CN110204929B - Method for covalently modifying graphene oxide by using six-membered heterocyclic ring - Google Patents
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Abstract
A method for covalently modifying graphene oxide by a six-membered heterocyclic ring relates to a method for modifying graphene oxide. The invention aims to solve the problems of poor dispersibility and poor interface strength of the existing graphene in the composite material. The method comprises the following steps: firstly, preparing graphene oxide; secondly, hydroxylation treatment of graphene oxide; thirdly, cyanuric chloride modifies graphene oxide; and fourthly, modifying the graphene oxide by using trihydroxyaminomethane to obtain the graphene oxide covalently modified by the six-membered heterocyclic ring. The hexatomic heterocycle covalent modified graphene oxide prepared by the method has better mechanical property by compounding with epoxy resin, and compared with the epoxy resin, the tensile strength is improved by more than 38%, and the bending strength is improved by more than 46%. The method can obtain the hexatomic heterocycle covalently modified graphene oxide.
Description
Technical Field
The invention relates to a method for modifying graphene oxide.
Background
Graphene is a nano material with excellent properties such as unique structure, layer atom thickness, high strength, high electrical conductivity and thermal conductivity, and is widely applied to the fields of aerospace, mechanical manufacturing, buildings and the like. Furthermore, there have been most experiments demonstrating that graphene and graphene oxide sheets are the most promising reinforcement materials in polymer composites because of their excellent mechanical properties. However, there are two major problems limiting the mechanical properties and applications of graphene epoxy composites: 1) due to strong van der waals force, the graphene is easy to irreversibly aggregate in the composite material, which leads to poor dispersibility of the graphene in the matrix; 2) since graphene is surface inert, the interface interaction with the substrate is weak, which also limits load transfer from the substrate to the sheet. In order to solve the above problems, a method of modifying the surface of graphene oxide is generally used, which mainly includes non-covalent modification and covalent modification. Non-covalent modifications are the attachment of molecules by weak binding interactions, such as hydrogen bonding, van der waals forces or electrostatic adsorption. The covalent modification is to generate a strong bonding effect through a chemical reaction between a functional group on the surface of the graphene oxide and other compounds, and thereby introduce a plurality of active groups on the surface of the graphene oxide, and effectively control the physical and chemical properties of the graphene composite material. In recent years, a great deal of research has been carried out on the surface modification of graphene oxide, but due to the limited number of active groups of the grafted chains on the surface of graphene, the improvement of the performance of the graphene/epoxy resin composite material is still limited, and the graphene/epoxy resin composite material is high in cost and low in efficiency. Therefore, an efficient graphene surface modification technology is urgently needed at present, and more active points are formed on the surface of the graphene surface modification technology to improve the dispersibility and the interface bonding performance of the graphene in epoxy resin, so that the mechanical property of the composite material is improved, and the application range of the composite material is expanded.
Numerous experiments have performed chemical modification of the surface of graphene oxide, but some disadvantages remain, such as the covalent grafting of graphene oxide leading to the destruction of the perfect structure of graphene, which leads to the reduction of the strength of the reinforcing component and the thermal properties of the composite.
Disclosure of Invention
The invention aims to solve the problems of poor dispersibility and poor interface strength of the existing graphene in a composite material, and provides a method for covalently modifying graphene oxide by using a six-membered heterocyclic ring.
A method for covalently modifying graphene oxide by using a six-membered heterocyclic ring is completed according to the following steps:
firstly, preparing graphene oxide:
adding graphite, sodium nitrate and concentrated sulfuric acid into a three-neck flask, placing the three-neck flask in 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 reaction liquid I;
the mass fraction of the concentrated sulfuric acid in the first step is 96-98%;
the ratio of the mass of the graphite to the volume of the concentrated sulfuric acid in the first step is (6 g-8 g): 360 mL-500 mL;
the mass ratio of the sodium nitrate to the concentrated sulfuric acid in the first step (2 g-4 g) is (360 mL-500 mL);
secondly, 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 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 first step to the graphite in the first step is (20-25) to (6-8);
thirdly, heating the reaction liquid II to 35-40 ℃, reacting for 17-19 h at the temperature of 35-40 ℃, and adding distilled water to obtain reaction liquid III;
the mass ratio of the volume of the distilled water in the first step to the graphite in the first step is (400 mL-600 mL): 6 g-8 g);
stirring the reaction solution III at the stirring speed of 300 r/min-400 r/min for reaction for 1 h-2 h, and then adding distilled water and a hydrogen peroxide solution with the mass fraction of 30% to obtain a reaction solution IV;
the mass ratio of the volume of the distilled water in the first step to the graphite in the first step is (600 mL-800 mL): 6 g-8 g);
the volume of the hydrogen peroxide solution with the mass fraction of 30 percent in the first step (IV) and the mass ratio of the graphite in the first step (IV) are (40 mL-60 mL) - (6 g-8 g);
fifthly, stirring the reaction solution IV at the stirring speed of 300 r/min-400 r/min for reaction for 20 min-40 min, then carrying out ultrasonic treatment at the ultrasonic power of 350W-360W for 30 min-50 min, then standing for 6 h-8 h, and pouring out the supernatant to obtain a mixture I;
sixthly, using hydrochloric acid with the mass fraction of 14-16% as a cleaning agent, cleaning the mixture I at the centrifugal speed of 6000-8000 r/min until no precipitation is generated when the supernatant of the mixture I is added with 0.1-0.15 mol/L barium chloride solution, and obtaining the mixture I after being cleaned by the hydrochloric acid;
seventhly, 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;
drying the mixture I cleaned by the deionized water in a freeze dryer to obtain a solid I, and finally grinding the solid I and sieving the solid I through a 300-mesh sieve to obtain a sieved substance, namely graphene oxide;
secondly, hydroxylation treatment of graphene oxide:
dissolving lithium aluminum hydride in tetrahydrofuran to obtain a tetrahydrofuran solution of the lithium aluminum hydride;
the mass ratio of the lithium aluminum hydride in the second step to the volume ratio of tetrahydrofuran is (4 g-5 g):100 mL-120 mL;
secondly, firstly adding graphene oxide into a tetrahydrofuran solution of lithium aluminum hydride, then carrying out ultrasonic treatment for 0.5-1 h at the ultrasonic power of 350-360W, and carrying out magnetic stirring reaction for 2-3 h at room temperature at the stirring speed of 300-400 r/min to obtain a mixture;
the mass ratio of the graphene oxide in the second step to the volume ratio of the tetrahydrofuran in the second step is (2 g-3 g):100 mL-120 mL;
thirdly, adding hydrochloric acid with the mass fraction of 37% into the mixture until the supernatant of the mixture becomes clear, then using deionized water to clean until the cleaning solution is neutral, and finally placing the mixture into a vacuum drying oven with the temperature of 80-90 ℃ to dry for 6-12 h to obtain hydroxylated graphene oxide;
thirdly, cyanuric chloride modified graphene oxide:
firstly, adding hydroxylated graphene oxide into tetrahydrofuran, performing ultrasonic treatment for 1-2 h at the ultrasonic power of 350-360W, adding cyanuric chloride and triethylamine, and heating, stirring and refluxing for 24-36 h at the temperature of 70-80 ℃ and the stirring speed of 300-400 r/min to obtain a reaction product I;
the volume ratio of the mass of the hydroxylated graphene oxide to the tetrahydrofuran in the third step is (1 g-2 g) 100 mL;
the volume ratio of the mass of the cyanuric chloride to the tetrahydrofuran in the third step (3 g-4 g) is 100 mL;
the volume ratio of the mass of the triethylamine to the volume of the tetrahydrofuran in the third step (4 g-6 g) is 100 mL;
secondly, washing the reaction product I for 3-5 times by using tetrahydrofuran, then washing for 3-8 times by using absolute ethyl alcohol, and finally drying for 4-6 hours in a vacuum drying oven at the temperature of 80-90 ℃ to obtain cyanuric chloride modified graphene oxide;
and IV, modifying the graphene oxide by using trihydroxyaminomethane:
adding cyanuric chloride modified graphene oxide into acetonitrile, performing ultrasonic dispersion for 1-2 h at the ultrasonic power of 350-360W, adding trihydroxyaminomethane and triethylamine, heating, stirring and refluxing for 12-18 h at the temperature of 70-80 ℃, and obtaining a reaction product II;
the volume ratio of the mass of the cyanuric chloride modified graphene oxide to the acetonitrile in the fourth step is (0.2 g-0.4 g): 30 mL-60 mL;
the volume ratio of the mass of the trihydroxy aminomethane to the acetonitrile in the fourth step is (0.4 g-0.6 g): 30 mL-60 mL;
the volume ratio of the triethylamine to the acetonitrile in the step IV is (4 g-6 g): 30 mL-60 mL;
secondly, washing the reaction product II for 3 to 8 times by using absolute ethyl alcohol, and drying the reaction product II for 4 to 6 hours in a vacuum drying oven at the temperature of between 80 and 90 ℃ to obtain the hexatomic heterocyclic ring covalent modified graphene oxide.
The principle of the invention is as follows:
according to the method, firstly, the graphene oxide is subjected to hydroxylation treatment, then, hydroxyl functional groups on the surface of the graphene oxide are chemically combined with active chlorine in cyanuric chloride, and cyanuric chloride is grafted to increase reaction sites for the surface of the graphene oxide; then the amino in the micromolecular trihydroxy aminomethane reacts with the unreacted chlorine of cyanuric chloride to generate strong chemical bonds. Modification of cyanuric chloride and trihydroxyaminomethane on graphene oxide not only increases active groups on the surface of graphene oxide, improves compatibility and interface combination with polymers, but also prevents agglomeration of graphene oxide in polymers by a grafted chain, and improves dispersibility of graphene oxide in a matrix.
The invention has the advantages that:
the cyanuric chloride has special structural characteristics of a stable triazine ring structure, a plurality of active chlorine reaction sites and the like, and provides multiple possibilities for modifying graphene oxide; micromolecule trihydroxy aminomethane has a plurality of active groups, so that the surface activity of the graphene oxide is improved; the cyanuric chloride and the trihydroxy aminomethane have low cost, mild reaction conditions with the graphene oxide, simple reaction process, low energy consumption, economy and environmental protection; the surface modification of the graphene oxide by the micromolecules does not cause the damage of the structure of the graphene oxide, and can effectively prevent the agglomeration phenomenon of the graphene oxide;
secondly, the hexatomic heterocycle covalent modified graphene oxide prepared by the method is compounded with epoxy resin to have better mechanical property, and compared with the epoxy resin, the tensile strength of the composite material is improved by more than 38%, and the bending strength is improved by more than 46%.
The method can obtain the hexatomic heterocycle covalently modified graphene oxide.
Drawings
Fig. 1 is an infrared spectrogram, wherein a is an infrared spectrum curve of graphene oxide obtained in the first step of the example, b is an infrared spectrum curve of cyanuric chloride modified graphene oxide obtained in the third step of the example, and c is an infrared spectrum curve of six-membered heterocyclic covalently modified graphene oxide obtained in the fourth step of the example;
fig. 2 is a raman spectrum, in which a is a raman curve of graphene oxide obtained in the first step of the example, b is a raman curve of cyanuric chloride modified graphene oxide obtained in the third step of the example, and c is a raman curve of six-membered heterocycle covalently modified graphene oxide obtained in the fourth step of the example;
fig. 3 is an XPS peak spectrum of graphene oxide obtained in one step one of the embodiment;
FIG. 4 is an XPS peak spectrum of a six-membered heterocycle covalently modified graphene oxide obtained in the fourth step of the example;
fig. 5 is an SEM image of graphene oxide obtained by one step of the example one;
FIG. 6 is an SEM image of a six-membered heterocycle covalently modified graphene oxide obtained in step IV of the embodiment;
fig. 7 is a bar graph of tensile strength, in which 1 is the tensile strength of pure epoxy resin, 2 is the tensile strength of graphene oxide/epoxy resin composite material prepared in example three, and 3 is the tensile strength of six-membered heterocyclic covalently modified graphene oxide/epoxy resin composite material prepared in example four;
fig. 8 is a bending strength bar graph, in which 1 is the bending strength of pure epoxy resin, 2 is the bending strength of the graphene oxide/epoxy resin composite material prepared in the third example, and 3 is the bending strength of the six-membered heterocyclic covalently modified graphene oxide/epoxy resin composite material prepared in the fourth example.
Detailed Description
The first embodiment is as follows: the embodiment is a method for covalently modifying graphene oxide by a six-membered heterocyclic ring, which is completed by the following steps:
firstly, preparing graphene oxide:
adding graphite, sodium nitrate and concentrated sulfuric acid into a three-neck flask, placing the three-neck flask in 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 reaction liquid I;
the mass fraction of the concentrated sulfuric acid in the first step is 96-98%;
the ratio of the mass of the graphite to the volume of the concentrated sulfuric acid in the first step is (6 g-8 g): 360 mL-500 mL;
the mass ratio of the sodium nitrate to the concentrated sulfuric acid in the first step (2 g-4 g) is (360 mL-500 mL);
secondly, 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 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 first step to the graphite in the first step is (20-25) to (6-8);
thirdly, heating the reaction liquid II to 35-40 ℃, reacting for 17-19 h at the temperature of 35-40 ℃, and adding distilled water to obtain reaction liquid III;
the mass ratio of the volume of the distilled water in the first step to the graphite in the first step is (400 mL-600 mL): 6 g-8 g);
stirring the reaction solution III at the stirring speed of 300 r/min-400 r/min for reaction for 1 h-2 h, and then adding distilled water and a hydrogen peroxide solution with the mass fraction of 30% to obtain a reaction solution IV;
the mass ratio of the volume of the distilled water in the first step to the graphite in the first step is (600 mL-800 mL): 6 g-8 g);
the volume of the hydrogen peroxide solution with the mass fraction of 30 percent in the first step (IV) and the mass ratio of the graphite in the first step (IV) are (40 mL-60 mL) - (6 g-8 g);
fifthly, stirring the reaction solution IV at the stirring speed of 300 r/min-400 r/min for reaction for 20 min-40 min, then carrying out ultrasonic treatment at the ultrasonic power of 350W-360W for 30 min-50 min, then standing for 6 h-8 h, and pouring out the supernatant to obtain a mixture I;
sixthly, using hydrochloric acid with the mass fraction of 14-16% as a cleaning agent, cleaning the mixture I at the centrifugal speed of 6000-8000 r/min until no precipitation is generated when the supernatant of the mixture I is added with 0.1-0.15 mol/L barium chloride solution, and obtaining the mixture I after being cleaned by the hydrochloric acid;
seventhly, 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;
drying the mixture I cleaned by the deionized water in a freeze dryer to obtain a solid I, and finally grinding the solid I and sieving the solid I through a 300-mesh sieve to obtain a sieved substance, namely graphene oxide;
secondly, hydroxylation treatment of graphene oxide:
dissolving lithium aluminum hydride in tetrahydrofuran to obtain a tetrahydrofuran solution of the lithium aluminum hydride;
the mass ratio of the lithium aluminum hydride in the second step to the volume ratio of tetrahydrofuran is (4 g-5 g):100 mL-120 mL;
secondly, firstly adding graphene oxide into a tetrahydrofuran solution of lithium aluminum hydride, then carrying out ultrasonic treatment for 0.5-1 h at the ultrasonic power of 350-360W, and carrying out magnetic stirring reaction for 2-3 h at room temperature at the stirring speed of 300-400 r/min to obtain a mixture;
the mass ratio of the graphene oxide in the second step to the volume ratio of the tetrahydrofuran in the second step is (2 g-3 g):100 mL-120 mL;
thirdly, adding hydrochloric acid with the mass fraction of 37% into the mixture until the supernatant of the mixture becomes clear, then using deionized water to clean until the cleaning solution is neutral, and finally placing the mixture into a vacuum drying oven with the temperature of 80-90 ℃ to dry for 6-12 h to obtain hydroxylated graphene oxide;
thirdly, cyanuric chloride modified graphene oxide:
firstly, adding hydroxylated graphene oxide into tetrahydrofuran, performing ultrasonic treatment for 1-2 h at the ultrasonic power of 350-360W, adding cyanuric chloride and triethylamine, and heating, stirring and refluxing for 24-36 h at the temperature of 70-80 ℃ and the stirring speed of 300-400 r/min to obtain a reaction product I;
the volume ratio of the mass of the hydroxylated graphene oxide to the tetrahydrofuran in the third step is (1 g-2 g) 100 mL;
the volume ratio of the mass of the cyanuric chloride to the tetrahydrofuran in the third step (3 g-4 g) is 100 mL;
the volume ratio of the mass of the triethylamine to the volume of the tetrahydrofuran in the third step (4 g-6 g) is 100 mL;
secondly, washing the reaction product I for 3-5 times by using tetrahydrofuran, then washing for 3-8 times by using absolute ethyl alcohol, and finally drying for 4-6 hours in a vacuum drying oven at the temperature of 80-90 ℃ to obtain cyanuric chloride modified graphene oxide;
and IV, modifying the graphene oxide by using trihydroxyaminomethane:
adding cyanuric chloride modified graphene oxide into acetonitrile, performing ultrasonic dispersion for 1-2 h at the ultrasonic power of 350-360W, adding trihydroxyaminomethane and triethylamine, heating, stirring and refluxing for 12-18 h at the temperature of 70-80 ℃, and obtaining a reaction product II;
the volume ratio of the mass of the cyanuric chloride modified graphene oxide to the acetonitrile in the fourth step is (0.2 g-0.4 g): 30 mL-60 mL;
the volume ratio of the mass of the trihydroxy aminomethane to the acetonitrile in the fourth step is (0.4 g-0.6 g): 30 mL-60 mL;
the volume ratio of the triethylamine to the acetonitrile in the step IV is (4 g-6 g): 30 mL-60 mL;
secondly, washing the reaction product II for 3 to 8 times by using absolute ethyl alcohol, and drying the reaction product II for 4 to 6 hours in a vacuum drying oven at the temperature of between 80 and 90 ℃ to obtain the hexatomic heterocyclic ring covalent modified graphene oxide.
The principle of the present embodiment:
according to the embodiment, firstly, the graphene oxide is subjected to hydroxylation treatment, then, hydroxyl functional groups on the surface of the graphene oxide are chemically combined with active chlorine in cyanuric chloride, and reactive sites are added on the surface of the graphene oxide by grafting of the cyanuric chloride; then the amino in the micromolecular trihydroxy aminomethane reacts with the unreacted chlorine of cyanuric chloride to generate strong chemical bonds. Modification of cyanuric chloride and trihydroxyaminomethane on graphene oxide not only increases active groups on the surface of graphene oxide, improves compatibility and interface combination with polymers, but also prevents agglomeration of graphene oxide in polymers by a grafted chain, and improves dispersibility of graphene oxide in a matrix.
The advantages of this embodiment:
the cyanuric chloride has special structural characteristics of a stable triazine ring structure, a plurality of active chlorine reaction sites and the like, and provides multiple possibilities for modifying graphene oxide; micromolecule trihydroxy aminomethane has a plurality of active groups, so that the surface activity of the graphene oxide is improved; the cyanuric chloride and the trihydroxy aminomethane have low cost, mild reaction conditions with the graphene oxide, simple reaction process, low energy consumption, economy and environmental protection; the surface modification of the graphene oxide by the micromolecules does not cause the damage of the structure of the graphene oxide, and can effectively prevent the agglomeration phenomenon of the graphene oxide;
secondly, the hexatomic heterocycle covalent modified graphene oxide prepared by the embodiment is compounded with epoxy resin to have better mechanical property, and compared with the epoxy resin, the tensile strength of the composite material is improved by more than 38%, and the bending strength is improved by more than 46%.
The embodiment can obtain the hexatomic heterocycle covalently modified graphene oxide.
The second embodiment is as follows: the present embodiment differs from the present embodiment in that: and the mass ratio of the lithium aluminum hydride in the second step to the tetrahydrofuran is (4.5 g-5 g): 110 mL-120 mL. Other steps are the same as in the first embodiment.
The third concrete implementation mode: the present embodiment differs from the first or second embodiment in that: the mass ratio of the graphene oxide in the second step to the volume ratio of the tetrahydrofuran in the second step is (2.5-3 g): 110-120 mL. 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: and the volume ratio of the mass of the hydroxylated graphene oxide to the volume of the tetrahydrofuran in the third step (1.5 g-2 g) is 100 mL. The other steps are the same as those in the first to third embodiments.
The fifth concrete implementation mode: the difference between this embodiment and one of the first to fourth embodiments is: the volume ratio of the mass of the cyanuric chloride to the tetrahydrofuran in the third step is (3.5 g-4 g):100 mL. The other steps are the same as those in the first to fourth embodiments.
The sixth specific implementation mode: the difference between this embodiment and one of the first to fifth embodiments is as follows: and the volume ratio of the mass of the triethylamine to the volume of the tetrahydrofuran in the third step (5 g-6 g) is 100 mL. 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: and the volume ratio of the mass of the cyanuric chloride modified graphene oxide to the acetonitrile in the fourth step is (0.3-0.4 g): 40-60 mL. 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: and the volume ratio of the mass of the trihydroxy aminomethane to the acetonitrile in the fourth step is (0.5 g-0.6 g): 45 mL-60 mL. 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: and the volume ratio of the triethylamine to the acetonitrile in the fourth step is (5 g-6 g): 45 mL-60 mL. 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 one of the first to ninth embodiments is as follows: and thirdly, adding hydroxylated graphene oxide into tetrahydrofuran, performing ultrasonic treatment for 1-2 h at the ultrasonic power of 350-360W, adding cyanuric chloride and triethylamine, and heating, stirring and refluxing for 24-32 h at the temperature of 75-80 ℃ and the stirring speed of 300-400 r/min to obtain a reaction product I. The other steps are the same as those in the first to ninth embodiments.
The following examples were used to demonstrate the beneficial effects of the present invention:
the first embodiment is as follows: a method for covalently modifying graphene oxide by using a six-membered heterocyclic ring is completed according to the following steps:
firstly, preparing graphene oxide:
adding 8g of graphite, 3.75g of sodium nitrate and 360mL of 98 mass percent concentrated sulfuric acid into a three-neck flask, placing the three-neck flask in an ice-water bath at 0 ℃, and stirring and reacting for 30min at the stirring speed of 400r/min to obtain a reaction solution I;
adding 22.5g of potassium permanganate into the reaction solution I, placing the three-neck flask in an ice water bath at 0 ℃, and stirring for reaction for 2 hours at the stirring speed of 400r/min to obtain a reaction solution II;
thirdly, heating the temperature of the reaction liquid II to 35 ℃, reacting for 17 hours at the temperature of 35 ℃, and then adding 400mL of distilled water to obtain a reaction liquid III;
stirring the reaction solution III at the stirring speed of 400r/min for reaction for 1h, and then adding 660mL of distilled water and 60mL of hydrogen peroxide solution with the mass fraction of 30% to obtain reaction solution IV;
fifthly, stirring the reaction solution IV for reaction for 20min at the stirring speed of 400r/min, then performing ultrasonic treatment for 30min at the ultrasonic power of 350W, standing for 6h, and pouring out the supernatant to obtain a mixture I;
sixthly, using hydrochloric acid with the mass fraction of 14% as a cleaning agent, cleaning the mixture I at the centrifugal speed of 7000r/min until no precipitation is generated when the supernatant of the mixture I is added with 0.1mol/L barium chloride solution, and obtaining the mixture I after being cleaned by the hydrochloric acid;
seventhly, 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;
drying the mixture I cleaned by the deionized water in a freeze dryer to obtain a solid I, and finally grinding the solid I and sieving the solid I through a 300-mesh sieve to obtain a sieved substance, namely graphene oxide;
secondly, hydroxylation treatment of graphene oxide:
dissolving 4g of lithium aluminum hydride in 100mL of tetrahydrofuran to obtain a tetrahydrofuran solution of the lithium aluminum hydride;
firstly, adding 2g of graphene oxide into a tetrahydrofuran solution of lithium aluminum hydride, then carrying out ultrasonic treatment for 0.5h under the ultrasonic power of 350W, and carrying out magnetic stirring reaction for 2h at room temperature at the stirring speed of 400r/min to obtain a mixture;
thirdly, adding hydrochloric acid with the mass fraction of 37% into the mixture until the supernatant of the mixture becomes clear, then washing the mixture by using deionized water until the washing liquid is neutral, and finally drying the mixture in a vacuum drying oven at the temperature of 80 ℃ for 6 hours to obtain hydroxylated graphene oxide;
thirdly, cyanuric chloride modified graphene oxide:
adding 1g of hydroxylated graphene oxide into 100mL of tetrahydrofuran, performing ultrasonic treatment for 1h at the ultrasonic power of 350W, adding 3.69g of cyanuric chloride and 4.0g of triethylamine, and heating, stirring and refluxing for 24h at the temperature of 70 ℃ and the stirring speed of 400r/min to obtain a reaction product I;
secondly, washing the reaction product I with tetrahydrofuran for 4 times, then washing with absolute ethyl alcohol for 5 times, and finally drying in a vacuum drying oven at the temperature of 80 ℃ for 4 hours to obtain cyanuric chloride modified graphene oxide;
and IV, modifying the graphene oxide by using trihydroxyaminomethane:
adding 0.2g of cyanuric chloride modified graphene oxide into 30mL of acetonitrile, performing ultrasonic dispersion for 1h under the ultrasonic power of 350W, adding 0.4g of trihydroxyaminomethane and 4g of triethylamine, and heating, stirring and refluxing for 12h at the temperature of 70 ℃ to obtain a reaction product II;
and secondly, washing the reaction product II for 5 times by using absolute ethyl alcohol, and drying for 4 hours in a vacuum drying oven at the temperature of 80 ℃ to obtain the hexatomic heterocyclic ring covalently modified graphene oxide.
Example two: a method for covalently modifying graphene oxide by using a six-membered heterocyclic ring is completed according to the following steps:
firstly, preparing graphene oxide:
adding 6g of graphite, 2g of sodium nitrate and 98% concentrated sulfuric acid by mass into a three-neck flask, placing the three-neck flask in an ice water bath at the temperature of 3 ℃, and stirring and reacting for 40min at the stirring speed of 300r/min to obtain a reaction solution I;
secondly, adding 20g of potassium permanganate into the reaction liquid I, placing the three-neck flask in an ice-water bath at the temperature of 3 ℃, and stirring and reacting for 3 hours at the stirring speed of 300r/min to obtain reaction liquid II;
thirdly, heating the temperature of the reaction liquid II to 35 ℃, reacting for 19 hours at the temperature of 35 ℃, and then adding 500mL of distilled water to obtain a reaction liquid III;
stirring the reaction solution III at the stirring speed of 300r/min for reaction for 1.5h, and then adding 800mL of distilled water and 40mL of hydrogen peroxide solution with the mass fraction of 30% to obtain reaction solution IV;
fifthly, stirring the reaction solution IV for reaction for 20min at the stirring speed of 300r/min, then performing ultrasonic treatment for 50min at the ultrasonic power of 350W, standing for 7h, and pouring out the supernatant to obtain a mixture I;
sixthly, cleaning the mixture I at a centrifugal speed of 8000r/min by using hydrochloric acid with a mass fraction of 15% as a cleaning agent until no precipitation is generated when the supernatant of the mixture I is added with 0.15mol/L barium chloride solution, thus obtaining the mixture I after being cleaned by the hydrochloric acid;
seventhly, 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;
drying the mixture I cleaned by the deionized water in a freeze dryer to obtain a solid I, and finally grinding the solid I and sieving the solid I through a 300-mesh sieve to obtain a sieved substance, namely graphene oxide;
secondly, hydroxylation treatment of graphene oxide:
dissolving 5g of lithium aluminum hydride in 120mL of tetrahydrofuran to obtain a tetrahydrofuran solution of the lithium aluminum hydride;
secondly, adding 3g of graphene oxide into a tetrahydrofuran solution of lithium aluminum hydride, then carrying out ultrasonic treatment for 1h at the ultrasonic power of 350W, and carrying out magnetic stirring reaction for 3h at room temperature at the stirring speed of 400r/min to obtain a mixture;
thirdly, adding hydrochloric acid with the mass fraction of 37% into the mixture until the supernatant of the mixture becomes clear, then washing the mixture by using deionized water until the washing liquid is neutral, and finally drying the mixture in a vacuum drying oven at the temperature of 90 ℃ for 12 hours to obtain hydroxylated graphene oxide;
thirdly, cyanuric chloride modified graphene oxide:
adding 2g of hydroxylated graphene oxide into 100mL of tetrahydrofuran, performing ultrasonic treatment for 2h at the ultrasonic power of 350W, adding 4g of cyanuric chloride and 6g of triethylamine, and heating, stirring and refluxing for 36h at the temperature of 80 ℃ and the stirring speed of 400r/min to obtain a reaction product I;
secondly, washing the reaction product I for 3 times by using tetrahydrofuran, then washing for 5 times by using absolute ethyl alcohol, and finally drying for 4 hours in a vacuum drying oven at the temperature of 90 ℃ to obtain cyanuric chloride modified graphene oxide;
and IV, modifying the graphene oxide by using trihydroxyaminomethane:
adding 0.4g of cyanuric chloride modified graphene oxide into 60mL of acetonitrile, performing ultrasonic dispersion for 2h under the ultrasonic power of 350W, adding 0.6g of trihydroxyaminomethane and 6g of triethylamine, and heating, stirring and refluxing for 18h at the temperature of 80 ℃ to obtain a reaction product II;
and secondly, washing the reaction product II for 5 times by using absolute ethyl alcohol, and drying for 6 hours in a vacuum drying oven at the temperature of 90 ℃ to obtain the hexatomic heterocyclic ring covalent modified graphene oxide.
Fig. 1 is an infrared spectrogram, wherein a is an infrared spectrum curve of graphene oxide obtained in the first step of the example, b is an infrared spectrum curve of cyanuric chloride modified graphene oxide obtained in the third step of the example, and c is an infrared spectrum curve of six-membered heterocyclic covalently modified graphene oxide obtained in the fourth step of the example;
as can be seen from FIG. 1, GO (graphene oxide) is 3100cm-1、1716cm-1、1608cm-1And 1039cm-1The peaks at (a) correspond to the stretching vibrations of O-H, C ═ O, C ═ C and C-O-C, respectively. This indicates that a large number of oxygen-containing functional groups are shown on the GO surface; the spectrum of cyanuric chloride modified graphene oxide obtained after cyanuric chloride grafting is 1714cm-1，1568cm-1And 934cm-1Three new peaks appear, corresponding to skeleton peaks and C-Cl stretching vibration of C ═ N and C-N bonds of the triazine ring; six-membered heterocyclic covalent modified graphene oxide and cyanuric chloride modified graphene oxideIn contrast, the absorption peak of C-Cl disappeared. These results preliminarily indicate that cyanuric chloride and trishydroxyaminomethane were successfully grafted onto the GO surface.
Fig. 2 is a raman spectrum, in which a is a raman curve of graphene oxide obtained in the first step of the example, b is a raman curve of cyanuric chloride modified graphene oxide obtained in the third step of the example, and c is a raman curve of six-membered heterocycle covalently modified graphene oxide obtained in the fourth step of the example;
as can be seen from FIG. 2, the Raman diffraction spectrum of (graphene oxide) GO and its derivatives mainly includes the D band (1335 cm)-1) And the G band (1581 cm)-1) The intensity ratio of the two bands, ID/IG, is a measure of the disordered graphite. The ID/IG ratio of GO is 1.74. Compared with GO, the ID/IG value of the six-membered heterocyclic covalently modified graphene oxide (GO-TCT-Tris) obtained in the fourth step of the embodiment is slightly increased from 1.74 to 2.03, because the six-membered heterocyclic covalently modified graphene oxide obtained in the fourth step of the embodiment forms a chemical bond with a functional group on the surface of GO. The grafting of the six-membered heterocyclic covalently modified graphene oxide obtained in the fourth step of the embodiment on the surface of GO increases the active sites thereof, but the sp2 structure of the graphene does not show obvious structural damage in the modification process.
The element contents of the graphene oxide obtained in the first step of the example and the graphene oxide covalently modified by the six-membered heterocycle obtained in the fourth step of the example are shown in table 1.
TABLE 1
Note: GO is graphene oxide obtained in the first step of the embodiment, and GO-TCT-Tris is graphene oxide covalently modified by a six-membered heterocyclic ring obtained in the fourth step of the embodiment.
As can be seen from table 1, the surface of the graphene oxide mainly consists of C (59.9%) and O (40.39%), and the modified graphene oxide (i.e., the graphene oxide covalently modified by the six-membered heterocycle obtained in the fourth step of the example) has new elements of N (3.73%) and Cl (0.25%).
Fig. 3 is an XPS peak spectrum of graphene oxide obtained in one step one of the embodiment;
FIG. 4 is an XPS peak spectrum of a six-membered heterocycle covalently modified graphene oxide obtained in the fourth step of the example;
from the peak spectra of C1s in fig. 3 and fig. 4, it is seen that graphene oxide contains five characteristic peaks, and the modified graphene oxide (i.e. the graphene oxide covalently modified by a six-membered heterocycle obtained in the fourth step of the example) has a reduced C-OH peak content at 285.3eV and a new C-N peak at 285.7 eV. This indicates that cyanuric chloride and trihydroxyaminomethane have been covalently grafted to the graphene oxide surface.
Fig. 5 is an SEM image of graphene oxide obtained by one step of the example one;
FIG. 6 is an SEM image of a six-membered heterocycle covalently modified graphene oxide obtained in step IV of the embodiment;
from fig. 5 it can be seen that GO is smooth and uniform in surface but strongly aggregated, forming three dimensional layers. In FIG. 6
In the fourth step, the surface edge of the obtained six-membered heterocyclic covalently modified graphene oxide shows more folds, and the interlayer structure is loose. Because the dendritic molecules grafted on the surface of the graphene oxide play a supporting role between layers, the agglomeration of the graphene oxide is prevented.
Example three: the preparation of the graphene oxide/epoxy resin composite material is completed according to the following steps:
firstly, adding 0.036g of graphene oxide obtained in the first step of the embodiment into 15mL of acetone, and then carrying out ultrasonic treatment for 60min under the ultrasonic power of 350W to obtain a mixed solution;
adding 36g of epoxy resin E-51 into the mixed solution, then performing ultrasonic treatment at the ultrasonic power of 350W for 30min, and drying at the temperature of 80 ℃ for 12h to obtain an epoxy resin mixture;
thirdly, adding 10.8g of curing agent H256 into the epoxy resin mixture, then mechanically stirring for 15min at the speed of 3000r/min, and finally drying for 1H in vacuum at the temperature of 80 ℃ to obtain the epoxy resin mixture added with the curing agent;
fourthly, pouring the epoxy resin mixture added with the curing agent 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, and curing to obtain the graphene oxide/epoxy resin composite material;
the curing process in the fourth step comprises the following steps: curing for 2h under the conditions of vacuum degree of-30 kPa and temperature of 80 ℃, curing for 2h under the conditions of vacuum degree of-30 kPa and temperature of 100 ℃, and curing for 4h under the conditions of vacuum degree of-30 kPa and temperature of 150 ℃.
Example four: the preparation of the hexatomic heterocycle covalent modified graphene oxide/epoxy resin composite material is completed according to the following steps:
firstly, 0.036g of graphene oxide covalently modified by a six-membered heterocyclic ring obtained in the fourth step of the embodiment is added into 15mL of acetone, and then ultrasonic treatment is carried out for 60min under the ultrasonic power of 350W to obtain a mixed solution;
adding 36g of epoxy resin E-51 into the mixed solution, then performing ultrasonic treatment at the ultrasonic power of 350W for 30min, and drying at the temperature of 80 ℃ for 12h to obtain an epoxy resin mixture;
thirdly, adding 10.8g of curing agent H256 into the epoxy resin mixture, then mechanically stirring for 15min at the speed of 3000r/min, and finally drying for 1H in vacuum at the temperature of 80 ℃ to obtain the epoxy resin mixture added with the curing agent;
fourthly, pouring the epoxy resin mixture added with the curing agent 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, and curing to obtain the hexatomic heterocyclic ring covalent modified graphene oxide/epoxy resin composite material;
the curing process in the fourth step comprises the following steps: curing for 2h under the conditions of vacuum degree of-30 kPa and temperature of 80 ℃, curing for 2h under the conditions of vacuum degree of-30 kPa and temperature of 100 ℃, and curing for 4h under the conditions of vacuum degree of-30 kPa and temperature of 150 ℃.
Fig. 7 is a bar graph of tensile strength, in which 1 is the tensile strength of pure epoxy resin, 2 is the tensile strength of graphene oxide/epoxy resin composite material prepared in example three, and 3 is the tensile strength of six-membered heterocyclic covalently modified graphene oxide/epoxy resin composite material prepared in example four;
fig. 8 is a bending strength bar graph, in which 1 is the bending strength of pure epoxy resin, 2 is the bending strength of the graphene oxide/epoxy resin composite material prepared in the third example, and 3 is the bending strength of the six-membered heterocyclic covalently modified graphene oxide/epoxy resin composite material prepared in the fourth example.
As can be seen from fig. 7 and 8, the tensile strength and the bending strength of the graphene oxide/epoxy resin composite material loaded with 0.10% GO were improved by 21.79% and 18.40%, respectively, compared to the pure epoxy resin. The tensile strength and the bending strength of the six-membered heterocyclic ring covalently modified graphene oxide/epoxy resin composite material containing 0.10% of GO are improved by 37.11% and 46.90% compared with those of pure epoxy resin. The result shows that the modified graphene oxide and epoxy resin composite material has better mechanical property, and the load is effectively transferred from the matrix to the GO sheet due to better dispersity and strong interface between GO-TCT-Tris and the epoxy resin matrix.
Claims (10)
1. A method for covalently modifying graphene oxide by a six-membered heterocyclic ring is characterized in that the method for covalently modifying graphene oxide by a six-membered heterocyclic ring is completed according to the following steps:
firstly, preparing graphene oxide:
adding graphite, sodium nitrate and concentrated sulfuric acid into a three-neck flask, placing the three-neck flask in 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 reaction liquid I;
the mass fraction of the concentrated sulfuric acid in the first step is 96-98%;
the ratio of the mass of the graphite to the volume of the concentrated sulfuric acid in the first step is (6 g-8 g): 360 mL-500 mL;
the mass ratio of the sodium nitrate to the concentrated sulfuric acid in the first step (2 g-4 g) is (360 mL-500 mL);
secondly, 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 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 first step to the graphite in the first step is (20-25) to (6-8);
thirdly, heating the reaction liquid II to 35-40 ℃, reacting for 17-19 h at the temperature of 35-40 ℃, and adding distilled water to obtain reaction liquid III;
the mass ratio of the volume of the distilled water in the first step to the graphite in the first step is (400 mL-600 mL): 6 g-8 g);
stirring the reaction solution III at the stirring speed of 300 r/min-400 r/min for reaction for 1 h-2 h, and then adding distilled water and a hydrogen peroxide solution with the mass fraction of 30% to obtain a reaction solution IV;
the mass ratio of the volume of the distilled water in the first step to the graphite in the first step is (600 mL-800 mL): 6 g-8 g);
the volume of the hydrogen peroxide solution with the mass fraction of 30 percent in the first step (IV) and the mass ratio of the graphite in the first step (IV) are (40 mL-60 mL) - (6 g-8 g);
fifthly, stirring the reaction solution IV at the stirring speed of 300 r/min-400 r/min for reaction for 20 min-40 min, then carrying out ultrasonic treatment at the ultrasonic power of 350W-360W for 30 min-50 min, then standing for 6 h-8 h, and pouring out the supernatant to obtain a mixture I;
sixthly, using hydrochloric acid with the mass fraction of 14-16% as a cleaning agent, cleaning the mixture I at the centrifugal speed of 6000-8000 r/min until no precipitation is generated when the supernatant of the mixture I is added with 0.1-0.15 mol/L barium chloride solution, and obtaining the mixture I after being cleaned by the hydrochloric acid;
seventhly, 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;
drying the mixture I cleaned by the deionized water in a freeze dryer to obtain a solid I, and finally grinding the solid I and sieving the solid I through a 300-mesh sieve to obtain a sieved substance, namely graphene oxide;
secondly, hydroxylation treatment of graphene oxide:
dissolving lithium aluminum hydride in tetrahydrofuran to obtain a tetrahydrofuran solution of the lithium aluminum hydride;
the mass ratio of the lithium aluminum hydride in the second step to the volume ratio of tetrahydrofuran is (4 g-5 g):100 mL-120 mL;
secondly, firstly adding graphene oxide into a tetrahydrofuran solution of lithium aluminum hydride, then carrying out ultrasonic treatment for 0.5-1 h at the ultrasonic power of 350-360W, and carrying out magnetic stirring reaction for 2-3 h at room temperature at the stirring speed of 300-400 r/min to obtain a mixture;
the mass ratio of the graphene oxide in the second step to the volume ratio of the tetrahydrofuran in the second step is (2 g-3 g):100 mL-120 mL;
thirdly, adding hydrochloric acid with the mass fraction of 37% into the mixture until the supernatant of the mixture becomes clear, then using deionized water to clean until the cleaning solution is neutral, and finally placing the mixture into a vacuum drying oven with the temperature of 80-90 ℃ to dry for 6-12 h to obtain hydroxylated graphene oxide;
thirdly, cyanuric chloride modified graphene oxide:
firstly, adding hydroxylated graphene oxide into tetrahydrofuran, performing ultrasonic treatment for 1-2 h at the ultrasonic power of 350-360W, adding cyanuric chloride and triethylamine, and heating, stirring and refluxing for 24-36 h at the temperature of 70-80 ℃ and the stirring speed of 300-400 r/min to obtain a reaction product I;
the volume ratio of the mass of the hydroxylated graphene oxide to the tetrahydrofuran in the third step is (1 g-2 g) 100 mL;
the volume ratio of the mass of the cyanuric chloride to the tetrahydrofuran in the third step (3 g-4 g) is 100 mL;
the volume ratio of the mass of the triethylamine to the volume of the tetrahydrofuran in the third step (4 g-6 g) is 100 mL;
secondly, washing the reaction product I for 3-5 times by using tetrahydrofuran, then washing for 3-8 times by using absolute ethyl alcohol, and finally drying for 4-6 hours in a vacuum drying oven at the temperature of 80-90 ℃ to obtain cyanuric chloride modified graphene oxide;
and IV, modifying the graphene oxide by using trihydroxyaminomethane:
adding cyanuric chloride modified graphene oxide into acetonitrile, performing ultrasonic dispersion for 1-2 h at the ultrasonic power of 350-360W, adding trihydroxyaminomethane and triethylamine, heating, stirring and refluxing for 12-18 h at the temperature of 70-80 ℃, and obtaining a reaction product II;
the volume ratio of the mass of the cyanuric chloride modified graphene oxide to the acetonitrile in the fourth step is (0.2 g-0.4 g): 30 mL-60 mL;
the volume ratio of the mass of the trihydroxy aminomethane to the acetonitrile in the fourth step is (0.4 g-0.6 g): 30 mL-60 mL;
the volume ratio of the triethylamine to the acetonitrile in the step IV is (4 g-6 g): 30 mL-60 mL;
secondly, washing the reaction product II for 3 to 8 times by using absolute ethyl alcohol, and drying the reaction product II for 4 to 6 hours in a vacuum drying oven at the temperature of between 80 and 90 ℃ to obtain the hexatomic heterocyclic ring covalent modified graphene oxide.
2. The method for covalently modifying graphene oxide through a six-membered heterocyclic ring according to claim 1, wherein the mass ratio of lithium aluminum hydride to tetrahydrofuran in the second (r) step is (4.5 g-5 g) - (110 mL-120 mL).
3. The method for covalently modifying graphene oxide through a six-membered heterocyclic ring according to claim 1, wherein the volume ratio of the mass of the graphene oxide in the second step to the tetrahydrofuran in the second step is (2.5-3 g) - (110-120 mL).
4. The method for covalently modifying graphene oxide through a six-membered heterocyclic ring according to claim 1, wherein the volume ratio of the mass of the hydroxylated graphene oxide to the tetrahydrofuran in the third (r) step is (1.5 g-2 g):100 mL.
5. The method for covalently modifying graphene oxide through a six-membered heterocyclic ring according to claim 1, wherein the volume ratio of the mass of cyanuric chloride to tetrahydrofuran in step three is (3.5 g-4 g):100 mL.
6. The method for covalently modifying graphene oxide through a six-membered heterocyclic ring according to claim 1, wherein the volume ratio of the triethylamine to the tetrahydrofuran in the third step (5 g-6 g) is 100 mL.
7. The method for covalently modifying graphene oxide through a six-membered heterocyclic ring according to claim 1, wherein the volume ratio of the mass of the cyanuric chloride modified graphene oxide to the acetonitrile in the fourth (r) step is (0.3 g-0.4 g): (40 mL-60 mL).
8. The method for covalently modifying graphene oxide through a six-membered heterocyclic ring according to claim 1, wherein the volume ratio of the mass of trihydroxyaminomethane to acetonitrile in step IV is (0.5 g-0.6 g): 45 mL-60 mL.
9. The method for covalently modifying graphene oxide through a six-membered heterocyclic ring according to claim 1, wherein the volume ratio of the triethylamine to the acetonitrile in the fourth step (5-6 g) to (45-60 mL).
10. The method for covalently modifying graphene oxide through a six-membered heterocyclic ring according to claim 1, wherein in the third step, hydroxylated graphene oxide is added into tetrahydrofuran, ultrasound is performed for 1h to 2h at an ultrasound power of 350W to 360W, cyanuric chloride and triethylamine are added, and heating, stirring and refluxing are performed for 24h to 32h at a temperature of 75 ℃ to 80 ℃ and a stirring speed of 300r/min to 400r/min to obtain a reaction product I.
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| CN102220144A (en) * | 2011-04-22 | 2011-10-19 | 中国科学院宁波材料技术与工程研究所 | Preparation method of flame retardant additive |
| EP2931781A1 (en) * | 2012-12-14 | 2015-10-21 | Blue Cube IP LLC | Modified epoxy resins |
| CN104058398A (en) * | 2014-07-15 | 2014-09-24 | 福建江夏学院 | Modified graphene and preparation method thereof |
| CN108342099A (en) * | 2018-02-08 | 2018-07-31 | 青岛大学 | A kind of method of surface of graphene oxide chemical modification and application |
| CN108864774A (en) * | 2018-07-20 | 2018-11-23 | 江南大学 | A kind of preparation method of the reactive self-dispersing nano carbon black of cotton fabric dyeing process |
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