CN112777590A - Preparation method of amphiphilic graphene oxide and surfactant containing amphiphilic graphene oxide - Google Patents
Preparation method of amphiphilic graphene oxide and surfactant containing amphiphilic graphene oxide Download PDFInfo
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Abstract
The application discloses a preparation method of amphiphilic graphene oxide, which comprises the following steps: (1) adding amino polyalcohol into dispersion liquid containing graphene oxide, and carrying out hydrophilic modification to obtain a precursor I; (2) and adding a silane coupling agent into the dispersion liquid containing the precursor I, and carrying out oleophylic modification to obtain the amphiphilic graphene oxide. The method obviously improves the hydrophilic and oleophilic performances of the graphene oxide.
Description
Technical Field
The application relates to amphiphilic graphene oxide, and belongs to the field of graphene modification.
Background
Graphene is a material with excellent properties developed in recent years and is formed by sp from carbon atoms2The single atomic layer of hybrid junctions constitutes the thinnest two-dimensional material currently found. This particular structure makes it possible to includeHas many peculiar physical and chemical properties, such as high specific surface area, excellent heat-conducting property, mechanical property, electron transfer capacity and the like. The graphene oxide has amphiphilic performance, and has certain hydrophilicity due to a large number of oxygen-containing groups such as hydroxyl, epoxy, carboxyl and the like on the surface, and the cyclic carbon skeleton has lipophilicity, so that the graphene oxide integrally shows certain amphiphilic performance; however, the limited amphiphilicity provided by the oxygen-containing group and the carbon backbone alone limits further applications of graphene oxide.
Disclosure of Invention
According to one aspect of the application, a method for preparing amphiphilic graphene oxide is provided, which aims at the defects of the existing graphene oxide material that the amphiphilic performance is insufficient and the graphene oxide material is difficult to be used as a surface active substance; and due to the fact that the graphene oxide is poor in hydrophilicity and poor in stability in water, the hydrophilicity and lipophilicity of the graphene oxide are improved.
The preparation method of the amphiphilic graphene oxide is characterized by comprising the following steps:
(1) adding amino polyalcohol into dispersion liquid containing graphene oxide, and carrying out hydrophilic modification to obtain a precursor I;
(2) and adding a silane coupling agent into the dispersion liquid containing the precursor I, and carrying out oleophylic modification to obtain the amphiphilic graphene oxide.
Optionally, the aminopolyol in step (1) is selected from at least one of glucosamine, tris (hydroxymethyl) aminomethane, 2-amino-1, 3-propanediol, 3-amino-1, 2-propanediol.
Optionally, the mass ratio of the amino polyol to the graphene oxide in the step (1) is 1: 100-100: 1;
the concentration of the graphene oxide in the dispersion liquid containing the graphene oxide is 0.01-10 mg/mL;
the particle size of the graphene oxide in the dispersion liquid containing the graphene oxide is 10-500 nm.
Optionally, the conditions for hydrophilic modification in step (1) are: and (3) reacting for 2-20 hours at 0-40 ℃ under stirring and/or ultrasonic conditions.
Optionally, performing separation after the hydrophilic modification in step (1);
the separation mode comprises the following steps: and adding a flocculating agent into the reaction system after hydrophilic modification, and separating to obtain the precursor I.
Optionally, the flocculant is selected from at least one of sodium chloride, calcium chloride, potassium chloride and magnesium chloride;
the mass ratio of the flocculating agent to the hydrophilically modified reaction system is 1: 10-20: 1.
Optionally, the silane coupling agent in step (2) is selected from at least one of hexadecyl trimethoxy silane, hexadecyl triethoxy silane, dodecyl trimethoxy silane, dodecyl triethoxy silane, octadecyl trimethoxy silane, and octadecyl triethoxy silane.
Optionally, the mass concentration of the precursor I in the dispersion containing the precursor I in the step (2) is 0.01-10 mg/mL.
Optionally, the solvent in the dispersion liquid containing the precursor I is an alcohol-water mixed solution of 1/10-10/1 v/v.
Optionally, the mass ratio of the silane coupling agent to the dispersion containing the precursor I is 1: 100-100: 1.
Optionally, the conditions of the oleophilic modification in step (2) are: and (3) reacting for 0.5-10 hours at 10-100 ℃ under at least one of stirring, shaking and shaking tables.
Optionally, the lipophilic modification is a two-stage reaction; the temperature of the first stage reaction is 45-55 ℃, and the time of the first stage reaction is 0.5-5 hours; the temperature of the second-stage reaction is 70-90 ℃, and the time of the second-stage reaction is 0.1-5 hours.
Optionally, the lipophilic modification is carried out under the condition that the pH value is 8-10;
optionally, the lipophilic modification is performed at a pH of 9.
Optionally, after the oleophylic modification in the step (2), separating, washing, and drying to obtain the amphiphilic graphene oxide.
According to another aspect of the present application, there is provided an amphiphilic graphene oxide prepared by the method. The amphiphilic graphene oxide greatly improves the amphiphilic performance of the graphene oxide.
According to still another aspect of the present application, there is provided a surfactant characterized by containing at least one of the amphiphilic graphene oxides prepared according to the method.
The beneficial effects that this application can produce include:
1) according to the preparation method of the amphiphilic graphene oxide, the prepared amphiphilic graphene oxide material has good activity and can obviously reduce the interfacial tension; the emulsifying property is obviously improved, and emulsion can be formed by adding water/heptane and can exist stably.
2) According to the preparation method of the amphiphilic graphene oxide, the hydrophilicity and the lipophilicity of the modified amphiphilic graphene oxide are improved, so that the solubility in water and oil is obviously enhanced.
Drawings
Fig. 1 is an infrared spectrum of graphene oxide before modification in example 1.
Fig. 2 is an infrared spectrum of sample 1 of modified amphiphilic graphene oxide in example 1.
FIG. 3 is a photograph of an emulsion formed in sample 1 of the present application.
FIG. 4 is a photograph of an emulsion formed in sample 1 of the present application after standing for 15 days.
Detailed Description
The present application will be described in detail with reference to examples, but the present application is not limited to these examples.
Unless otherwise specified, the raw materials and catalysts in the examples of the present application were purchased commercially, wherein the source of graphene oxide was Hexah materials science and technology, Inc.
In the examples, the mass ratio of sodium chloride to water in the brine solution was 1: 100.
The analysis method in the examples of the present application is as follows:
the chemical structure analysis of the material was performed by using a seemer fiyer Nicolet is50 fourier transform infrared spectrometer.
Example 1 preparation method of amphiphilic graphene oxide
1) Dispersing 0.5g of graphene oxide in 100ml of deionized water, slowly adding 0.5g of glucosamine under the stirring condition, stirring for 10min after dropwise adding is finished, and then carrying out ultrasonic reaction for 5 hours;
2) after the reaction is finished, adding 1g of sodium chloride into the solution, stirring for 10 minutes, centrifuging (rotating speed of 3000rpm for 5min), and collecting precipitates; after washing the precipitate with brine three times, dispersing the precipitate in 100ml of ethanol/water mixed solution (ethanol/water volume ratio is 50: 50);
3) adding 1g of silane coupling agent hexadecyl trimethoxy silane into the mixed solution under the stirring condition, adjusting the pH value of the whole solution to 9 by using 1mol/L sodium hydroxide solution, stirring and reacting for 1 hour at 50 ℃, and then heating to 80 ℃ and stirring and reacting for 5 hours;
4) after the reaction, the reaction mixture was cooled to room temperature, centrifuged (at 3000rpm for 5min), and the precipitate was collected and washed with an ethanol/water mixed solution (ethanol/water volume ratio of 50: 50) and centrifuging and cleaning for three times to remove unreacted silane coupling agent, and drying to obtain the amphiphilic graphene oxide, namely the sample 1.
Example 2 preparation method of amphiphilic graphene oxide
The procedure was the same as in example 1 except that tris (hydroxymethyl) aminomethane was used as glucosamine in step 1), to prepare sample 2.
Example 3 preparation method of amphiphilic graphene oxide
The procedure was the same as in example 1, except that 2-amino-1, 3-propanediol was used as glucosamine in step 1), to prepare sample 3.
Example 4 preparation method of amphiphilic graphene oxide
The procedure was the same as in example 1, except that 3-amino-1, 2-propanediol was used as glucosamine in step 1), and sample 4 was prepared.
Example 5 preparation method of amphiphilic graphene oxide
The specific operation was the same as in example 1, except that octadecyltrimethoxysilane was used as the silane coupling agent in step 3), and sample 5 was prepared.
Example 6 preparation method of amphiphilic graphene oxide
The procedure of example 1 was followed except that the reaction time in step 3) was 2 hours, to prepare sample 6.
Example 7 preparation method of amphiphilic graphene oxide
The procedure of example 1 was followed except that the reaction time in step 3) was 4 hours, to prepare sample 7.
Example 8 Infrared Spectroscopy testing of amphiphilic graphene oxide
The graphene oxide before modification and the modified sample 1 in example 1 were dried and then placed in a fourier transform infrared spectrometer for testing.
Fig. 1 is an infrared spectrum of graphene oxide before modification, and fig. 2 is a spectrum of an amphiphilic graphene oxide sample 1 after modification.
Compared with the infrared spectrogram of graphene oxide before modification, 1727cm in graphene oxide on the infrared spectrum after modification can be seen-1The absorption peak of carbonyl stretching vibration disappears, and secondary alcohol and ether (1134 cm) appear-1) The infrared characteristic absorption peak of the glucosamine proves that the glucosamine is successfully grafted on the graphene oxide; it can also be seen that the modified IR spectrum has a strong methyl group (1376 cm)-1And 2954cm-1) Methylene (1457 cm)-1，2851cm-1And 2922cm-1) And an infrared characteristic absorption peak at 1049cm-1A stretching vibration absorption peak representing a Si-O-Si bond appears, and the success of grafting the hexadecyl trimethoxy silane on the graphene oxide is proved.
Example 9 emulsification Performance testing of amphiphilic graphene oxide
The emulsion formed by sample 1 is shown in fig. 3, and the emulsion after standing for 15 days is shown in fig. 4, and the emulsion is stable and has no obvious change.
The stability of the emulsions formed by the other samples was similar to that of sample 1.
Example 10 emulsification Performance testing of amphiphilic graphene oxide
The stability of the emulsions formed by the other samples was similar to that of sample 1.
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 (10)
1. A preparation method of amphiphilic graphene oxide is characterized by comprising the following steps:
(1) adding amino polyalcohol into dispersion liquid containing graphene oxide, and carrying out hydrophilic modification to obtain a precursor I;
(2) and adding a silane coupling agent into the dispersion liquid containing the precursor I, and carrying out oleophylic modification to obtain the amphiphilic graphene oxide.
2. The method according to claim 1, wherein the aminopolyol in step (1) is at least one selected from the group consisting of glucosamine, tris (hydroxymethyl) aminomethane, 2-amino-1, 3-propanediol and 3-amino-1, 2-propanediol.
3. The preparation method according to claim 1, wherein the mass ratio of the aminopolyol to the graphene oxide in the step (1) is 1:100 to 100: 1;
the concentration of the graphene oxide in the dispersion liquid containing the graphene oxide is 0.01-10 mg/mL;
the particle size of the graphene oxide in the dispersion liquid containing the graphene oxide is 10-500 nm.
4. The production method according to claim 1, wherein the conditions for the hydrophilic modification in step (1) are: and (3) reacting for 2-20 hours at 0-40 ℃ under stirring and/or ultrasonic conditions.
5. The production method according to claim 1, wherein the hydrophilic modification in step (1) is followed by separation;
the separation mode comprises the following steps: adding a flocculating agent into the reaction system after hydrophilic modification, and separating to obtain the precursor I;
preferably, the flocculating agent is selected from at least one of sodium chloride, calcium chloride, potassium chloride and magnesium chloride;
the mass ratio of the flocculating agent to the hydrophilically modified reaction system is 1: 10-20: 1.
6. The method according to claim 1, wherein the silane coupling agent in the step (2) is at least one selected from the group consisting of hexadecyl trimethoxysilane, hexadecyl triethoxysilane, dodecyl trimethoxysilane, dodecyl triethoxysilane, octadecyl trimethoxysilane, and octadecyl triethoxysilane.
7. The preparation method according to claim 1, wherein the mass concentration of the precursor I in the dispersion containing the precursor I in the step (2) is 0.01 to 10 mg/mL;
preferably, the solvent in the dispersion liquid containing the precursor I is an alcohol-water mixed solution of 1/10-10/1 v/v;
preferably, the mass ratio of the silane coupling agent to the dispersion containing the precursor I is 1:100 to 100: 1.
8. The method according to claim 1, wherein the conditions of the oleophilic modification in step (2) are as follows: reacting for 0.5-10 hours at 10-100 ℃ under at least one of stirring, shaking and shaking tables;
preferably, the lipophilic modification is a two-stage reaction; the temperature of the first stage reaction is 45-55 ℃, and the time of the first stage reaction is 0.5-5 hours; the temperature of the second-stage reaction is 70-90 ℃, and the time of the second-stage reaction is 0.1-5 hours;
preferably, the lipophilic modification is carried out under the condition that the pH value is 8-10;
preferably, the amphiphilic graphene oxide is obtained by separation, washing and drying after the lipophilic modification in the step (2).
9. An amphiphilic graphene oxide prepared by the method of any one of claims 1 to 8.
10. A surfactant comprising at least one of the amphiphilic graphene oxides prepared by the method according to any one of claims 1 to 8.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114181716A (en) * | 2021-10-19 | 2022-03-15 | 太原理工大学 | Gas response type Pickering emulsifier, preparation method and application in Suzuki reaction |
| CN114773534A (en) * | 2022-03-24 | 2022-07-22 | 广东邦固化学科技有限公司 | Conductive PUA composite emulsion and preparation method thereof |
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Patent Citations (4)
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| CN102887507A (en) * | 2012-09-28 | 2013-01-23 | 上海理工大学 | Simple preparation method of amphipathic graphene |
| CN103553028A (en) * | 2013-10-24 | 2014-02-05 | 深圳市沃特新材料股份有限公司 | Graphene capable of being stably compounded with engineering plastics, and composite engineering plastics |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114181716A (en) * | 2021-10-19 | 2022-03-15 | 太原理工大学 | Gas response type Pickering emulsifier, preparation method and application in Suzuki reaction |
| CN114181716B (en) * | 2021-10-19 | 2023-08-15 | 太原理工大学 | Gas response type Pickering emulsifier, preparation method and application thereof in Suzuki reaction |
| CN114773534A (en) * | 2022-03-24 | 2022-07-22 | 广东邦固化学科技有限公司 | Conductive PUA composite emulsion and preparation method thereof |
| CN114773534B (en) * | 2022-03-24 | 2023-11-07 | 广东邦固化学科技有限公司 | Conductive PUA composite emulsion and preparation method thereof |
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Application publication date: 20210511 |