CN111763405B - Preparation method of nano-silica-modified graphene oxide/epoxy resin composite material - Google Patents
Preparation method of nano-silica-modified graphene oxide/epoxy resin composite material Download PDFInfo
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Abstract
A preparation method of a nano-silica modified graphene oxide/epoxy resin composite material relates to a preparation method of an epoxy resin composite material. The invention aims to solve the problems of poor mechanical property of epoxy resin and reduced strength performance of epoxy resin composite materials caused by filler reinforced epoxy resin. The method comprises the following steps: 1. silanization of nano silicon dioxide; 2. nano silicon dioxide grafted hyperbranched polymer; 3. preparing a graphene oxide-nano silicon dioxide hybrid material; 4. and (4) compounding. According to the invention, the problem of weak interface strength between graphene oxide and epoxy resin can be solved, and by contrast, the graphene oxide-nano silicon dioxide hybrid material has a better enhancement effect than pure graphene oxide or nano silicon dioxide. The method is suitable for surface modification of graphene oxide and preparation and application of the epoxy resin composite material.
Description
Technical Field
The invention relates to a preparation method of an epoxy resin composite material.
Background
Epoxy resin has been widely used in civil and military fields as a versatile material. However, epoxy resins are inherently brittle due to high crosslink density after curing. Epoxy resins used in engineering applications are generally limited by their brittleness and poor electrical and thermal properties. Furthermore, the lack of toughness is a major cause of hindering the widespread use of epoxy resins in various applications. Accordingly, the work of toughening epoxy resins has been a focus of research and has attracted the research interest of many scholars. Generally, the most common method of enhancing mechanical properties is to add a filler to the epoxy resin. When the epoxy resin acts as a matrix, the filler acts as a toughening phase to toughen the epoxy resin. In recent years, many different fillers have been investigated as second phases, which in many studies include graphene, carbon nanotubes, fibers, clays, rubbers or thermoplastic polymers. Most of these fillers are effective at toughening epoxy resins, but also result in a decrease in the strength properties of the epoxy resin composite.
Disclosure of Invention
The invention aims to solve the problems of poor mechanical property of epoxy resin and reduced strength property of an epoxy resin composite material caused by filler reinforced epoxy resin, and provides a preparation method of a nano silicon dioxide modified graphene oxide/epoxy resin composite material.
A preparation method of a nano-silica modified graphene oxide/epoxy resin composite material comprises the following steps:
1. silanization of nano silicon dioxide:
(1) dispersing the nano silicon dioxide in a mixed solution of absolute ethyl alcohol and water, and then carrying out ultrasonic treatment to obtain a nano silicon dioxide dispersion solution;
(2) adding a silane coupling agent into the nano silicon dioxide dispersion liquid, and stirring and refluxing for 6-8 h at the constant temperature of 70-80 ℃ to obtain a reaction liquid I;
(3) firstly, washing reaction liquid I, and then drying in vacuum to obtain silane functionalized nano silicon dioxide;
2. nano silicon dioxide grafted hyperbranched polymer:
(1) dispersing silane functionalized nano silicon dioxide in a mixed solution of methanol and water, and then carrying out ultrasonic treatment to obtain a silane functionalized nano silicon dioxide dispersion solution;
(2) adding N, N' -methylene bisacrylamide into the silane-functionalized nano silicon dioxide dispersion liquid, and stirring and refluxing for 18-24 h at the constant temperature of 40-50 ℃ to obtain a reaction liquid II;
(3) adding diethylenetriamine into the reaction liquid II, and stirring and refluxing for 18-24 h at the constant temperature of 40-50 ℃ to obtain reaction liquid III;
(4) firstly, washing reaction liquid III, and then drying in vacuum to obtain hyperbranched polymer grafted nano silicon dioxide;
3. preparing a graphene oxide-nano silicon dioxide hybrid material:
(1) dispersing graphene oxide and hyperbranched polymer grafted nano silicon dioxide in N, N-dimethylformamide, and then carrying out ultrasonic treatment to obtain a mixture I;
(2) adding an initiator into the mixture I, and stirring and refluxing for 4-6 h at the constant temperature of 70-80 ℃ to obtain a reaction solution IV;
(3) firstly, washing the reaction solution IV for 3-4 times by using N, N-dimethylformamide, and then drying in vacuum to obtain a graphene oxide-nano silicon dioxide hybrid material;
4. compounding:
(1) adding the graphene oxide-nano silicon dioxide hybrid material into acetone, and performing ultrasonic treatment to obtain a graphene oxide-nano silicon dioxide hybrid material solution;
(2) adding epoxy resin into the graphene oxide-nano silicon dioxide hybrid material solution, then carrying out ultrasonic treatment, and drying to obtain an epoxy resin mixture;
(3) adding a curing agent into the epoxy resin mixture, mechanically stirring, and drying to obtain an epoxy resin mixture;
(4) and pouring the epoxy resin mixture into a preheating mould with the temperature of 80-90 ℃ in a vacuum drying oven with the temperature of 80-90 ℃ and the vacuum degree of-30 KPa-35 KPa for curing, and finishing curing to obtain the nano silicon dioxide modified graphene oxide/epoxy resin composite material.
The principle of the invention is as follows:
the invention adopts amidation reaction of carboxyl and amino to successfully graft nano silicon dioxide into a graphene oxide lamella. Firstly, carrying out silane functionalization on nano silicon dioxide, then grafting hyperbranched polymer, and finally carrying out amidation reaction under the action of a condensing agent to obtain the graphene oxide-nano silicon dioxide hybrid material.
The invention has the advantages that:
1. the invention can solve the problem of poor dispersibility of graphene in the epoxy resin matrix, and the nano silicon dioxide on the surface of the oxidized graphene can inhibit reaggregation, thereby improving the dispersibility in the epoxy resin matrix. Due to the existence of the hyperbranched polymer of the amino terminal group on the graphene oxide-nano silicon dioxide hybrid material, a large number of covalent bonds can be generated with the epoxy resin, so that the interlocking effect and the interface adhesive force of the graphene oxide-nano silicon dioxide hybrid material with the epoxy resin are enhanced. In addition, the nano silicon dioxide adhered to the surface of the graphene oxide makes the surface of the graphene oxide rough, and makes crack paths more tortuous when cracks occur, so that the synergistic toughening effect is exerted, and the mechanical property of the composite material is improved;
2. according to the graphene oxide-nano silicon dioxide/epoxy resin composite material, the problem of weak interface strength between graphene oxide and epoxy resin can be solved, through comparison, the graphene oxide-nano silicon dioxide hybrid material has a better reinforcing effect than pure graphene oxide or nano silicon dioxide, and compared with a graphene oxide/epoxy resin composite material containing 0.1wt%, the tensile strength, bending strength and impact strength of the graphene oxide-nano silicon dioxide/epoxy resin composite material prepared by the method can be respectively improved by 37.81%,42.09% and 86.86% compared with pure epoxy resin.
The method is suitable for surface modification of graphene oxide and preparation and application of the epoxy resin composite material.
Drawings
FIG. 1 is an infrared spectrum; in the figure, a is nano-silica, b is silane functionalized nano-silica prepared in the first step of the example, c is hyperbranched polymer grafted nano-silica prepared in the second step of the example, d is graphene oxide prepared in the first step of the example, and e is graphene oxide-nano-silica hybrid material prepared in the third step of the example;
FIG. 2 is an XRD spectrum; in the figure, a is graphene oxide prepared in the first step of the example, b is nano-silica, c is silane-functionalized nano-silica prepared in the first step of the example, d is hyperbranched polymer-grafted nano-silica prepared in the second step of the example, and e is graphene oxide-nano-silica hybrid material prepared in the third step of the example;
FIG. 3 is an XPS peak spectrum of graphene oxide prepared in the first example;
FIG. 4 is an XPS peak spectrum of a graphene oxide-nano silica hybrid material prepared in the third step of the example;
fig. 5 is a TEM image of graphene oxide prepared in example one;
FIG. 6 is a TEM image of a graphene oxide-nano-silica hybrid material prepared in the third step of the example;
FIG. 7 is a thermogram; in the figure, a is nano-silica, b is silane-functionalized nano-silica prepared in the first step of the example, c is hyperbranched polymer-grafted nano-silica prepared in the second step of the example, d is graphene oxide-nano-silica hybrid material prepared in the third step of the example, and e is graphene oxide prepared in the first step of the example;
FIG. 8 is a graph comparing tensile strength, in FIG. 8 EP is pure epoxy resin, GO/EP is graphene oxide/epoxy resin composite material prepared in comparative example 1, siO 2/ EP is a nanosilica/epoxy composite prepared in comparative example 2, GO-SiO 2/ EP is the nano-silica modified graphene oxide/epoxy composite prepared in example one;
FIG. 9 is a graph comparing flexural strength, in FIG. 9 EP is pure epoxy resin, GO/EP is graphene oxide/epoxy resin composite material prepared in comparative example 1, siO 2/ EP Nano-silica/epoxy composite, GO-SiO, prepared in comparative example 2 2/ EP is the nano-silica modified graphene oxide/epoxy composite prepared in example one;
FIG. 10 is a graph comparing impact strength, and EP in FIG. 10 is a pure ringOxygen resin, GO/EP graphene oxide/epoxy composite, siO prepared in comparative example 1 2/ EP Nano-silica/epoxy composite, GO-SiO, prepared in comparative example 2 2/ EP is the nano-silica modified graphene oxide/epoxy composite prepared in example one.
Detailed Description
The first specific implementation way is as follows: the preparation method of the nano-silica modified graphene oxide/epoxy resin composite material is completed according to the following steps:
1. silanization of nano-silica:
(1) dispersing the nano silicon dioxide in a mixed solution of absolute ethyl alcohol and water, and then carrying out ultrasonic treatment to obtain a nano silicon dioxide dispersion solution;
(2) adding a silane coupling agent into the nano silicon dioxide dispersion liquid, and stirring and refluxing for 6-8 h at the constant temperature of 70-80 ℃ to obtain a reaction liquid I;
(3) firstly, washing reaction liquid I, and then drying in vacuum to obtain silane functionalized nano silicon dioxide;
2. nano silicon dioxide grafted hyperbranched polymer:
(1) dispersing the silane functionalized nano silicon dioxide in a mixed solution of methanol and water, and then performing ultrasonic treatment to obtain a silane functionalized nano silicon dioxide dispersion solution;
(2) adding N, N' -methylene bisacrylamide to the silane-functionalized nano-silica dispersion liquid, and stirring and refluxing for 18-24 hours at the constant temperature of 40-50 ℃ to obtain a reaction liquid II;
(3) adding diethylenetriamine into the reaction liquid II, and stirring and refluxing for 18-24 h at the constant temperature of 40-50 ℃ to obtain reaction liquid III;
(4) firstly, washing reaction liquid III, and then drying in vacuum to obtain hyperbranched polymer grafted nano silicon dioxide;
3. preparing a graphene oxide-nano silicon dioxide hybrid material:
(1) dispersing the graphene oxide and the hyperbranched polymer grafted nano silicon dioxide in N, N-dimethylformamide, and then carrying out ultrasonic treatment to obtain a mixture I;
(2) adding an initiator into the mixture I, and stirring and refluxing for 4-6 h at a constant temperature of 70-80 ℃ to obtain a reaction solution IV;
(3) firstly, washing the reaction solution IV for 3-4 times by using N, N-dimethylformamide, and then drying in vacuum to obtain a graphene oxide-nano silicon dioxide hybrid material;
4. compounding:
(1) adding the graphene oxide-nano silicon dioxide hybrid material into acetone, and performing ultrasonic treatment to obtain a graphene oxide-nano silicon dioxide hybrid material solution;
(2) adding epoxy resin into the graphene oxide-nano silicon dioxide hybrid material solution, then carrying out ultrasonic treatment, and drying to obtain an epoxy resin mixture;
(3) adding a curing agent into the epoxy resin mixture, mechanically stirring, and drying to obtain an epoxy resin mixture;
(4) and pouring the epoxy resin mixture into a preheating mould with the temperature of 80-90 ℃ in a vacuum drying oven with the temperature of 80-90 ℃ and the vacuum degree of-30 KPa-35 KPa for curing, and finishing curing to obtain the nano silicon dioxide modified graphene oxide/epoxy resin composite material.
The advantages of this embodiment:
1. the embodiment can solve the problem that graphene is poor in dispersibility in an epoxy resin matrix, and the nano silicon dioxide on the surface of the oxidized graphene can inhibit reaggregation, so that the dispersibility in the epoxy resin matrix is improved. Due to the existence of the hyperbranched polymer with the amino end group on the graphene oxide-nano silicon dioxide hybrid material, a large number of covalent bonds can be generated with the epoxy resin, so that the interlocking effect and the interface adhesive force with the epoxy resin are enhanced. In addition, the nano silicon dioxide adhered to the surface of the graphene oxide makes the surface of the graphene oxide rough, and makes crack paths more tortuous when cracks occur, so that the synergistic toughening effect is exerted, and the mechanical property of the composite material is improved;
2. the embodiment can solve the problem of weak interface strength between graphene oxide and epoxy resin, and by contrast, the graphene oxide-nano silicon dioxide hybrid material has a better reinforcing effect than pure graphene oxide or nano silicon dioxide, and compared with the graphene oxide/epoxy resin composite material containing 0.1wt%, the tensile strength, bending strength and impact strength of the graphene oxide-nano silicon dioxide/epoxy resin composite material prepared by the embodiment can be respectively improved by 37.81%,42.09% and 86.86% compared with pure epoxy resin.
The method is suitable for surface modification of graphene oxide and preparation and application of the epoxy resin composite material.
The second embodiment is as follows: the present embodiment differs from the present embodiment in that: the ultrasonic power in the step one (1) is 180W-200W, and the ultrasonic time is 30 min-60 min; the volume ratio of the mass of the nano silicon dioxide to the mixed solution of the absolute ethyl alcohol and the water in the step one (1) is (1 g-2 g): 100 mL-200 mL; the volume ratio of the absolute ethyl alcohol to the water in the mixed liquid of the absolute ethyl alcohol and the water in the step one (1) is (90-180) to (10-20). Other steps are the same as in the first embodiment.
The third concrete implementation mode: the difference between this embodiment and the first or second embodiment is: the silane coupling agent in the step one (2) is 3-aminopropyltriethoxysilane; the mass ratio of the silane coupling agent in the step one (2) to the nano silicon dioxide in the nano silicon dioxide dispersion liquid is (2-4) to (1-2). The other steps are the same as in the first or second embodiment.
The fourth concrete implementation mode: the difference between this embodiment and one of the first to third embodiments is as follows: in the step one (3), firstly, absolute ethyl alcohol is used for washing the reaction solution I for 3 to 4 times, then distilled water is used for washing for 3 to 4 times, and finally, the reaction solution is placed into a vacuum drying oven with the temperature of 80 to 90 ℃ for drying for 8 to 12 hours to obtain the silane functionalized nano silicon dioxide. The other steps are the same as those in the first to third embodiments.
The fifth concrete implementation mode is as follows: the difference between this embodiment and the first to the fourth embodiments is: the volume ratio of the methanol to the water in the mixed solution of the methanol and the water in the step two (1) is (100-200) to (50-100); the volume ratio of the mass of the silane functionalized nano silicon dioxide to the mixed solution of the methanol and the water in the step two (1) is (0.5 g-1 g): 100 mL-200 mL; the ultrasonic power in the step two (1) is 180W-200W, and the ultrasonic time is 30 min-60 min. The other steps are the same as those in the first to fourth embodiments.
The sixth specific implementation mode is as follows: the difference between this embodiment and one of the first to fifth embodiments is as follows: the mass ratio of the N, N' -methylene bisacrylamide in the step two (2) to the silane functionalized nano-silica in the silane functionalized nano-silica dispersion liquid is (0.5-1 g) to (0.5-1); the mass ratio of the diethylenetriamine in the step two (3) to the silane-functionalized nano-silica in the silane-functionalized nano-silica dispersion liquid in the step two (2) is (0.5-1 g) to (0.5-1); in the second step (4), the reaction solution III is washed by methanol for 3 to 4 times, then washed by distilled water for 3 to 4 times, and finally dried in a vacuum drying oven at the temperature of 80 to 90 ℃ for 8 to 12 hours to obtain the hyperbranched polymer grafted nano-silicon dioxide. The other steps are the same as those in the first to fifth embodiments.
The seventh embodiment: the difference between this embodiment and one of the first to sixth embodiments is: the ultrasonic power in the step three (1) is 180W-200W, and the ultrasonic time is 1 h-2 h; the mass ratio of the graphene oxide to the hyperbranched polymer grafted nano silicon dioxide in the step three (1) is 1; the volume ratio of the mass of the graphene oxide to the volume of the N, N-dimethylformamide in the step three (1) is (0.05-0.2 g): 50-200 mL; the initiator in the step three (2) is N-hydroxy-7-azobenzotriazole; the mass ratio of the initiator in the third step (2) to the graphene oxide in the third step (1) is 0.2; and the vacuum drying temperature in the step three (3) is 80-100 ℃, and the vacuum drying time is 8-12 h. The other steps are the same as those in the first to sixth embodiments.
The specific implementation mode is eight: the difference between this embodiment and one of the first to seventh embodiments is: the preparation method of the graphene oxide in the third step (1) is completed according to the following steps:
(1) adding graphite, sodium nitrate and concentrated sulfuric acid into a three-neck flask, placing the three-neck flask into an ice water bath at the temperature of 0-5 ℃, and stirring and reacting for 30-40 min at the stirring speed of 300-400 r/min to obtain a reaction solution I;
the mass fraction of the concentrated sulfuric acid in the step (1) is 96-98%;
the volume ratio of the mass of the graphite to the volume of the concentrated sulfuric acid in the step (1) is (6 g-8 g): 360 mL-500 mL;
the volume ratio of the mass of the sodium nitrate to the volume of the concentrated sulfuric acid in the step (1) is (2 g-4 g): 360 mL-500 mL;
(2) adding potassium permanganate into the reaction liquid I, placing the three-neck flask in ice-water bath at 0-5 ℃, and stirring and reacting for 2-3 hours at the stirring speed of 300-400 r/min to obtain reaction liquid II;
the mass ratio of the potassium permanganate in the step (2) to the graphite in the step (1) is (20 g-25 g) - (6 g-8 g);
(3) heating the temperature of the reaction liquid II to 35-40 ℃, reacting for 17-19 h at the temperature of 35-40 ℃, and adding distilled water to obtain a reaction liquid III;
the mass ratio of the volume of the distilled water in the step (3) to the graphite in the step (1) is (400-600 mL) to (6-8 g);
(4) stirring the reaction solution III at the stirring speed of 300-400 r/min for reaction for 1-2 h, and then adding distilled water and 30% by mass of hydrogen peroxide to obtain a reaction solution IV;
the mass ratio of the volume of the distilled water in the step (4) to the graphite in the step one (1) is (600 mL-800 mL): 6 g-8 g;
the mass ratio of the volume of the hydrogen peroxide with the mass fraction of 30% in the step (4) to the mass of the graphite in the step (1) is (40 mL-60 mL): 6 g-8 g;
(5) stirring and reacting the reaction solution IV for 20-40 min at the stirring speed of 300-400 r/min, then carrying out ultrasonic treatment for 30-50 min at the ultrasonic power of 180-200W, standing for 6-8 h, and pouring out the supernatant to obtain a mixture I;
(6) taking a hydrogen chloride solution with the mass fraction of 14% -16% as a cleaning agent, cleaning the mixture I at a centrifugal speed of 6000-8000 r/min until no sediment is generated when the barium chloride solution with the mass fraction of 0.1-0.15 mol/L is added into the supernatant of the mixture I, and obtaining a mixture I after the hydrogen chloride solution is cleaned;
(7) cleaning the mixture I cleaned by the hydrogen chloride solution by using deionized water until the pH value of the cleaning solution is 7 to obtain the mixture I cleaned by the deionized water;
(8) putting the mixture I cleaned by the deionized water into a freeze dryer, drying to obtain a solid I, and finally grinding the solid I and sieving by using a 300-mesh sieve to obtain undersize, namely graphene oxide;
and (8) putting the mixture I cleaned by the deionized water into a freeze dryer, and freeze-drying for 24-36 h at the temperature of-10-5 ℃. The other steps are the same as those in the first to seventh embodiments.
The specific implementation method nine: the difference between this embodiment and the first to eighth embodiments is: the ultrasonic power in the step four (1) is 180W-200W, and the ultrasonic time is 30 min-60 min; the mass ratio of the graphene oxide-nano silicon dioxide hybrid material in the step four (1) to the volume ratio of acetone is (0.033 g-0.036 g) to (10 mL-15 mL); the ultrasonic power in the step four (2) is 180W-200W, and the ultrasonic time is 30 min-60 min; the drying process in the fourth step (2) comprises the following steps: drying for 10-12 h in a vacuum drying oven with the temperature of 80 ℃ and the vacuum degree of-30 KPa to-35 KPa; the mass ratio of the epoxy resin in the step four (2) to the graphene oxide-nano silicon dioxide hybrid material in the graphene oxide-nano silicon dioxide hybrid material solution is (33 g-36 g) to (0.033 g-0.036 g). The other steps are the same as those in the first to eighth embodiments.
The detailed implementation mode is ten: the difference between this embodiment and the first to ninth embodiments is: the epoxy resin in the step four (2) is E-51; the curing agent in the fourth step (3) is H-256; the mechanical stirring speed in the step four (3) is 3000r/min, and the stirring time is 15-20 min; the drying process in the fourth step (3) comprises the following steps: drying for 1-1.5 h in a vacuum drying oven with the temperature of 80-90 ℃ and the vacuum degree of-30 KPa-35 KPa; the mass ratio of the curing agent in the step four (3) to the epoxy resin in the step four (2) is 32; the curing process in the fourth step (4) comprises the following steps: under the condition that the vacuum degree is-30 KPa to-35 KPa, firstly curing for 2 hours at 80-90 ℃, then curing for 2 hours at 100-120 ℃, and finally curing for 3-4 hours at 150 ℃. The other steps are the same as those in the first to ninth embodiments.
The following examples were employed to demonstrate the beneficial effects of the present invention:
the first embodiment is as follows: nano-silica-modified graphene oxide/epoxy resin composite material (GO-SiO) 2/ EP) is prepared according to the following steps:
1. silanization of nano-silica:
(1) dispersing the nano silicon dioxide in a mixed solution of absolute ethyl alcohol and water, and then carrying out ultrasonic treatment to obtain a nano silicon dioxide dispersion solution;
the ultrasonic power in the step one (1) is 180W, and the ultrasonic time is 30min;
the volume ratio of the mass of the nano silicon dioxide in the step one (1) to the mixed solution of absolute ethyl alcohol and water is 1g;
the volume ratio of the absolute ethyl alcohol to the water in the mixed solution of the absolute ethyl alcohol and the water in the first step (1) is 90;
(2) adding a silane coupling agent into the nano silicon dioxide dispersion liquid, and stirring and refluxing for 6 hours at a constant temperature of 70 ℃ to obtain a reaction liquid I;
the silane coupling agent in the step one (2) is 3-aminopropyltriethoxysilane;
the mass ratio of the silane coupling agent in the step one (2) to the nano silicon dioxide in the nano silicon dioxide dispersion liquid is 2;
(3) firstly, washing the reaction solution I, and then drying in vacuum to obtain silane functionalized nano silicon dioxide;
in the first step (3), firstly, washing the reaction solution I for 3 times by using absolute ethyl alcohol, then washing the reaction solution I for 3 times by using distilled water, and finally, putting the reaction solution I into a vacuum drying oven with the temperature of 80 ℃ for drying for 8 hours to obtain silane functionalized nano silicon dioxide;
2. nano silicon dioxide grafted hyperbranched polymer:
(1) dispersing silane functionalized nano silicon dioxide in a mixed solution of methanol and water, and then carrying out ultrasonic treatment to obtain a silane functionalized nano silicon dioxide dispersion solution;
the volume ratio of methanol to water in the mixed solution of methanol and water in the step two (1) is 100;
the volume ratio of the mass of the silane functionalized nano silicon dioxide to the mixed solution of methanol and water in the step two (1) is 0.5g;
the ultrasonic power in the step two (1) is 180W, and the ultrasonic time is 30min;
(2) adding N, N' -methylene bisacrylamide into the silane-functionalized nano-silica dispersion liquid, and stirring and refluxing for 18 hours at constant temperature of 40 ℃ to obtain reaction liquid II;
the mass ratio of the N, N' -methylene bisacrylamide in the step two (2) to the silane-functionalized nano-silica in the silane-functionalized nano-silica dispersion is 1;
(3) adding diethylenetriamine into the reaction liquid II, and stirring and refluxing for 18h at the constant temperature of 40 ℃ to obtain a reaction liquid III;
the mass ratio of the diethylenetriamine in the step two (3) to the silane-functionalized nano-silica in the silane-functionalized nano-silica dispersion liquid in the step two (2) is 1;
(4) firstly, washing the reaction solution III, and then drying in vacuum to obtain hyperbranched polymer grafted nano silicon dioxide;
in the second step (4), firstly, washing the reaction solution III for 3 times by using methanol, then washing the reaction solution III for 3 times by using distilled water, and finally, drying the reaction solution III for 8 hours in a vacuum drying oven at the temperature of 80 ℃ to obtain hyperbranched polymer grafted nano silicon dioxide;
3. preparing a graphene oxide-nano silicon dioxide hybrid material:
(1) dispersing the graphene oxide and the hyperbranched polymer grafted nano silicon dioxide in N, N-dimethylformamide, and then carrying out ultrasonic treatment to obtain a mixture I;
the ultrasonic power in the step three (1) is 180W, and the ultrasonic time is 1h;
the mass ratio of the graphene oxide to the hyperbranched polymer grafted nano silicon dioxide in the step three (1) is 1;
the volume ratio of the mass of the graphene oxide to the volume of the N, N-dimethylformamide in the step three (1) is 0.05g;
(2) adding an initiator into the mixture I, and stirring and refluxing for 4 hours at a constant temperature of 70 ℃ to obtain a reaction solution IV;
the initiator in the step three (2) is N-hydroxy-7-azobenzotriazole;
the mass ratio of the initiator in the step three (2) to the graphene oxide in the step three (1) is 0.2;
(3) firstly, washing the reaction solution IV for 3 times by using N, N-dimethylformamide, and then drying in vacuum to obtain a graphene oxide-nano silicon dioxide hybrid material;
the vacuum drying temperature in the step three (3) is 80 ℃, and the vacuum drying time is 8 hours;
4. compounding:
(1) adding the graphene oxide-nano silicon dioxide hybrid material into acetone, and performing ultrasonic treatment to obtain a graphene oxide-nano silicon dioxide hybrid material solution;
the ultrasonic power in the step four (1) is 180W, and the ultrasonic time is 30min;
the volume ratio of the mass of the graphene oxide-nano silicon dioxide hybrid material to the volume of acetone in the step four (1) is 0.033g;
(2) adding epoxy resin into the graphene oxide-nano silicon dioxide hybrid material solution, then carrying out ultrasonic treatment, and drying to obtain an epoxy resin mixture;
the epoxy resin in the step four (2) is E-51;
the ultrasonic power in the step four (2) is 180W, and the ultrasonic time is 30min;
the drying process in the step four (2) comprises the following steps: drying in a vacuum drying oven with the temperature of 80 ℃ and the vacuum degree of-30 KPa for 10 hours;
the mass ratio of the epoxy resin in the step four (2) to the graphene oxide-nano silicon dioxide hybrid material in the graphene oxide-nano silicon dioxide hybrid material solution is 33g;
(3) adding a curing agent into the epoxy resin mixture, mechanically stirring, and drying to obtain an epoxy resin mixture;
the curing agent in the fourth step (3) is H-256;
the mass ratio of the curing agent in the step four (3) to the epoxy resin in the step four (2) is 32:100;
the mechanical stirring speed in the step four (3) is 3000r/min, and the stirring time is 15min; the drying process in the fourth step (3) comprises the following steps: drying for 1h in a vacuum drying oven with the temperature of 80 ℃ and the vacuum degree of-30 KPa;
(4) pouring the epoxy resin mixture into a preheating mould with the temperature of 80 ℃ in a vacuum drying oven with the temperature of 80 ℃ and the vacuum degree of-30 KPa for curing, and obtaining the nano silicon dioxide modified graphene oxide/epoxy resin composite material (GO-SiO) 2/ EP)；
The curing process in the fourth step (4) comprises the following steps: curing at the vacuum degree of-30 KPa for 2h at 80 ℃, then curing at 100 ℃ for 2h, and finally curing at 150 ℃ for 3h.
The preparation method of graphene oxide described in the third step (1) of the embodiment is completed by the following steps:
(1) adding graphite, sodium nitrate and concentrated sulfuric acid into a three-neck flask, placing the three-neck flask into an ice water bath at 0 ℃, and stirring and reacting for 30min at the stirring speed of 300r/min to obtain a reaction solution I;
the mass fraction of the concentrated sulfuric acid in the step (1) is 96%;
the volume ratio of the mass of the graphite to the concentrated sulfuric acid in the step (1) is 6 g/360mL;
the volume ratio of the mass of the sodium nitrate to the concentrated sulfuric acid in the step (1) is 2g;
(2) adding potassium permanganate into the reaction solution I, placing the three-neck flask in an ice water bath at 0 ℃, and stirring at the stirring speed of 300r/min for reaction for 2 hours to obtain a reaction solution II;
the mass ratio of the potassium permanganate in the step (2) to the graphite in the step (1) is 20g;
(3) heating the temperature of the reaction liquid II to 35 ℃, reacting for 17 hours at the temperature of 35 ℃, and then adding distilled water to obtain a reaction liquid III;
the mass ratio of the volume of the distilled water in the step (3) to the graphite in the step (1) is 400mL;
(4) stirring the reaction solution III at the stirring speed of 300r/min for reacting for 1h, and then adding distilled water and 30% by mass of hydrogen peroxide to obtain a reaction solution IV;
the mass ratio of the volume of the distilled water in the step (4) to the graphite in the step one (1) is 600mL;
the mass ratio of the volume of the hydrogen peroxide with the mass fraction of 30% in the step (4) to the graphite in the step (1) is 40mL;
(5) stirring the reaction solution IV at a stirring speed of 300r/min for reaction for 20min, then performing ultrasonic treatment at an ultrasonic power of 180W for 30min, standing for 6h, and pouring out the supernatant to obtain a mixture I;
(6) cleaning the mixture I at a centrifugal speed of 6000r/min by taking a hydrogen chloride solution with a mass fraction of 14% as a cleaning agent until no precipitation is generated when a barium chloride solution of 0.1mol/L is added into the supernatant of the mixture I, so as to obtain a mixture I after the hydrogen chloride solution is cleaned;
(7) cleaning the mixture I cleaned by the hydrogen chloride solution by using deionized water until the pH value of the cleaning solution is 7 to obtain the mixture I cleaned by the deionized water;
(8) putting the mixture I cleaned by the deionized water into a freeze dryer, drying to obtain a solid I, and finally grinding the solid I and sieving by using a 300-mesh sieve to obtain a sieved substance, namely graphene oxide;
and (8) putting the mixture I cleaned by the deionized water into a freeze dryer, and freeze-drying at-10 ℃ for 24h.
Comparative example 1: the preparation method of the graphene oxide/epoxy resin composite material (GO/EP) is completed according to the following steps:
(1) adding graphene oxide into acetone, and performing ultrasonic treatment to obtain a graphene oxide solution;
the ultrasonic power in the step four (1) is 180W, and the ultrasonic time is 30min;
the volume ratio of the mass of the graphene oxide to the volume of the acetone in the step four (1) is 0.033g;
(2) adding epoxy resin into the graphene oxide solution, then carrying out ultrasonic treatment, and drying to obtain an epoxy resin mixture;
the epoxy resin in the step (2) is E-51;
the ultrasonic power in the step (2) is 180W, and the ultrasonic time is 30min;
the drying process in the step (2) comprises the following steps: drying in a vacuum drying oven with the temperature of 80 ℃ and the vacuum degree of-30 KPa for 10 hours;
the mass ratio of the epoxy resin in the step (2) to the graphene oxide in the graphene oxide solution is 33g;
(3) adding a curing agent into the epoxy resin mixture, mechanically stirring, and drying to obtain an epoxy resin mixture;
the curing agent in the step (3) is H-256;
the mass ratio of the curing agent in the step (3) to the epoxy resin in the step four (2) is 32;
the mechanical stirring speed in the step (3) is 3000r/min, and the stirring time is 15min;
the drying process in the step (3) comprises the following steps: drying for 1h in a vacuum drying oven with the temperature of 80 ℃ and the vacuum degree of-30 KPa;
(4) pouring the epoxy resin mixture into a preheating mould at the temperature of 80 ℃ in a vacuum drying oven at the temperature of 80 ℃ and the vacuum degree of-30 KPa for curing, and obtaining a graphene oxide/epoxy resin composite material (GO/EP) after curing;
the curing process in the fourth step comprises the following steps: curing at the vacuum degree of-30 KPa for 2h at 80 ℃, then curing at 100 ℃ for 2h, and finally curing at 150 ℃ for 3h.
Comparative example 2: silicon dioxide/epoxy resin composite material (SiO) 2/ EP) is prepared by the following steps:
(1) adding the nano silicon dioxide into acetone, and then carrying out ultrasonic treatment to obtain a nano silicon dioxide solution;
the ultrasonic power in the step four (1) is 180W, and the ultrasonic time is 30min;
the volume ratio of the mass of the nano silicon dioxide to the volume of the acetone in the step four (1) is 0.033g to 10mL;
(2) adding epoxy resin into the nano silicon dioxide, then carrying out ultrasonic treatment, and drying to obtain an epoxy resin mixture;
the epoxy resin in the step (2) is E-51;
the ultrasonic power in the step (2) is 180W, and the ultrasonic time is 30min;
the drying process in the step (2) comprises the following steps: drying in a vacuum drying oven at 80 deg.C and vacuum degree of-30 KPa for 10 hr;
the mass ratio of the epoxy resin in the step (2) to the nano-silica in the nano-silica solution is 33g;
(3) adding a curing agent into the epoxy resin mixture, mechanically stirring, and drying to obtain an epoxy resin mixture;
the curing agent in the step (3) is H-256;
the mass ratio of the curing agent in the step (3) to the epoxy resin in the step four (2) is 32;
the mechanical stirring speed in the step (3) is 3000r/min, and the stirring time is 15min;
the drying process in the step (3) comprises the following steps: drying in a vacuum drying oven at 80 deg.C and vacuum degree of-30 KPa for 1h;
(4) pouring the epoxy resin mixture into a preheating mould with the temperature of 80 ℃ in a vacuum drying oven with the temperature of 80 ℃ and the vacuum degree of-30 KPa for curing, and obtaining the nano silicon dioxide/epoxy resin composite material (SiO) 2/ EP)；
The curing process in the fourth step comprises the following steps: curing at the vacuum degree of-30 KPa for 2h at 80 ℃, then curing at 100 ℃ for 2h, and finally curing at 150 ℃ for 3h.
FIG. 1 is an infrared spectrum; in the figure, a is nano-silica, b is silane functionalized nano-silica prepared in the first step of the example, c is hyperbranched polymer grafted nano-silica prepared in the second step of the example, d is graphene oxide prepared in the first step of the example, and e is graphene oxide-nano-silica hybrid material prepared in the third step of the example;
as can be seen from FIG. 1, the nano-silica is 1077cm -1 ，804cm -1 948cm corresponding to Si-O-Si bonds -1 Corresponding to Si-OH bonds; the typical band of silane-functionalized nano-silica is 2943cm -1 、2888cm -1 The vicinity corresponds to the C-H stretching vibration. At the same time, is positioned at 1564cm -1 Is considered to be an N-H bending vibration, which indicates that the nanosilica has been successfully silanized. After grafting of the hyperbranched polymer, at 1535cm -1 And 1651cm -1 The bands attributed to N-H bending vibration and C = O stretching vibration; graphene oxide at 3100cm -1 、1716cm -1 、1608cm -1 And 1039cm -1 Corresponding characteristic peaks are respectively O-H, C = O, C = C and C-O-C bonds; in the spectrum of the graphene oxide-nano silicon dioxide hybrid material, it can be seen that the carboxyl absorption peak of the graphene oxide has disappeared. At the same time, N-C = O tensile vibration occurred at 1653cm -1 The chemical grafting between the graphene oxide and the nano silicon dioxide is proved. In addition, at 1039cm -1 At disappearance of C-O-C and at 1072cm -1 And 796cm -1 In the presence of Si-O-SiIndicating that the nano silicon dioxide is successfully attached to the surface of the graphene oxide through a covalent bond.
FIG. 2 is an XRD spectrum; in the figure, a is graphene oxide prepared in the first step of the example, b is nano-silica, c is silane-functionalized nano-silica prepared in the first step of the example, d is hyperbranched polymer-grafted nano-silica prepared in the second step of the example, and e is graphene oxide-nano-silica hybrid material prepared in the third step of the example;
as can be seen from fig. 2, graphene oxide shows a strong characteristic peak at 10.86 °, which corresponds to an interlayer distance of 0.81nm. The nanosilica, silane functionalized nanosilica and hyperbranched polymer grafted nanosilica show weak broad peaks at 23 °, indicating that the nanosilica is an amorphous and disordered structure. For the graphene oxide-nanosilica hybrid material, it can be seen that the diffraction peak intensity at 9.57 ° is significantly reduced compared to graphene oxide, which corresponds to an interlayer spacing of 0.92 nm. Meanwhile, siO 2 A broad diffraction peak was shown around 23 °. It is shown that the insertion of nano-silica into graphene oxide sheets not only improves the interlayer spacing but also prevents the aggregation of graphene oxide sheets.
FIG. 3 is an XPS peak profile of graphene oxide prepared in example one;
FIG. 4 is an XPS peak spectrum of a graphene oxide-nano-silica hybrid material prepared in the third step of the example;
as seen from the C1s peak profile of fig. 3, graphene oxide contains five characteristic peaks including C = C (284.4 eV), C-C (285.2 eV), C-O (286.6 eV), C = O (288.0 eV) and O-C = O (289.2 eV). And because amine modified nano silicon dioxide is introduced into the nano silicon dioxide modified graphene oxide, two new peaks are established at 285.8eV and 288.8eV, which correspond to C-N and N-C = O respectively. In addition, a peak appears at 284.4eV, which corresponds to C-Si, confirming the success of chemical grafting of nanosilica onto graphene oxide surfaces.
Table 1 shows the element content changes before and after graphene oxide is changed;
TABLE 1
As can be seen from table 1, the peaks of graphene oxide were observed to be two peaks of carbon element (69.9%) and oxygen element (30.1%). Silane functionalized nanosilica showed two characteristic peaks of C1s and N1s, which demonstrated successful functionalization with silane on nanosilica. The carbon and nitrogen peak intensities of the nanosilica gradually increase after functionalization with the hyperbranched polymer. For graphene oxide-nanosilica hybrid materials, si2p and N1s were observed, indicating that nanosilica has been successfully grafted to the graphene oxide surface.
Fig. 5 is a TEM image of graphene oxide prepared in example one;
FIG. 6 is a TEM image of a graphene oxide-nano-silica hybrid material prepared in the third step of the example;
FIG. 7 is a thermogram; in the figure, a is nano-silica, b is silane-functionalized nano-silica prepared in the first step of the example, c is hyperbranched polymer-grafted nano-silica prepared in the second step of the example, d is graphene oxide-nano-silica hybrid material prepared in the third step of the example, and e is graphene oxide prepared in the first step of the example;
as can be seen from FIG. 7, the nanosilica has very high stability, and the residue rate at 800 ℃ is 94.73%. For silane functionalized nanosilica, there are two stages of mass loss: the first weight loss is in the range of 30 ℃ to 100 ℃, which is due to evaporation of water on the surface of the silane-functionalized nanosilica. The second weight loss that occurred at 500 ℃ was probably due to decomposition of the amine and carbon chains of the silane molecules. Compared with silane functionalized nano-silica, the residual carbon content of the hyperbranched polymer grafted nano-silica is reduced from 90.90% to 84.70%, and is reduced by 6.20%. The reduction of the carbon residue is mainly due to the decomposition of the hyperbranched polymer, which shows that the nano silicon dioxide is successfully modified by the hyperbranched polymer. Thermal decomposition losses of graphene oxide occur mainly in three temperature intervals: (1) The weight loss from 30 ℃ to 140 ℃ is due to the evaporation of the absorbed water; (2) The weight loss in the temperature range of 140-330 ℃ is due to the decomposition of oxygen-containing functional groups on the surface of the graphene oxide. (3) the weight loss at 330 ℃ or higher is attributed to decomposition of the carbon skeleton. The decomposition behavior of the graphene oxide-nano silicon dioxide hybrid material is similar to that of graphene oxide. However, compared with graphene oxide, the thermal stability of the graphene oxide-nano silicon dioxide hybrid material is greatly improved. In addition, the decomposition rate of the graphene oxide-nano silicon dioxide hybrid material is significantly slower than that of graphene oxide, mainly because the surface of graphene oxide is connected with nano silicon dioxide of a hyperbranched polymer coating. Therefore, the nano silicon dioxide is grafted on the surface of the graphene oxide, so that the thermal stability is improved.
FIG. 8 is a graph comparing tensile strength, in FIG. 8 EP is pure epoxy resin, GO/EP is graphene oxide/epoxy resin composite material prepared in comparative example 1, siO 2/ EP Nano-silica/epoxy composite, GO-SiO, prepared in comparative example 2 2/ EP is the nano-silica modified graphene oxide/epoxy composite prepared in example one;
FIG. 9 is a graph comparing flexural strength, in FIG. 9 EP is pure epoxy resin, GO/EP is graphene oxide/epoxy resin composite material prepared in comparative example 1, siO 2/ EP Nano-silica/epoxy composite, GO-SiO, prepared in comparative example 2 2/ EP is the nano-silica modified graphene oxide/epoxy composite prepared in example one;
compared with pure epoxy resin, the tensile strength of the graphene oxide/epoxy resin composite material and the tensile strength of the nano silicon dioxide/epoxy resin composite material are both improved to a certain extent, and are respectively improved by 20.28% and 19.32%. The result shows that the addition of a small amount of nano material in the epoxy resin has obvious reinforcing effect. It is worth noting that the tensile strength of the nano-silica modified graphene oxide/epoxy resin composite material is 88.82 +/-4.34 MPa, which is 37.81% higher than that of pure epoxy resin respectively. This indicates that the graphene oxide-nano silicon dioxide hybrid material improves the tensile property of the epoxy resin, far exceeding that of graphene oxide and nano silicon dioxide. Similarly, the bending performance of the nano-silica modified graphene oxide/epoxy composite material shows better improvement than that of the graphene oxide/epoxy composite material and the nano-silica/epoxy composite material, and the bending strength is increased by 42.09% to 163.07 +/-8.15 MPa from 114.76 +/-5.35 MPa. This may be attributed to the enhanced dispersion of nanosilica on graphene oxide sheets in the epoxy resin. In addition, the nano silicon dioxide can enhance the interlocking effect with the epoxy resin, and effectively transfer the load to the nano material, thereby improving the mechanical property of the composite material.
FIG. 10 is a graph comparing impact strength, in FIG. 10 EP is pure epoxy resin, GO/EP is graphene oxide/epoxy resin composite material prepared in comparative example 1, siO 2/ EP Nano-silica/epoxy composite, GO-SiO, prepared in comparative example 2 2/ EP is the nano-silica modified graphene oxide/epoxy composite prepared in example one;
compared with pure epoxy resin, the graphene oxide/epoxy resin composite material and the nano silicon dioxide/epoxy resin composite material can bear higher load. The nano-silica modified graphene oxide/epoxy composite prepared by adding 0.1wt% of the graphene oxide-nano-silica hybrid material has an impact strength of 39.54 + -3.02 kJ/m 2 86.86 percent higher than that of pure epoxy resin. The results show that the graphene oxide-nano silicon dioxide hybrid material can better absorb and promote energy transfer when being impacted by external force, so that the impact strength of the composite material is improved.
Claims (10)
1. A preparation method of a nano-silica modified graphene oxide/epoxy resin composite material is characterized in that the preparation method of the nano-silica modified graphene oxide/epoxy resin composite material is completed according to the following steps:
1. silanization of nano-silica:
(1) dispersing the nano silicon dioxide in a mixed solution of absolute ethyl alcohol and water, and then carrying out ultrasonic treatment to obtain a nano silicon dioxide dispersion solution;
(2) adding a silane coupling agent into the nano-silica dispersion liquid, and stirring and refluxing for 6 to 8 hours at the constant temperature of between 70 and 80 ℃ to obtain a reaction liquid I;
(3) firstly, washing reaction liquid I, and then drying in vacuum to obtain silane functionalized nano silicon dioxide;
2. nano silicon dioxide grafted hyperbranched polymer:
(1) dispersing silane functionalized nano silicon dioxide in a mixed solution of methanol and water, and then carrying out ultrasonic treatment to obtain a silane functionalized nano silicon dioxide dispersion solution;
(2) adding N, N' -methylenebisacrylamide into the silane-functionalized nano-silica dispersion liquid, and stirring and refluxing for 18hours to 24h at the constant temperature of 40 ℃ to 50 ℃ to obtain a reaction liquid II;
the mass ratio of the N, N' -methylene bisacrylamide in the step two (2) to the silane-functionalized nano-silica in the silane-functionalized nano-silica dispersion is (0.5 to 1): 0.5 to 1;
(3) adding diethylenetriamine into the reaction liquid II, and stirring and refluxing for 18h to 24h at the constant temperature of 40-50 ℃ to obtain a reaction liquid III;
the mass ratio of the diethylenetriamine in the step two (3) to the silane-functionalized nano-silica in the silane-functionalized nano-silica dispersion liquid in the step two (2) is (0.5 to 1): 0.5 to 1;
(4) firstly, washing reaction liquid III, and then drying in vacuum to obtain hyperbranched polymer grafted nano silicon dioxide;
3. preparing a graphene oxide-nano silicon dioxide hybrid material:
(1) dispersing graphene oxide and hyperbranched polymer grafted nano silicon dioxide in N, N-dimethylformamide, and then carrying out ultrasonic treatment to obtain a mixture I;
the mass ratio of the graphene oxide to the hyperbranched polymer grafted nano silicon dioxide in the step three (1) is 1;
the mass of the graphene oxide in the third step (1) and the dosage ratio of the N, N-dimethylformamide are (0.05g to 0.2g) to (50 mL to 200 mL);
(2) adding an initiator into the mixture I, and stirring and refluxing for 4 to 6 hours at the constant temperature of 70 to 80 ℃ to obtain a reaction liquid IV;
the initiator in the step three (2) is N-hydroxy-7-azobenzotriazole;
the mass ratio of the initiator in the third step (2) to the graphene oxide in the third step (1) is 0.2;
(3) firstly, washing the reaction solution IV for 3-4 times by using N, N-dimethylformamide, and then drying in vacuum to obtain a graphene oxide-nano silicon dioxide hybrid material;
4. compounding:
(1) adding the graphene oxide-nano silicon dioxide hybrid material into acetone, and performing ultrasonic treatment to obtain a graphene oxide-nano silicon dioxide hybrid material solution;
(2) adding epoxy resin into the graphene oxide-nano silicon dioxide hybrid material solution, then carrying out ultrasonic treatment, and drying to obtain an epoxy resin mixture;
(3) adding a curing agent into the epoxy resin mixture, mechanically stirring, and drying to obtain an epoxy resin curing agent mixture;
(4) pouring the epoxy resin curing agent mixture into a preheating mould at the temperature of 80-90 ℃ in a vacuum drying box at the temperature of 80-90 ℃ and the vacuum degree of-30 KPa-35 KPa for curing, and obtaining the nano silicon dioxide modified graphene oxide/epoxy resin composite material after curing.
2. The preparation method of the nano-silica modified graphene oxide/epoxy resin composite material according to claim 1, wherein the ultrasonic power in the step one (1) is 180W to 200W, and the ultrasonic time is 30min to 60min; the ratio of the mass of the nano silicon dioxide in the step one (1) to the using amount of the mixed solution of the absolute ethyl alcohol and the water is (1g) - (2g): (100mL) - (200mL); the volume ratio of the absolute ethyl alcohol to the water in the mixed liquid of the absolute ethyl alcohol and the water in the step one (1) is (90-180): (10-20).
3. The method for preparing a nano-silica modified graphene oxide/epoxy resin composite material according to claim 1, wherein the silane coupling agent in the step one (2) is 3-aminopropyltriethoxysilane; the mass ratio of the silane coupling agent in the step one (2) to the nano silicon dioxide in the nano silicon dioxide dispersion liquid is (2 to 4) to (1 to 2).
4. The preparation method of the nano-silica-modified graphene oxide/epoxy resin composite material according to claim 1, wherein in the step one (3), the reaction solution I is washed for 3 to 4 times by using absolute ethyl alcohol, then washed for 3 to 4 times by using distilled water, and finally dried in a vacuum drying oven at a temperature of 80 to 90 ℃ for 8 to 12h to obtain the silane-functionalized nano-silica.
5. The preparation method of the nano-silica modified graphene oxide/epoxy resin composite material according to claim 1, wherein the volume ratio of methanol to water in the mixed solution of methanol and water in the step two (1) is (100 to 200): (50 to 100); the ratio of the mass of the silane functionalized nano silicon dioxide in the step two (1) to the using amount of a mixed solution of methanol and water is (0.5g to 1g) to (100mL to 200mL); the ultrasonic power in the step two (1) is 180W-200W, and the ultrasonic time is 30min-60min.
6. The preparation method of the nano-silica modified graphene oxide/epoxy resin composite material according to claim 1, wherein in the second step (4), the reaction solution III is washed 3-4 times with methanol, washed 3-4 times with distilled water, and finally dried in a vacuum drying oven at 80-90 ℃ for 8-12h to obtain the hyperbranched polymer grafted nano-silica.
7. The preparation method of the nano-silica-modified graphene oxide/epoxy resin composite material according to claim 1, wherein the ultrasonic power in the third step (1) is 180W to 200W, and the ultrasonic time is 1h to 2h; and in the third step (3), the vacuum drying temperature is 80-100 ℃, and the vacuum drying time is 8hours to 12hours.
8. The method for preparing nano-silica modified graphene oxide/epoxy resin composite material according to claim 1, wherein the method for preparing graphene oxide in step three (1) is completed according to the following steps:
(1) adding graphite, sodium nitrate and concentrated sulfuric acid into a three-neck flask, placing the three-neck flask in an ice water bath at the temperature of 0-5 ℃, and stirring at the stirring speed of 300-400 r/min for reaction for 30min-40min to obtain a reaction liquid I;
the mass fraction of the concentrated sulfuric acid in the step (1) is 96% -98%;
the ratio of the mass of the graphite to the using amount of concentrated sulfuric acid in the step (1) is (6g-8g) to (360mL-500mL);
the ratio of the mass of the sodium nitrate to the using amount of the concentrated sulfuric acid in the step (1) is (2g to 4g) to (360mL to 500mL);
(2) adding potassium permanganate into the reaction liquid I, placing the three-neck flask in an ice water bath at the temperature of 0-5 ℃, and stirring at the stirring speed of 300-400 r/min for reaction for 2-3h to obtain a reaction liquid II;
the mass ratio of the potassium permanganate in the step (2) to the graphite in the step (1) is (20g to 25g) to (6g to 8g);
(3) heating the temperature of the reaction liquid II to 35-40 ℃, reacting at the temperature of 35-40 ℃ for 17h to 19h, and then adding distilled water to obtain a reaction liquid III;
the volume ratio of the distilled water in the step (3) to the graphite in the step (1) is (400mL to 600mL) to (6g to 8g);
(4) stirring the reaction liquid III at a stirring speed of 300-400 r/min for reaction for 1h-2h, and then adding distilled water and 30% by mass of hydrogen peroxide to obtain a reaction liquid IV;
the volume ratio of the distilled water in the step (4) to the graphite in the step (1) is (600mL-800mL): (6g-8g);
the ratio of the volume of the hydrogen peroxide with the mass fraction of 30% in the step (4) to the using amount of the graphite in the step (1) is (40mL-60mL) to (6g-8g);
(5) stirring the reaction liquid IV at the stirring speed of 300 r/min-400 r/min for reaction for 20 min-40min, then carrying out ultrasonic treatment at the ultrasonic power of 180W-200W for 30min-50min, then standing for 6 h-8h, and pouring out the supernatant to obtain a mixture I;
(6) cleaning the mixture I at a centrifugal speed of 6000-8000 r/min by taking a hydrogen chloride solution with the mass fraction of 14% -16% as a cleaning agent until no precipitation is generated when 0.1-0.15mol/L barium chloride solution is added into the supernatant of the mixture I, so as to obtain a mixture I cleaned by the hydrogen chloride solution;
(7) cleaning the mixture I cleaned by the hydrogen chloride solution by using deionized water until the pH value of the cleaning solution is 7 to obtain the mixture I cleaned by the deionized water;
(8) putting the mixture I cleaned by the deionized water into a freeze dryer, drying to obtain a solid I, and finally grinding the solid I and sieving by using a 300-mesh sieve to obtain a sieved substance, namely graphene oxide;
and (8) putting the mixture I cleaned by the deionized water into a freeze dryer, and freeze-drying at the temperature of minus 10 ℃ to minus 5 ℃ for 24h to 36h.
9. The preparation method of the nano-silica modified graphene oxide/epoxy resin composite material according to claim 1, wherein the ultrasonic power in the fourth step (1) is 180W to 200W, and the ultrasonic time is 30min to 60min; the mass of the graphene oxide-nano silicon dioxide hybrid material in the step four (1) to the dosage of acetone is (0.033g to 0.036 g) to (10mL to 15mL); the ultrasonic power in the step four (2) is 180W to 200W, and the ultrasonic time is 30min to 60min; the drying process in the step four (2) comprises the following steps: drying for 10h to 12h in a vacuum drying box with the temperature of 80 ℃ and the vacuum degree of-30 KPa to-35 KPa; the mass ratio of the epoxy resin in the step four (2) to the mass of the graphene oxide-nano silicon dioxide hybrid material in the graphene oxide-nano silicon dioxide hybrid material solution is (33g) - (36g) - (0.033g) - (0.036 g).
10. The method for preparing a nano-silica modified graphene oxide/epoxy resin composite material according to claim 1, wherein the epoxy resin in the step four (2) is E-51; the curing agent in the fourth step (3) is H-256; the mechanical stirring speed in the step four (3) is 3000r/min, and the stirring time is 15min to 20min; the drying process in the fourth step (3) comprises the following steps: drying for 1h to 1.5h in a vacuum drying oven at the temperature of 80-90 ℃ and the vacuum degree of-30 KPa to-35 KPa; the mass ratio of the curing agent in the step four (3) to the epoxy resin in the step four (2) is 32; the curing process in the fourth step (4) comprises the following steps: under the vacuum degree of-30 KPa to-35 KPa, firstly curing for 2h at 80-90 ℃, then curing for 2h at 100-120 ℃, and finally curing for 3h to 4h at 150 ℃.
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