CN109252365B - Antistatic flame-retardant casein-based graphene composite fabric and preparation method thereof - Google Patents
Antistatic flame-retardant casein-based graphene composite fabric and preparation method thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 85
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 59
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 title claims abstract description 54
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- D06M13/50—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with organometallic compounds; with organic compounds containing boron, silicon, selenium or tellurium atoms
- D06M13/51—Compounds with at least one carbon-metal or carbon-boron, carbon-silicon, carbon-selenium, or carbon-tellurium bond
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- C01B32/00—Carbon; Compounds thereof
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Abstract
本发明具体涉及一种抗静电阻燃型酪素基石墨烯复合织物及其制备方法。首先，采用改进Hummers法制备氧化石墨烯（GO）,并配置GO溶液使其带负电荷；然后，通过己内酰胺改性酸溶解酪素，使其带正电荷；最后，采用层层自组装法在酪素基体中引入纳米粒子石墨烯来制备抗静电阻燃型酪素基GO复合织物，再用NaBH4进行还原，即得最终产物为抗静电阻燃型酪素基石墨烯复合织物。本发明制备的抗静电阻燃型酪素基石墨烯复合织物，提高了织物的抗静电性能和阻燃性能，且有望应用于皮革、食品、造纸等领域。
The invention specifically relates to an antistatic flame-retardant casein-based graphene composite fabric and a preparation method thereof. First, graphene oxide (GO) was prepared by the modified Hummers method, and the GO solution was configured to make it negatively charged; then, the casein was dissolved by caprolactam-modified acid to make it positively charged; finally, the layer-by-layer self-assembly method was used in the Nanoparticle graphene was introduced into the casein matrix to prepare an antistatic and flame-retardant casein-based GO composite fabric, which was then reduced with NaBH 4 to obtain the final product as an antistatic and flame-retardant casein-based graphene composite fabric. The antistatic and flame-retardant casein-based graphene composite fabric prepared by the invention improves the antistatic performance and flame-retardant performance of the fabric, and is expected to be applied to the fields of leather, food, papermaking and the like.
Description
Technical Field
The invention belongs to the technical field of composite materials, and particularly relates to an antistatic flame-retardant casein-based graphene composite fabric and a preparation method thereof.
Background
In recent years, environmental issues have been of concern. Casein is a pure natural protein, and is widely applied to the fields of leather, papermaking, textiles, medicine and the like due to good biodegradability, affinity, low cost and the synthesis of various derivatives from various reaction groups in a molecular chain. However, the functionality of casein as a coating still has some defects, such as poor antistatic performance and flame retardant performance, which limits the application range to a certain extent. Graphene is a carbon material with a two-dimensional honeycomb structure, has a unique single-atom layered structure and excellent mechanical and thermal properties, and draws great attention of researchers at home and abroad[1-3]. According to literature reports, the performances of the graphene are improved to a certain extent by introducing the graphene into different polymer matrixes. Such as good conductivity and hygroscopicity of graphene, can be usedA continuous water film is formed on the surface of the base material, thereby indirectly improving the surface conductivity[4-6]. Also, the graphene lamellar structure as a whole is dense and continuous, which can prevent oxygen from entering deep into the material. In addition, the graphene has very good heat conduction, and locally too high heat can be quickly conducted to the rest parts of the material, so that the heat can be well dispersed, and the fire is not easy to spread and diffuse to achieve the flame-retardant effect[7-9]. However, at present, introduction of graphene into a casein system and improvement of flame retardant performance and antistatic performance thereof have been reported. ([1]Lan Y,Liu H,Cao X H,et al.Electrically conductive thermoplastic polyurethane/polypropylene nanocomposites with selectively distributed grapheme [J].Polymer,2016,97:11-19.[2] Ding Y,Zhu J Q,Wang C H,et al.Multifunctional three-dimensional graphene nanoribbons composite sponge[J].Carbon,2016,104:133-140.[3] Han N R,Cho J W.Click coupled stitched graphene sheets and their polymer nanocomposites with enhanced photothermal and mechanical properties [J].Composites Part A:Applied Science & Manufacturing,2016,87:78-85.[4]Study of graphene/polymer conductive composite material in Liulin and Zhangdong [ J]Functional material 2014,45(S1):7-11 [5 ]] Wang T,Ge H,Zhang K.A novel core-shell silica@graphene straticulate structured antistatic anticorrosion composite coating[J].Journal of Alloys & Compounds,2018.[6]Preparation and modification of heroic graphene and application of graphene in antistatic coating [ D]University of eastern China, 2013.[7 ]]Application and action mechanism of Chennan, Zhonggui Ling, Zhanggufeng graphene in polymer flame-retardant material [ J]Application chemistry, 2018,35(03):307-] Bao C，Guo Y，Yuan B，et al． Functionalized Graphene Oxide for Fire Safety Applications of Polymers: A Combination of Condensed Phase Flame Retardant Strategies［J］． J Mater Chem，2012，22( 43) : 23057-23063．[9] Wei H，Zhu Z，Sun H，et al． Graphene and Poly ( ionic liquid) Modified Polyurethane Sponges with Enhanced Flame Retardant Properties［J］．J Appl Polym Sci，2017，134( 44) : 45477．）。
Disclosure of Invention
The invention aims to provide an antistatic flame-retardant casein-based graphene composite fabric and a preparation method thereof.
The technical scheme adopted by the invention is as follows:
the preparation method of the antistatic flame-retardant casein-based graphene composite fabric comprises the following steps:
the method comprises the following steps: preparing Graphene Oxide (GO) by an improved Hummers method:
adding 7.5-7.8 mL of concentrated sulfuric acid into a three-neck flask, slowly adding potassium persulfate and phosphorus pentoxide into the concentrated sulfuric acid at a mass ratio of (1: 1-1: 3) under vigorous stirring, and heating the mixture to 70-90 ℃; then, adding graphite into the mixed solution, stirring for 8-12 h, stopping heating, cooling to room temperature, washing the obtained product after the reaction is finished, standing and airing;
adding 20-30 ml of concentrated sulfuric acid into a three-neck flask, uniformly mixing pretreated graphite and sodium nitrate (the mass ratio of the graphite to the sodium nitrate is 1: 1-1: 3), and slowly adding the mixture into the concentrated sulfuric acid, wherein the reaction temperature of the system is kept at 3-4 ℃; slowly adding potassium permanganate (the mass ratio of graphite to potassium permanganate is 1: 1-1: 3), reacting for 30-50 min, heating to 30-50 ℃, and reacting for 2 h; then adding 30-50 mL of deionized water, heating to 80-90 ℃, and reacting for 10-20 min; finally, adding 100-150 mL of deionized water to terminate the reaction, adding 8-12 mL of hydrogen peroxide to change the system from brown to dark yellow, washing with HCl, and then washing, centrifuging and drying the reaction product;
step two: preparation of modified casein emulsion (CA):
2-6 g of casein is dissolved in 3-5 wt% of acidic aqueous solution and added into a three-neck flask, and then 150ml of distilled water is added, heated in a water bath and stirred; then, dropwise adding a modifier solution with the mass fraction of 25% at the speed of 1d/2s, and reacting at the temperature of 75 ℃ for 1 h;
step three: preparing an antistatic flame-retardant casein-based graphene composite fabric:
soaking cotton fabric in a KH550 (gamma-aminopropyltriethoxysilane) solution for 30min, cleaning and drying; then, soaking the cotton fabric into a negatively charged GO water solution (5-8 mg/mL) for 20min, cleaning and drying; then, soaking the cotton fabric in 3-5 wt% of positively charged casein dissolving solution for 20min, cleaning and drying; the process is an assembly cycle, and a GO/CA double molecular layer can be formed on the surface of the cotton fabric; repeating the assembly cycle to obtain (GO/CA)nCotton fabric samples;
will (GO/CA)nPlacing a cotton fabric sample into a three-neck flask, adding 300mL of distilled water, then dropwise adding 3-5 wt% of sodium carbonate solution, and adjusting the pH of a reaction system to 9-10; and adding a reducing agent into the three-neck flask, heating in a water bath, and washing and drying a product after the reaction is finished to obtain the RGO/CA composite fabric with different assembly layers.
In the first step, the drying temperature and the drying time are respectively 60 ℃ and 24 hours.
In the second step, the acidic aqueous solution is an acetic acid aqueous solution, a citric acid aqueous solution or a boric acid aqueous solution.
In the second step, the modifier solution is a caprolactam solution, a acrylonitrile monomer solution, an organic silicon solution or a polyurethane solution.
In the second step, the temperature of water bath heating and the reaction time are 65 ℃ and 2h respectively.
In the third step, the temperature of water bath heating and the reaction time are respectively 80 ℃ and 1h.
In the third step, the reducing agent is sodium borohydride (NaBH)4) The mass ratio of the reducing agent to the graphene oxide is 8: 1-6: 1.
The invention has the following advantages:
the invention provides an antistatic flame-retardant casein-based graphene composite fabric and a preparation method thereof. The method is simple to operate and complete in assembly, the casein serving as a raw material used in the experiment is a natural product, the cost is low, the product is easy to degrade, and the graphene has a layered two-dimensional structure and excellent performance. The casein-based graphene composite fabric prepared by the method disclosed by the invention shows both antistatic performance and flame retardant performance, so that the quality and grade of the coated fabric are improved, and the casein-based graphene composite fabric is expected to be applied to the fields of leather, food, papermaking and the like, so that the commercial value of the casein-based graphene composite fabric is increased; the obtained product has good stability, and lays a good foundation for realizing industrialization of the product.
Drawings
FIG. 1 is a preparation method (layer-by-layer self-assembly) mechanism diagram of the present invention
FIG. 2 shows the number of layers of different assemblies (RGO/CA) prepared according to the present inventionnComparative figure of appearance before and after burning of the composite fabric ((a: 0 layer b:5 layers c:10 layers) (a ': 0 layer b ': 5 layers c ': 10 layers)).
Detailed Description
The present invention will be described in detail with reference to specific embodiments.
The preparation method of the antistatic flame-retardant casein-based graphene composite fabric comprises the following steps:
the method comprises the following steps: preparing Graphene Oxide (GO) by an improved Hummers method:
adding 7.5-7.8 mL of concentrated sulfuric acid into a three-neck flask, slowly adding potassium persulfate and phosphorus pentoxide into the concentrated sulfuric acid at a mass ratio of (1: 1-1: 3) under vigorous stirring, and heating the mixture to 70-90 ℃; then, adding graphite into the mixed solution, stirring for 8-12 h, stopping heating, cooling to room temperature, washing the obtained product after the reaction is finished, standing and airing;
adding 20-30 ml of concentrated sulfuric acid into a three-neck flask, uniformly mixing pretreated graphite and sodium nitrate (the mass ratio of the graphite to the sodium nitrate is 1: 1-1: 3), and slowly adding the mixture into the concentrated sulfuric acid, wherein the reaction temperature of the system is kept at 3-4 ℃; slowly adding potassium permanganate (the mass ratio of graphite to potassium permanganate is 1: 1-1: 3), reacting for 30-50 min, heating to 30-50 ℃, and reacting for 2 h; then adding 30-50 mL of deionized water, heating to 80-90 ℃, and reacting for 10-20 min; finally, adding 100-150 mL of deionized water to terminate the reaction, adding 8-12 mL of hydrogen peroxide to change the system from brown to dark yellow, washing with HCl, and then washing, centrifuging and drying the reaction product;
step two: preparation of modified casein emulsion (CA):
2-6 g of casein is dissolved in 3-5 wt% of acidic aqueous solution and added into a three-neck flask, and then 150ml of distilled water is added, heated in a water bath and stirred; then, dropwise adding a modifier solution with the mass fraction of 25% at the speed of 1d/2s, and reacting at the temperature of 75 ℃ for 1 h;
step three: preparing an antistatic flame-retardant casein-based graphene composite fabric:
soaking cotton fabric in a KH550 (gamma-aminopropyltriethoxysilane) solution for 30min, cleaning and drying; then, soaking the cotton fabric into a negatively charged GO water solution (5-8 mg/mL) for 20min, cleaning and drying; then, soaking the cotton fabric in 3-5 wt% of positively charged casein dissolving solution for 20min, cleaning and drying; the process is an assembly cycle, and a GO/CA double molecular layer can be formed on the surface of the cotton fabric; repeating the assembly cycle to obtain (GO/CA)nCotton fabric samples;
will (GO/CA)nPlacing a cotton fabric sample into a three-neck flask, adding 300mL of distilled water, then dropwise adding 3-5 wt% of sodium carbonate solution, and adjusting the pH of a reaction system to 9-10; and adding a reducing agent into the three-neck flask, heating in a water bath, and washing and drying a product after the reaction is finished to obtain the RGO/CA composite fabric with different assembly layers.
In the first step, the drying temperature and the drying time are respectively 60 ℃ and 24 hours.
In the second step, the acidic aqueous solution is an acetic acid aqueous solution, a citric acid aqueous solution or a boric acid aqueous solution.
In the second step, the modifier solution is a caprolactam solution, a acrylonitrile monomer solution, an organic silicon solution or a polyurethane solution.
In the second step, the temperature of water bath heating and the reaction time are 65 ℃ and 2h respectively.
In the third step, the temperature of water bath heating and the reaction time are respectively 80 ℃ and 1h.
In the third step, the reducing agent is sodium borohydride, and the mass ratio of the reducing agent to the graphene oxide is 8: 1-6: 1.
Example 1
The method comprises the following steps: preparation of Graphene Oxide (GO) by improved Hummers method
Adding 7.5mL of concentrated sulfuric acid into a 100mL three-neck flask, slowly adding potassium persulfate and phosphorus pentoxide into the concentrated sulfuric acid at a mass ratio of 1:1 under strong stirring, adding the phosphorus pentoxide to cause heat release, and heating the mixture to 70 ℃; and then adding graphite, cleaning the graphite stained on the wall of the bottle by using 3-6 mL of concentrated sulfuric acid, stirring for 8 hours, stopping heating, cooling to room temperature, transferring to a 500mL beaker, adding 500mL of distilled water into the beaker, standing for 24 hours for waiting for precipitation, pouring out supernatant and suspension, adding 500mL of distilled water, stirring and standing, repeating for 4-5 times, performing suction filtration, cleaning to neutrality by using distilled water, standing for 1 hour at room temperature, and airing.
Adding 18ml of concentrated sulfuric acid into a three-neck flask, uniformly mixing pretreated graphite and sodium nitrate (the mass ratio is 1: 1), slowly adding the mixture into the concentrated sulfuric acid, and keeping the temperature of the system at 1 ℃; slowly adding potassium permanganate (the mass ratio of graphite to potassium permanganate is 1: 1) into the system, heating to 30 ℃ after 0.5h, and reacting for 2 h; then 30ml of deionized water is added, and the temperature is raised to 85 ℃ for reaction for 20 min; and finally, adding 100ml of deionized water to terminate the reaction, adding 10ml of hydrogen peroxide, washing with a small amount of 3% HCl by volume, washing the product with the deionized water for multiple times, centrifuging, and finally drying in an oven at 40 ℃ for 24 hours.
Step two: preparation of modified casein emulsion (CA):
2g of casein dissolved in a 3wt% aqueous acid solution was added to a three-necked flask, followed by 150ml of distilled water, and the system was kept stirred in a water bath at 65 ℃ for 2 hours; then dropwise adding 25% caprolactam solution at the speed of 1d/2s, and reacting for 1h at 75 ℃; (in the second step, the acidic aqueous solution is an acetic acid aqueous solution, a citric acid aqueous solution or a boric acid aqueous solution.)
Step three: preparing an antistatic flame-retardant casein-based graphene composite fabric:
soaking cotton fabric in a KH550 (amino functional group silane) solution for 30min, cleaning and drying, then soaking the cotton fabric in a 5mg/mL negatively charged GO aqueous solution for 20min, cleaning and drying; then soaking the cotton fabric in positively charged casein dissolving solution (mass fraction is 3%) for 20min, cleaning and drying; the process is an assembly cycle, and a GO/CA double molecular layer is formed on the surface of the cotton fabric; repeating the assembly cycle to obtain (GO/CA)nA fabric sample;
will (GO/CA)nPlacing a cotton fabric sample into a three-neck flask, adding 300mL of distilled water, then dropwise adding a 3wt% sodium carbonate solution, adjusting the pH of a reaction system to 9, and adding a reducing agent sodium borohydride (the mass ratio of the sodium borohydride to the graphene oxide is 8: 1); heating in water bath, washing and drying the product after the reaction is finished to obtain the product (RGO/CA) with different assembly layersnThe composite fabric is subjected to combustion experiments on fabrics with different assembly layers, and the flame retardance and the surface resistivity of the composite fabric are tested.
Example 2
The method comprises the following steps: preparation of Graphene Oxide (GO) by improved Hummers method
Adding 7.6mL of concentrated sulfuric acid into a three-neck flask, slowly adding potassium persulfate and phosphorus pentoxide into the concentrated sulfuric acid at a mass ratio of 1:2 under strong stirring, adding the phosphorus pentoxide to cause heat release, heating the mixture to 80 ℃, adding graphite into the three-neck flask, and cleaning the graphite stained on the wall of the flask by using 3-6 mL of concentrated sulfuric acid; stirring for 10h, stopping heating, cooling to room temperature, transferring to a 500mL beaker, adding 500mL distilled water, standing for 24h for precipitation, and pouring out the supernatant and the suspension; and adding 500mL of distilled water, stirring and standing, repeatedly washing for 4-5 times, performing suction filtration, washing to be neutral by using distilled water, standing for 2h at room temperature, and drying in the air.
Adding 25ml of concentrated sulfuric acid into a three-neck flask, uniformly mixing the pretreated graphite and sodium nitrate (the mass ratio is 3: 1), slowly adding the mixture into the concentrated sulfuric acid, and keeping the temperature of the system at 3 ℃; slowly adding potassium permanganate (the mass ratio of graphite to potassium permanganate is 1: 2) into the system, heating to 40 ℃ after half an hour, and reacting for 2 hours; and adding 10 ℃ and 40ml of deionized water, heating to 85 ℃ for reaction for 15min, adding 140ml of deionized water to stop the reaction, adding 8ml of hydrogen peroxide to change the system from tan to dark yellow, washing with a small amount of 5% HCl, washing the product with 500ml of deionized water for multiple times, centrifuging, and drying in an oven at 60 ℃ for 24 h.
Step two: preparation of modified Casein emulsion (CA)
4g of casein dissolved in a 4% acidic aqueous solution was added to a three-necked flask, followed by 150ml of distilled water, and the system was kept stirred in a water bath at 65 ℃ for 2 hours; then dropwise adding 25% caprolactam solution at the speed of 1d/2s, and reacting for 1h at 75 ℃; (in the second step, the acidic aqueous solution is an acetic acid aqueous solution, a citric acid aqueous solution or a boric acid aqueous solution.)
Step three: preparing an antistatic flame-retardant casein-based graphene (RGO) composite fabric.
Soaking cotton fabric in a KH550 (gamma-aminopropyltriethoxysilane) solution for 30min, cleaning, drying, soaking the cotton fabric in a negatively charged GO aqueous solution (6 mg/mL) for 20min, cleaning, and drying; then soaking the cotton fabric in positively charged casein dissolving solution (mass fraction is 4%) for 20min, cleaning and drying; the process is an assembly cycle, and a GO/CA double molecular layer is formed on the surface of the cotton fabric; repeating the assembly cycle to obtain (GO/CA)nA fabric sample;
will (GO/CA)nPlacing a cotton fabric sample into a three-neck flask, adding 300mL of distilled water, dropwise adding a 4wt% sodium carbonate solution, adjusting the pH value of a reaction system to 9, then adding a reducing agent sodium borohydride (the mass ratio of the sodium borohydride to the graphene oxide is 7: 1), heating in a water bath, washing and drying a product after the reaction is finished, and thus obtaining the (RGO/CA) with different assembly layersnThe composite fabric is subjected to combustion experiments on fabrics with different assembly layers, and the flame retardance and the surface resistivity of the composite fabric are tested.
Example 3
The method comprises the following steps: preparation of Graphene Oxide (GO) by improved Hummers method
7.6mL of concentrated sulfuric acid was charged in a 100mL three-necked flask, and potassium persulfate (K) was added2S2O8) And phosphorus pentoxide (P)2O5) Slowly adding the mixture into concentrated sulfuric acid with the mass ratio of 1:3 under strong stirring, adding P2O5 to generate heat, and heating the mixture to 90 ℃; then adding graphite into a three-neck flask, and cleaning the graphite stained on the wall of the flask by using 3-6 ml of concentrated sulfuric acid; stirring for 12h, stopping heating, cooling to room temperature, transferring to a 500mL beaker, adding 500mL distilled water, standing for 24h for waiting for precipitation, pouring out supernatant and suspension, adding 500mL distilled water, stirring, standing, repeating for 4-5 times, filtering, washing with distilled water to neutrality, standing at room temperature for 1h, and air drying. Taking 23ml of concentrated sulfuric acid, namely a three-neck flask, uniformly mixing pretreated graphite and sodium nitrate (the mass ratio of the graphite to the potassium permanganate is 2: 1), slowly adding the graphite and the sodium nitrate into the concentrated sulfuric acid, keeping the temperature of the system at 3-4 ℃, then slowly adding potassium permanganate (the mass ratio of the graphite to the potassium permanganate is 1: 3) into the system, heating to 35 ℃ after half an hour, reacting for 2 hours, adding 10 ℃ and 40ml of deionized water, heating to 85 ℃ for reaction for 15 minutes, finally adding 140ml of deionized water to stop the reaction, adding 10ml of hydrogen peroxide, changing the system from tan to dark yellow, washing with a small amount of 5% HCl, washing the product with 500ml of deionized water for multiple times, centrifuging, and drying in an oven at 60 ℃ for 24 hours.
Step two: preparation of modified Casein emulsion (CA)
6g of casein dissolved in a 5% acidic aqueous solution was added to a three-necked flask, followed by 150ml of distilled water, and the system was kept stirred in a water bath at 65 ℃ for 2 hours; then, 25% caprolactam solution was added dropwise at a rate of 1d/2s, and the mixture was reacted at 75 ℃ for 1 hour (in the second step, the acidic aqueous solution was an aqueous acetic acid solution, an aqueous citric acid solution or an aqueous boric acid solution.)
Step three: and preparing the antistatic flame-retardant casein-based graphene composite fabric.
Soaking cotton fabric in a KH550 (gamma-aminopropyltriethoxysilane) solution for 30min, cleaning, drying, soaking the cotton fabric in a negatively charged GO aqueous solution (8 mg/mL) for 20min, cleaning, and drying; then will beSoaking the cotton fabric in a casein dissolving solution (5% by mass) with positive charges of 5% for 20min, cleaning and drying; the process is an assembly cycle, and a GO/CA double molecular layer is formed on the surface of the cotton fabric; repeating the assembly cycle to obtain (GO/CA)nA fabric sample;
will (GO/CA)nPlacing a cotton fabric sample into a three-neck flask, adding 300mL of distilled water, then dropwise adding a 5wt% sodium carbonate solution, adjusting the pH of a reaction system to 10, and adding a reducing agent sodium borohydride (the mass ratio of the sodium borohydride to the graphene oxide is 6: 1); then heating in water bath, washing and drying the product after the reaction is finished, thus obtaining the (RGO/CA) with different assembly layersnThe composite fabric is subjected to combustion experiments on fabrics with different assembly layers, and the flame retardance and the surface resistivity of the composite fabric are tested.
The invention adopts a layer-by-layer self-assembly method to prepare antistatic flame-retardant casein-based graphene, carries out combustion experiments on composite fabrics with different assembly layers, tests the flame retardance and the surface resistivity of the composite fabrics to obtain the following conclusion, and is specifically explained by combining the accompanying drawings: as can be seen from fig. 1, the composite coating is prepared by a layer-by-layer self-assembly method, which is an assembly mechanism by combining positive and negative charges. From Table 1 for different number of layers of assembly (RGO/CA)nThe antistatic performance of the composite fabric is characterized in that the antistatic performance is judged by measuring the surface resistivity through a BEST-212 resistance tester (the antistatic performance is divided into 3 grades in total; the surface resistivity<10^7Is A grade, 10^ s7~10^10Is class B, 10^ s10~10^13The order of the C-level is C,>10^13no antistatic properties). As can be seen from Table 2, the surface resistivity of 1BL is 2.278X 10^ s10The surface resistivity of omega, 5BL is 8.679 x 10^ s9Surface resistivity of omega, 10BL 1.649 x 10^ s9Ω, reaching antistatic class B, leading to a conclusion: the anti-static flame-retardant casein-based RGO composite fiber coating can endow fabric with anti-static performance. As can be seen in FIG. 2, the RGO assembled fabric after combustion forms a continuous protective carbon layer that inhibits heat and mass transfer and improves the flame retardant properties of the fabric, from the different assembled layers of Table 2Numerical (RGO/CA)nThe flame-retardant performance test results of the composite fabric show that the oxygen concentration is gradually increased along with the increase of the number of the assembled layers, which indicates that the flame-retardant performance of the fabric is gradually enhanced. Referring to fig. 1, table 1, fig. 2 and table 2, it can be seen that the composite fabric prepared by the present invention is a fabric having both antistatic and flame retardant functions.
TABLE 1 different number of layers of assembly (RGO/CA)nCharacterization of antistatic Properties of composite fabrics
TABLE 2 different number of layers of assembly (RGO/CA)nFlame retardancy test results of composite fabrics
Note: 0BL is pure fiber fabric; 5BL is 5 layers of coated fiber fabric; 10BL is a fiber fabric coated with 10 layers.
The invention is not limited to the examples, and any equivalent changes to the technical solution of the invention by a person skilled in the art after reading the description of the invention are covered by the claims of the invention.
Claims (8)
1. The preparation method of the antistatic flame-retardant casein-based graphene composite fabric is characterized by comprising the following steps of:
the method comprises the following steps: preparing graphene oxide GO by an improved Hummers method:
adding 7.5-7.8 mL of concentrated sulfuric acid into a three-neck flask, slowly adding potassium persulfate and phosphorus pentoxide into the concentrated sulfuric acid at a mass ratio of 1: 1-1: 3 under vigorous stirring, and heating the mixture to 70-90 ℃; then, adding graphite into the mixed solution, stirring for 8-12 h, stopping heating, cooling to room temperature, washing the obtained product after the reaction is finished, standing and airing;
adding 20-30 ml of concentrated sulfuric acid into a three-neck flask, uniformly mixing pretreated graphite and sodium nitrate according to a mass ratio of 1: 1-1: 3, and slowly adding the mixture into the concentrated sulfuric acid, wherein the reaction temperature of the system is kept at 3-4 ℃; slowly adding potassium permanganate, wherein the mass ratio of graphite to potassium permanganate is 1: 1-1: 3, reacting for 30-50 min, heating to 30-50 ℃, and reacting for 2 h; then adding 30-50 mL of deionized water, heating to 80-90 ℃, and reacting for 10-20 min; finally, adding 100-150 mL of deionized water to terminate the reaction, adding 8-12 mL of hydrogen peroxide to change the system from brown to dark yellow, washing with HCl, and then washing, centrifuging and drying the reaction product;
step two: preparing modified casein emulsion CA:
2-6 g of casein is dissolved in 3-5 wt% of acidic aqueous solution and added into a three-neck flask, and then 150ml of distilled water is added, heated in a water bath and stirred; then, dropwise adding a modifier solution with the mass fraction of 25% at the speed of 1d/2s, and reacting at the temperature of 75 ℃ for 1 h;
step three: preparing an antistatic flame-retardant casein-based graphene composite fabric:
soaking the cotton fabric in a KH550 (gamma-aminopropyltriethoxysilane) solution for 30min, cleaning and drying, then soaking the cotton fabric in a negatively charged GO water solution with the concentration of 5-8 mg/mL for 20min, cleaning and drying; then, soaking the cotton fabric in 3-5 wt% of positively charged casein dissolving solution for 20min, cleaning and drying; the process is an assembly cycle, and a GO/CA double molecular layer can be formed on the surface of the cotton fabric; repeating the assembly cycle to obtain (GO/CA)nCotton fabric samples;
will (GO/CA)nPlacing a cotton fabric sample into a three-neck flask, adding 300mL of distilled water, then dropwise adding 3-5 wt% of sodium carbonate solution, and adjusting the pH of a reaction system to 9-10; adding a reducing agent into the three-neck flask, heating in water bath, washing and drying the product after the reaction is finished, and obtaining the (RGO/CA) with different assembly layersnA composite fabric.
2. The preparation method of the antistatic flame-retardant casein-based graphene composite fabric according to claim 1, characterized in that:
in the first step, the drying temperature and the drying time are respectively 60 ℃ and 24 hours.
3. The preparation method of the antistatic flame-retardant casein-based graphene composite fabric according to claim 1, characterized in that:
in the second step, the acidic aqueous solution is an acetic acid aqueous solution, a citric acid aqueous solution or a boric acid aqueous solution.
4. The method for preparing an antistatic flame-retardant casein-based graphene composite fabric according to claim 1,
in the second step, the modifier solution is a caprolactam solution, a acrylonitrile monomer solution, an organic silicon solution or a polyurethane solution.
5. The method for preparing an antistatic flame-retardant casein-based graphene composite fabric according to claim 1,
in the second step, the temperature of water bath heating and the reaction time are 65 ℃ and 2h respectively.
6. The preparation method of the antistatic flame-retardant casein-based graphene composite fabric according to claim 1, characterized in that:
in the third step, the temperature of water bath heating and the reaction time are respectively 80 ℃ and 1h.
7. The preparation method of the antistatic flame-retardant casein-based graphene composite fabric according to claim 1, characterized in that:
in the third step, the reducing agent is sodium borohydride, and the mass ratio of the reducing agent to the graphene oxide is 8: 1-6: 1.
8. The antistatic flame-retardant casein-based graphene composite fabric prepared by the preparation method according to claim 1.
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