvent, washing a solid product by using distilled water and ethanol, and fully drying to obtain the silane coupling agent grafted modified nano boron nitride-graphene composite material 4.
(4) Preparing a high-thermal-conductivity flame-retardant acrylic resin coating 4: adding distilled water solvent, 5 parts of modified nano boron nitride-graphene composite material 4, 25 parts of methacrylic acid, 12.5 parts of styrene and 32 parts of methyl acrylate into a reaction bottle, stirring uniformly, adding 11 parts of condensing agent 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride, placing the reaction bottle into a constant-temperature water bath kettle, heating to 70 ℃, stirring at a constant speed for reaction for 15 hours, adding 13 parts of styrene and 15.5 parts of initiator ammonium persulfate, heating to 75 ℃, stirring at a constant speed for reaction for 3 hours, adding ammonia water to adjust the pH of the solution to be neutral, and performing a high-speed emulsification process on the solution to prepare the high-thermal-conductivity flame-retardant acrylic resin coating 4.
Example 5
(1) Preparation of aminated boron nitride nanosheet component 5: adding a mixed solvent of distilled water and methanol into a reaction bottle, wherein the volume ratio of the distilled water to the mixed solvent of methanol is 2:1, adding boric acid and urea, the mass ratio of the boric acid to the urea is 1:28, stirring uniformly, freeze drying the solution to remove the solvent, placing the solid product in an atmosphere resistance furnace, introducing ammonia gas, heating at the rate of 5 ℃/min, calcining at 880 ℃ for 5h under heat preservation, washing the solid product with distilled water and ethanol, fully drying to obtain boron nitride nanosheets with layered structures, adding ethanol solvent, the boron nitride nanosheets and urea into a planetary ball mill at a mass ratio of 1:70, wherein the revolution speed of the planetary ball mill is 650rpm, the rotation speed of the planetary ball mill is 325rpm, carrying out ball milling for 30h, concentrating the solution under reduced pressure to remove the solvent, placing the solid product in a dialysis bag, adding distilled water to perform dialysis impurity removal process, and preparing to obtain the aminated boron nitride nanosheet component 5.
(2) Preparing a nano boron nitride modified graphene aerogel component 5: adding distilled water, an aminated boron nitride nanosheet component 5 and reduced graphene oxide into a reaction bottle, after uniform ultrasonic dispersion, adding cross-linking agents of glutaraldehyde and resorcinol in a mass ratio of 1:0.8:0.1:0.4, continuing ultrasonic dispersion treatment for 2 hours, placing the reaction bottle into a constant-temperature water bath kettle, heating to 60 ℃, stirring at a constant speed for reaction for 8 hours, and carrying out freeze drying on the solution to prepare the nano boron nitride modified graphene aerogel component 5.
(3) Preparing a modified nano boron nitride-graphene composite material 5: introducing nitrogen into a reaction bottle to discharge air, adding a mixed solvent of distilled water and ethanol, wherein the volume ratio of the distilled water to the ethanol is 1:8, adding a ground nano boron nitride modified graphene aerogel component 5, uniformly performing ultrasonic dispersion, adding a silane coupling agent N- (beta-aminoethyl) -gamma-aminopropyltrimethoxysilane, wherein the mass ratio of the silane coupling agent N- (beta-aminoethyl) -gamma-aminopropyltrimethoxysilane to the nano boron nitride modified graphene aerogel is 1:2, placing the mixture into a constant-temperature water bath, heating to 100 ℃, uniformly stirring for reaction for 20 hours, filtering the solution to remove the solvent, washing a solid product by using distilled water and ethanol, and fully drying to obtain the silane coupling agent grafted modified nano boron nitride-graphene composite material 5.
(4) Preparing a high-thermal-conductivity flame-retardant acrylic resin coating 5: adding distilled water solvent, 6 parts of modified nano boron nitride-graphene composite material 5, 35 parts of methacrylic acid, 15 parts of styrene and 25 parts of methyl acrylate into a reaction bottle, stirring uniformly, adding 12 parts of condensing agent 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride, placing the reaction bottle into a constant-temperature water bath kettle, heating to 70 ℃, stirring at a constant speed for reaction for 15 hours, adding 15 parts of styrene and 17 parts of initiator ammonium persulfate, heating to 90 ℃, stirring at a constant speed for reaction for 6 hours, adding ammonia water to adjust the pH of the solution to be neutral, and performing a high-speed emulsification process on the solution to prepare the high-thermal-conductivity flame-retardant acrylic resin coating 5.
The high-thermal-conductivity flame-retardant acrylic resin coating in the examples 1 to 5 is cured into a film, and the limit oxygen index and the flame retardant property of the film material are tested by using a 5801A full-automatic oxygen index tester, and the test standards GB/T2406.1-2008 and GB/T2406.2-2009 are adopted.
In summary, the high-thermal-conductivity flame-retardant acrylic resin coating takes distilled water and methanol as dispersion media, boric acid and urea as raw materials, boron nitride nanosheets with huge specific surface areas are prepared by a freeze-drying method and an ammonia atmosphere high-temperature nitridation method, then the urea is taken as an ammonia source and is subjected to ball-milling blending modification with the boron nitride nanosheets, the urea can promote stripping of the boron nitride nanosheets, boron nitride lamella is protected from being damaged in the high-speed ball-milling process, amino is modified into the lamella structure of the boron nitride nanosheets, glutaraldehyde and resorcinol are taken as cross-linking agents, amino in reduced graphene oxide is subjected to cross-linking reaction, the nano boron nitride modified graphene aerogel is prepared by the freeze-drying method, the boron nitride nanosheets are tightly combined with graphene through the bonding effect of chemical bonds, and the two are difficult to fall off and separate, compared with single-component boron nitride and graphene, the nano boron nitride modified graphene aerogel is higher in heat conductivity coefficient.
Silane coupling agent N- (beta-aminoethyl) -gamma-aminopropyltrimethoxysilane is used for reacting with hydroxyl in reduced graphene oxide to prepare modified nano boron nitride-graphene composite material grafted with N- (beta-aminoethyl) -gamma-aminopropyltrimethoxysilane, 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride is used as a condensing agent, amino in N- (beta-aminoethyl) -gamma-aminopropyltrimethoxysilane, methacrylic acid and carboxyl in methyl acrylate are subjected to condensation reaction, the boron nitride-graphene composite material is grafted to a matrix of acrylic resin through chemical bonds, and the dispersibility and compatibility of nano boron nitride and graphene with the acrylic resin are greatly improved, the heat-conducting property of the acrylic resin coating is obviously enhanced, the boron nitride and nanosheet-graphene aerogel material has a three-dimensional nano flaky structure, a flaky protective layer is formed in an acrylic resin matrix, when the acrylic resin coating burns, the three-dimensional flaky structure plays a role in uniformly transferring heat and reducing the phenomenon of heat concentration and aggregation, the three-dimensional flaky structure reduces the permeation of oxygen, and the acrylic coating is endowed with excellent flame retardant property under the synergistic effect.
Claims (8)
1. The high-thermal-conductivity flame-retardant acrylic resin coating comprises the following formula raw materials in parts by weight and components, and is characterized in that: 2-6 parts of modified nano boron nitride-graphene composite material, 8-12 parts of condensing agent, 22-35 parts of methacrylic acid, 8-15 parts of styrene, 25-50 parts of methyl acrylate and 10-17 parts of initiator.
2. The highly thermally conductive flame-retardant acrylic resin coating according to claim 1, wherein: the condensing agent is 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride.
3. The highly thermally conductive flame-retardant acrylic resin coating according to claim 1, wherein: the initiator is ammonium persulfate.
4. The highly thermally conductive flame-retardant acrylic resin coating according to claim 1, wherein: the preparation method of the modified nano boron nitride-graphene composite material comprises the following steps:
(1) adding boric acid and urea into a mixed solvent of distilled water and methanol with a volume ratio of 1-2:1, uniformly stirring, freeze-drying the solution to remove the solvent, placing the solid product in an atmosphere resistance furnace, introducing ammonia gas, heating at a rate of 2-5 ℃/min, carrying out heat preservation and calcination at 850-880 ℃ for 3-5h, washing the solid product and drying to obtain a boron nitride nanosheet with a layered structure, adding an ethanol solvent, the boron nitride nanosheet and urea into a planetary ball mill, carrying out ball milling at a revolution speed of 600-880 rpm and a rotation speed of 300-325rpm for 25-30h, placing the solid product after reduced pressure concentration in a dialysis bag, and carrying out a dialysis impurity removal process to obtain an aminated boron nitride nanosheet;
(2) Adding an aminated boron nitride nanosheet and reduced graphene oxide into distilled water, after uniform ultrasonic dispersion, adding cross-linking agents of glutaraldehyde and resorcinol, continuing ultrasonic dispersion treatment for 1-2h, heating the solution to 40-60 ℃, reacting for 5-8h, and preparing the nano boron nitride modified graphene aerogel from the solution by a freeze-drying method;
(3) introducing nitrogen into a reaction bottle to discharge air, adding a mixed solvent of distilled water and ethanol with a volume ratio of 1:5-8, and the ground nano boron nitride modified graphene aerogel, uniformly dispersing by using ultrasonic waves, adding a silane coupling agent, heating to 80-100 ℃, reacting for 15-20h, filtering, washing and drying to obtain the silane coupling agent grafted modified nano boron nitride-graphene composite material.
5. The highly thermally conductive flame-retardant acrylic resin coating according to claim 4, wherein: the mass ratio of the boric acid to the nitrogen source urea in the step (1) is 1:22-28, and the mass ratio of the boron nitride nanosheet to the amino source urea is 1: 55-70.
6. The highly thermally conductive flame-retardant acrylic resin coating according to claim 4, wherein: the mass ratio of the aminated boron nitride nanosheet, the reduced graphene oxide, the glutaraldehyde and the resorcinol in the step (2) is 1:0.4-0.8:0.06-0.1: 0.2-0.4.
7. The highly thermally conductive flame-retardant acrylic resin coating according to claim 4, wherein: the silane coupling agent in the step (3) is N- (beta-aminoethyl) -gamma-aminopropyltrimethoxysilane, and the mass ratio of the silane coupling agent to the nano boron nitride modified graphene aerogel is 1: 1.2-2.
8. The highly thermally conductive flame-retardant acrylic resin coating according to claim 1, wherein: the preparation method of the high-thermal-conductivity flame-retardant acrylic resin coating comprises the following steps:
(1) adding 2-6 parts of modified nano boron nitride-graphene composite material, 22-35 parts of methacrylic acid, 8-15 parts of styrene, 25-50 parts of methyl acrylate and 8-12 parts of condensing agent 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride into a distilled water solvent, heating to 40-70 ℃, reacting for 10-15h, adding 8-15 parts of styrene and 10-17 parts of initiator ammonium persulfate, heating to 75-90 ℃, reacting for 3-6h, adding ammonia water to adjust the pH value of the solution to be neutral, and performing a high-speed emulsification process on the solution to prepare the high-thermal-conductivity flame-retardant acrylic resin coating.
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