CN110343406B - Fluorine-containing silane modified graphene oxide and preparation method and application thereof - Google Patents
Fluorine-containing silane modified graphene oxide and preparation method and application thereof Download PDFInfo
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Abstract
The application discloses fluorine-containing silane modified graphene oxide and a preparation method and application thereof. The preparation method of the fluorine-containing silane modified graphene oxide comprises the following steps: and mixing the graphene oxide dispersion liquid with a fluorine-containing silane solution, and reacting under the action of a template agent to obtain the fluorine-containing silane modified graphene oxide. According to the preparation method, a template method is adopted, the fluorine-containing silane and the graphene oxide are subjected to a grafting reaction, the amphiphilic graphene oxide with good performance can be obtained, the dispersibility of the graphene oxide in water and an oil solvent is greatly improved, and the application of the graphene oxide is further expanded.
Description
Technical Field
The application relates to fluorine-containing silane modified graphene oxide, in particular to fluorine-containing silane modified graphene oxide and a preparation method and application thereof, and belongs to the field of chemical materials.
Background
Graphene is the thinnest material known, and has excellent corrosion resistance, super-strong electric conductivity and heat conductivity due to a unique lamellar structure. The material has attracted much attention in the fields of paint, battery, electronic material, heat dissipating material, etc. The graphene oxide is a graphene derivative material with a large number of oxygen-containing groups on the surface, and the oxygen-containing groups on the surface of the graphene oxide material can enable the material to be modified in various ways, so that the controllable design of functions can be realized. The surface of the graphene oxide contains oxygen-containing groups such as carboxyl, epoxy, hydroxyl and the like, and the surfaces of the oxygen-containing groups are extremely hydrophilic, so that the graphene oxide has dispersibility in an aqueous solution and does not have dispersibility in most oily solvents, and the application of the graphene oxide in the fields of composite materials and the like is greatly limited. Therefore, it is necessary to modify graphene oxide through amphiphilic modification to improve the dispersibility of graphene oxide in an oily solvent. How to realize graphene oxide with an amphiphilic function and improve the general performance of the graphene oxide is a difficult point in the field of graphene oxide functionalization.
At present, the preparation of the amphiphilic graphene oxide mainly comprises the step of reacting aliphatic amine (such as polyaniline, perfluorooctylamine, hexadecylamine and the like) containing long carbon chains, amphiphilic polymer, halogenated alkane and the like with active groups of the graphene oxide to obtain the amphiphilic graphene oxide. For example:
the invention patent with application publication number CN107722352A discloses a preparation method of long-chain alkylamine functionalized graphene, which mainly comprises the steps of adding graphene oxide into an acid solution, adjusting the pH to be less than 7, adding an ethanol solution of long-chain alkylamine, carrying out a grafting reaction of the graphene oxide under a heating condition, and repeatedly washing and centrifuging to obtain long-chain alkylamine chemically functionalized graphene powder. In the method, sulfuric acid, nitric acid and sulfuric acid are added as catalysts in the reaction process, so that certain danger is generated, and the graphene oxide part is reduced after the reaction, so that the structure of the graphene is damaged, and the electric conduction and heat conduction performances of the graphene are influenced.
The invention patent with application publication number CN103819880A discloses a method for modifying graphene modified epoxy resin by an amphiphilic polymer, which mainly comprises the following steps: and (2) sequentially adding glycidyl methacrylate, vinyl carbazole, an initiator and a solvent into the round-bottom flask, and reacting for 8-16h at 50-100 ℃ under the condition of introducing nitrogen to obtain the amphiphilic graphene oxide. The method requires reaction under high-temperature and closed conditions, and the conditions are strict and are not suitable for industrial production.
The invention patent with application publication number CN103771400A discloses a method for actually preparing graphene dispersion liquid by utilizing pyrenebenzoic acid polyether ester amphipathy, which comprises the steps of taking polyethylene glycol monomethyl ether, p-aminobenzoic acid and 1-pyreneboric acid as raw materials, obtaining hydrophilic p-aminobenzoic acid polyether ester through esterification reaction, introducing HBr reacted with the 1-pyreneboric acid, and then reacting with the pyreneboric acid to synthesize the amphiphilic graphene stripping agent; dissolving the compound and graphene in H2And (4) in the O solution, performing ultrasonic treatment, centrifuging and washing to obtain the amphiphilic graphene oxide. The method has the advantages of easily available raw materials, complicated preparation process, and suitability for mass production.
The invention patent with application publication number CN108043242A discloses a preparation method of a graphene oxide film with adjustable surface wettability, which mainly comprises the following steps: firstly, preparing graphene oxide, then loading an initiator on the surface of the graphene oxide, and then reacting polar or nonpolar monomers (esters) containing double bonds with the graphene oxide by utilizing yard transfer radical polymerization to obtain the hydrophilic, hydrophobic and amphiphilic graphene oxide self-assembled film. The method adopts amphiphilic graphene oxide prepared from different polar and nonpolar monomers, and is only suitable for respective oil/water systems.
In the existing methods for modifying graphene oxide, fatty amine (dodecylamine, hexadecylamine, octadecylamine and polyaniline) and the like are mostly adopted to modify carboxyl and epoxy groups of graphene oxide. The studies suggest that graphene oxide sheets are large, the contact probability with aliphatic amine is small, and the reactivity of carboxyl and amino groups is not very high. Therefore, the amphiphilic graphene oxide obtained by modifying graphene oxide with fatty amine has not very good performance. The method for modifying through the amphiphilic polymer needs to prepare the amphiphilic polymer firstly, and the method has the advantages of difficult obtainment of raw materials, complex preparation process and unsuitability for batch production. Therefore, there is a need for a method for preparing modified graphene oxide having a simple process and good dispersibility in both water and oily reagents.
Disclosure of Invention
According to the first aspect of the application, a template method is adopted in the preparation method, the fluorine-containing silane and the graphene oxide are subjected to a grafting reaction, the amphiphilic graphene oxide with good performance can be obtained, the dispersibility of the graphene oxide in water and an oil solvent is greatly improved, and the application of the graphene oxide is further expanded.
The preparation method of the fluorine-containing silane modified graphene oxide is characterized by comprising the following steps: and mixing the graphene oxide dispersion liquid with a fluorine-containing silane solution, and reacting under the action of a template agent to obtain the fluorine-containing silane modified graphene oxide.
Preferably, the preparation method of the graphene oxide dispersion liquid comprises the following steps: and dispersing graphene oxide in a solvent, and shearing to obtain the graphene oxide dispersion liquid.
Preferably, the solvent is deionized water, and the concentration of the graphene oxide in the graphene oxide dispersion liquid is 0.1-0.5 mg/ml.
Preferably, the shearing is ultrasonic shearing or high-speed shearing; the high-speed shearing rotating speed is 1000-2000 rpm.
Preferably, the particle size of the graphene oxide in the graphene oxide dispersion liquid is in the range of 100nm to 300 nm.
Preferably, the solvent of the fluorine-containing silane solution is an alcohol solvent.
Preferably, the alcohol solvent is at least one selected from methanol, ethanol, propanol, butanol, propylene glycol and butylene glycol.
Preferably, the fluorine-containing silane is selected from at least one of perfluorodecyltriethoxysilane, perfluorodecyltrimethoxysilane, perfluorododecylsilane, tridecafluorooctyltrimethoxysilane.
Preferably, the template agent is selected from at least one of kerosene and paraffin. A fluorine-containing silane substance is reacted with carboxyl and hydroxyl groups on one side of graphene oxide by using a template agent, and a hydrophobic group is grafted to one side of graphene oxide, so that the one side presents excellent oleophilic properties, and the other side maintains hydrophilic characteristics, thereby converting the graphene oxide from two-sided hydrophilicity to one-sided hydrophilicity and oleophilic properties. The template used in the present invention is not limited to kerosene and paraffin, and any template that can perform the same function as kerosene and paraffin in the present invention should be considered within the scope of the present invention.
Preferably, the mass ratio of the graphene oxide to the fluorine-containing silane is 1:1 to 1: 10.
Preferably, the templating agent, the fluorosilane, and the alcohol solvent form a templating agent/fluorosilane/alcohol solvent dispersion.
Preferably, the ratio of the volume of the template agent to the volume of the template agent/fluorine-containing silane/alcohol solvent dispersion liquid is 1:3 to 5: 6.
Preferably, in the template/fluorine-containing silane/alcohol solvent dispersion liquid, the concentration of the fluorine-containing silane is 3-7 mg/ml.
In a preferred embodiment, the graphene oxide dispersion liquid is mixed with a fluorine-containing silane solution and then reacts under the action of a template agent, and the method comprises the following steps:
a) shearing graphene oxide dispersed in a solvent to obtain a graphene oxide dispersion liquid;
b) mixing the fluorine-containing silane with an alcohol solvent, and then adding a template agent to obtain a template agent/fluorine-containing silane/alcohol solvent dispersion liquid;
c) and mixing and reacting the graphene oxide dispersion liquid with the template agent/fluorine-containing silane/alcohol solvent dispersion liquid to obtain the fluorine-containing silane modified graphene oxide.
Preferably, the reaction in step c) is a stirred reaction; the conditions of the stirring reaction are as follows: the stirring speed is 700-1000 rpm; the stirring time is 6-8 hours.
Preferably, the duration of the reaction is in the range of 10 hours to 16 hours.
Preferably, separation and cleaning are carried out after the reaction; the separation comprises centrifugation; the centrifugal separation conditions are as follows: centrifugation at 3000-.
Preferably, the washing is performed with water, deionized water or a combination thereof. In the invention, kerosene adsorbed on the surface of the nanosheet, unreacted fluorine-containing silane and graphene oxide can be cleaned off by performing centrifugation and cleaning for multiple times, which is beneficial to subsequent dispersion of fluorine-containing silane modified graphene oxide in water and an oily reagent.
As a specific embodiment, the preparation method of the fluorine-containing silane modified graphene oxide comprises the following steps:
step (1): diluting graphene oxide with deionized water, and obtaining graphene oxide with a smaller particle size by adopting a high-speed shearing method;
step (2): weighing a certain amount of kerosene as a template agent, hydrolyzing fluorine-containing silane in ethanol, and preparing kerosene/fluorine-containing silane/ethanol dispersion liquid;
and (3): slowly adding the graphene oxide with the smaller particle size in the step (1) into the kerosene/fluorine-containing silane/ethanol dispersion liquid prepared in the step (2), stirring at medium speed, reacting for a period of time, centrifuging, cleaning, and centrifuging to obtain the amphiphilic graphene oxide.
Optionally, the amphiphilic graphene oxide is dispersed by ethanol, dripped onto a glass slide, dried by an oven, and subjected to contact angle test of water and oil.
Alternatively, the amphiphilic graphene oxide was dispersed in various solvents, and the phenomenon was observed.
According to a second aspect of the present application, there is provided a fluorine-containing silane modified graphene oxide prepared according to the above preparation method. The graphene oxide has good dispersibility in water and an oily solvent.
According to a third aspect of the application, the application of the fluorine-containing silane modified graphene oxide in electronic materials, batteries, hydrogen storage materials, heat dissipation materials and coatings is provided.
The beneficial effects that this application can produce include:
1) in the preparation method, the fluorine-containing silane is grafted to one end of the graphene oxide by a template method and a one-step method to obtain the graphene oxide with good amphiphilic property, and the interfacial tension between water and oil is reduced. The preparation process is safe and simple, and the prepared amphiphilic graphene oxide has lower contact angles for water and oil and has good dispersibility in water and various oily solvents.
2) The fluorine-containing silane modified graphene oxide provided by the invention can be applied to the fields of electronic materials, batteries, hydrogen storage materials, heat dissipation materials, coatings and the like.
Drawings
Fig. 1 is an infrared spectrum before and after modification of Graphene Oxide (GO) according to example 1 of the present invention.
Fig. 2 shows the dispersion of amphiphilic graphene oxide in water, ethanol, toluene, xylene, and cyclohexane.
Detailed Description
The present application will be described in detail with reference to examples, but the present application is not limited to these examples.
The raw materials in the examples of the present application were all purchased commercially, unless otherwise specified.
Wherein the graphene oxide is purchased from Hexagon scientific and technology corporation, model SE-3122.
The analysis method in the examples of the present application is as follows:
the contact angle test was performed using a JC2000D3 contact angle tester (available from shanghai zhongchen digital devices technologies, inc.).
The infrared test was performed using a Nicolet iS50 Fourier transform infrared spectrometer (available from Saimer Feishell science Co., Ltd.).
Example 1
(1) Diluting the purchased graphene oxide with deionized water, carrying out high-speed shearing on the deionized water dispersion liquid of the graphene oxide by adopting a high-speed stirrer, controlling the stirring speed to be 2000rpm, and stirring for 3 hours to obtain the water dispersion liquid of the graphene oxide, wherein in the water dispersion liquid of the graphene oxide, the concentration of the graphene oxide is 0.5mg/ml, and the particle size of the sheared graphene oxide is 100-300 nm.
(2) 0.15g of perfluorodecyl triethoxysilane was hydrolyzed in 12ml of ethanol to form a perfluorodecyl triethoxysilane solution, and 18ml of kerosene was added as a template to the perfluorodecyl triethoxysilane solution to prepare 30ml of kerosene/perfluorodecyl triethoxysilane/ethanol dispersion.
(3) And (3) taking 300ml of the graphene oxide aqueous dispersion in the step (1), slowly adding the graphene oxide aqueous dispersion into the kerosene/perfluorodecyl triethoxysilane/ethanol dispersion prepared in the step (2), and stirring the mixed solution at the speed of 700rpm for 6 hours to react the graphene oxide with the perfluorodecyl triethoxysilane.
(4) After 10 hours of reaction, centrifuging, cleaning and centrifuging the reaction product to obtain the amphiphilic graphene oxide, wherein the centrifuging speed is 3000rpm, and the centrifuging time is 2 hours.
Example 2
(1) Diluting the purchased graphene oxide with deionized water, and shearing the deionized water dispersion liquid of the graphene oxide at a high speed by using a high-speed stirrer, wherein the stirring speed is controlled to be 1500rpm, and the stirring time is 2.5 hours, so as to obtain the aqueous dispersion liquid of the graphene oxide, wherein in the aqueous dispersion liquid of the graphene oxide, the concentration of the graphene oxide is 0.2mg/ml, and the particle size of the sheared graphene oxide is 100-300 nm.
(2) 0.21g of perfluorodecyltrimethoxysilane-containing solution was hydrolyzed in 17ml of methanol to form a perfluorodecyltrimethoxysilane solution, and 13g of paraffin wax was added to the perfluorodecyltrimethoxysilane solution as a template to prepare a 30ml paraffin wax/perfluorodecyltrimethoxysilane/methanol dispersion.
(3) And (3) taking 400ml of the graphene oxide aqueous dispersion in the step (1), slowly adding the graphene oxide aqueous dispersion into the paraffin/perfluorodecyl trimethoxy silane/methanol dispersion prepared in the step (2), and stirring the mixed solution at the speed of 800rpm for 7 hours to react the graphene oxide with the perfluorodecyl trimethoxy silane.
(4) After the reaction is carried out for 12 hours, the reaction product is centrifuged, cleaned and centrifuged to obtain the amphiphilic graphene oxide, wherein the centrifugation speed is 4500rpm, and the centrifugation time is 3 hours.
Example 3
(1) Diluting the purchased graphene oxide with deionized water, carrying out high-speed shearing on the deionized water dispersion liquid of the graphene oxide by adopting a high-speed stirrer, controlling the stirring speed to be 1000rpm, and stirring for 4 hours to obtain the water dispersion liquid of the graphene oxide, wherein in the water dispersion liquid of the graphene oxide, the concentration of the graphene oxide is 0.1mg/ml, and the particle size of the sheared graphene oxide is 100-300 nm.
(2) 0.09g of tridecafluorooctyltrimethoxysilane was hydrolyzed in 7ml of propanol to form a tridecafluorooctyltrimethoxysilane solution, and 23ml of kerosene was added as a template to the tridecafluorooctyltrimethoxysilane solution to prepare a 30ml kerosene/tridecafluorooctyltrimethoxysilane/propanol dispersion.
(3) And (3) taking 200ml of the graphene oxide aqueous dispersion in the step (1), slowly adding the graphene oxide aqueous dispersion into the kerosene/tridecafluorooctyltrimethoxysilane/propanol dispersion prepared in the step (2), and stirring the mixed solution at the speed of 1000rpm for 8 hours to react the graphene oxide with the tridecafluorooctyltrimethoxysilane.
(4) After 16 hours of reaction, centrifuging, cleaning and centrifuging the reaction product to obtain the amphiphilic graphene oxide, wherein the centrifuging speed is 5000rpm, and the centrifuging time is 4 hours.
Analysis of the product
The infrared spectrograms of graphene oxide before modification and amphiphilic graphene oxide after modification with perfluorodecyltriethoxysilane in example 1 were measured, and the results are shown in fig. 1. Fig. 1 is an infrared spectrum of Graphene Oxide (GO) before and after modification with perfluorodecyltriethoxysilane. As can be seen from FIG. 1, for GO, at 1620cm-1And 1727cm-1The characteristic absorption peaks at (a) are attributed to C ═ C and C ═ O bonds, respectively. These peaks are almost the same for the amphiphilic graphene oxide compared to GO. After the reaction, Si-O-C (1128 cm) was formed-1) Characteristic absorption peak, and C-F (1230 cm)-1) Characteristic absorption peak. The infrared spectrum preliminarily proves that the fluorine-containing silane and the graphene oxide have a grafting reaction.
And (3) performance testing:
(1) contact angle test: the amphiphilic graphene oxide prepared in examples 1 to 3 and graphene oxide before being modified by the fluorine-containing silane were dispersed with deionized water, dropped on a glass slide, oven-dried, and then subjected to a contact angle test of water and oil using a JC2000D3 contact angle measuring instrument, the test results are shown in table 1, wherein when the contact angle with oil was measured, the reagent used was n-hexadecane.
Table 1 contact angle test results
| Water contact Angle (°) | Oil contact Angle (°) | |
| Graphene oxide (before modification) | 31.5 | 77.5 |
| Example 1 | 48 | 17.0 |
| Example 2 | 43 | 23.0 |
| Example 3 | 41.5 | 28.5 |
As can be seen from table 1, the water contact angle and the oil contact angle of the unmodified graphene oxide are 31.5 ° and 77.5 °, respectively, which indicates that the unmodified graphene oxide is stronger in hydrophilicity and poorer in lipophilicity; the water contact angle of the amphiphilic graphene oxide obtained after modification by the fluorine-containing silane is 40-50 degrees, the oil contact angle is reduced to 15-30 degrees, and the result shows that the amphiphilic graphene oxide modified by the fluorine-containing silane has good hydrophilicity and lipophilicity, so that the fact that the fluorine-containing silane is successfully grafted with the graphene oxide is further proved.
(2) And (3) testing the dispersibility: the amphiphilic graphene oxides prepared in examples 1 to 3 were dispersed in water, ethanol, toluene, xylene, and cyclohexane, respectively, and the phenomenon was observed as shown in fig. 2.
After standing dispersions of amphiphilic graphene oxide in different solvents (water, ethanol, toluene, xylene and cyclohexane) at room temperature for 48 hours, no precipitate is generated, and the dispersions are still uniformly dispersed solutions. The amphiphilic graphene oxide has good dispersibility in solvents such as water, ethanol, toluene, xylene and cyclohexane, and the method provided by the invention is further proved to be capable of successfully modifying the graphene oxide by using the fluorine-containing silane, so that the fluorine-containing silane modified graphene oxide has good hydrophilicity and good lipophilicity, and can be widely applied to the fields of electronic materials, batteries, hydrogen storage materials, heat dissipation materials, coatings and the like.
Although the present application has been described with reference to a few embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the application as defined by the appended claims.
Claims (15)
1. A preparation method of fluorine-containing silane modified graphene oxide is characterized by comprising the following steps:
mixing the graphene oxide dispersion liquid with a fluorine-containing silane solution, and reacting under the action of a template agent to obtain fluorine-containing silane modified graphene oxide;
the template agent is selected from kerosene;
the particle size of the graphene oxide in the graphene oxide dispersion liquid is within the range of 100nm to 300 nm.
2. The method according to claim 1, wherein the graphene oxide dispersion liquid is prepared by a method comprising:
and dispersing graphene oxide in a solvent, and shearing to obtain the graphene oxide dispersion liquid.
3. The preparation method according to claim 2, wherein the solvent is deionized water, and the concentration of the graphene oxide in the graphene oxide dispersion liquid is 0.1-0.5 mg/ml.
4. The production method according to claim 2, wherein the shearing is ultrasonic shearing or high-speed shearing; the high-speed shearing rotating speed is 1000-2000 rpm.
5. The method according to claim 1, wherein the solvent of the fluorine-containing silane solution is an alcohol solvent.
6. The method according to claim 5, wherein the alcoholic solvent is at least one selected from methanol, ethanol, propanol, butanol, propylene glycol and butylene glycol.
7. The method according to claim 1, wherein the fluorine-containing silane is at least one selected from the group consisting of perfluorodecyltriethoxysilane, perfluorodecyltrimethoxysilane, perfluorododecylsilane, and tridecafluorooctyltrimethoxysilane.
8. The preparation method according to claim 1, wherein the mass ratio of the graphene oxide to the fluorine-containing silane is 1:1 to 1: 10.
9. The method according to claim 5, wherein the template, the fluorine-containing silane, and the alcohol solvent form a template/fluorine-containing silane/alcohol solvent dispersion.
10. The method according to claim 9, wherein the ratio of the volume of the template agent to the volume of the template agent/fluorine-containing silane/alcohol solvent dispersion is 1:3 to 5: 6.
11. The method according to claim 9, wherein the concentration of the fluorine-containing silane in the template/fluorine-containing silane/alcohol solvent dispersion liquid is 3 to 7 mg/ml.
12. The preparation method of claim 1, wherein the graphene oxide dispersion liquid is mixed with the fluorine-containing silane solution and then reacts under the action of a template agent, and the preparation method comprises the following steps:
a) shearing graphene oxide dispersed in a solvent to obtain a graphene oxide dispersion liquid;
b) mixing the fluorine-containing silane with an alcohol solvent, and then adding a template agent to obtain a template agent/fluorine-containing silane/alcohol solvent dispersion liquid;
c) and mixing and reacting the graphene oxide dispersion liquid with the template agent/fluorine-containing silane/alcohol solvent dispersion liquid to obtain the fluorine-containing silane modified graphene oxide.
13. The method according to claim 12, wherein the reaction in step c) is a stirring reaction;
the conditions of the stirring reaction are as follows: the stirring speed is 700-1000 rpm;
the stirring time is 6-8 hours.
14. The method of claim 12, wherein the duration of the reaction is in the range of 10 hours to 16 hours.
15. The production method according to claim 12, wherein separation and washing are performed after the reaction;
the separation comprises centrifugation;
the centrifugal separation conditions are as follows: centrifugation at 3000-.
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