CN105131596A - Preparation method of graphene/polyaniline composite hollow microspheres - Google Patents
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/02—Polyamines
- C08G73/026—Wholly aromatic polyamines
- C08G73/0266—Polyanilines or derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/26—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a solid phase from a macromolecular composition or article, e.g. leaching out
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/02—Polyamines
Abstract
The invention discloses a preparation method of graphene/polyaniline composite hollow microspheres. According to the method, firstly, a graphene/polyaniline composite material is prepared; the graphene/polyaniline composite material is used as a particle emulsifier (pickering emulsifier) and is dispersed in water to be used as a water phase; styrene and initiating agents are used as oil phases for emulsification to obtain O/W type emulsion; after a dispersion phase of styrene is polymerized, polystyrene is dissolved by the solvents; the graphene/polyaniline composite hollow microspheres are obtained. The preparation method has the advantages that a pickering emulsion polymerization method is used for preparing the graphene/polyaniline composite hollow microspheres; emulsion drips with different sizes can be obtained through regulating the factors such as the consumption of the emulsifier, the oil-water ratio and the shearing rate; the size of the hollow microsphere can be simply and conveniently regulated and controlled; the method is simple and efficient; the prepared hollow microspheres have the potential application in the aspects of catalysis, sensors, supercapacitors and the like.
Description
Technical field:
The present invention relates to the preparation field of graphene composite material, particularly a kind of preparation method of graphene/polyaniline compound hollow microballoon.
Background technology:
Graphene is tightly packed by the carbon atom of individual layer and individual layer bi-dimensional cellular shape structure crystal that is that formed.In carbon nanomaterial, Graphene has large specific surface area, high conductivity because of it, good chemical property and mechanical stability, has attracted the extensive concern of investigators.The performance of these excellences makes Graphene have potential application at numerous areas, as ultracapacitor, pH sensor, field-effect transistor, gas sensor, biosensor etc.
Polyaniline is a kind of conducting polymer composite with conjugated molecule structure, there is the doping/solution doping characteristic of cheap, good environmental stability, the excellent advantage such as electroactive and uniqueness, in electricity, optics and electrochemical field extensive application.In many decades in the past, grapheme/polyaniline composite material receives the extensive concern of investigators, because matrix material has new or more excellent performance.The characteristic that two-dimensional graphene is easily reunited, makes its actual specific surface area greatly reduce, have impact on Graphene performance in actual applications.Therefore, investigators start to probe into three-dimensional graphene composite material, to obtain high performance grapheme material.Dong etc. (MaterialsChemistryandPhysics, 2012,134:576-580) take nickel foam as base material, obtain three-dimensional grapheme by chemical Vapor deposition process (CVD).The three-dimensional grapheme obtained has continuous print three-dimensional communication structure, and after itself and polyaniline compound, compare the Graphene-polyaniline of conventional two-dimensional structure, the chemical property of matrix material obtains effective raising.But adopt chemical Vapor deposition process growing graphene in article, need to carry out under 1000 DEG C of high temperature, can remaining H after reaction terminates
2etc. inflammable and explosive gas, but the three-dimensional grapheme prepared has very large porosity (>=95%) and low volume density, and whole building-up process is relatively complicated.
In recent years, hollow microspheres is paid close attention to widely because of the characteristic of its excellence, and such as specific surface area is large, density is little, good penetrability etc.Macromolecular material, inorganic materials, metal oxide materials etc. all can be made into hollow structure, are widely used in the various fields such as drug release, photoelectric material, catalysis.Less for the research of three-dimensional grapheme/polyaniline composite material at present, the particularly graphene composite material of three-dimensional hollow micro-sphere structure.
The method preparing hollow microspheres has multiple, and wherein, microemulsion polymerization method is the common method preparing tiny balloon.Be adsorbed in oil/water interface by solid particulate to carry out the emulsion that stable emulsion droplets formed and be called as Pickering emulsion, emulsifying agent used is called as particle emulsifying agents (sometimes also referred to as Pickering emulsifying agent).Pickering emulsion still has the characteristic that the stable emulsion of conventional surfactant has, therefore Pickering emulsifying agent can substitution tables surface-active agent, and Pickering emulsion compensate for, and conventional emulsion has toxicity, poor stability, emulsifying agent are difficult to the shortcomings such as separation with not enough.
Summary of the invention:
The invention provides a kind of preparation method of graphene/polyaniline compound hollow microballoon material, the method uses the method for Pickering letex polymerization to prepare graphene/polyaniline compound hollow microballoon, without the need to additionally adding tensio-active agent in preparation process, technique is simple, reaction conditions is gentleer, raw material is easy to get, with low cost.
A preparation method for graphene/polyaniline compound hollow microballoon material, comprises the steps:
(1) preparation of grapheme/polyaniline composite material: be dispersed in water by graphene oxide, add hydrazine hydrate, at 80 ~ 100 DEG C, reaction obtains Graphene in 6 ~ 12 hours.Above-mentioned graphene dispersing solution is mixed supersound process 12 ~ 24 hours with a certain amount of polystyrolsulfon acid, obtains stable black dispersion liquid; A certain amount of aniline monomer is added in above-mentioned graphene dispersing solution, add oxygenant ammonium persulphate under stirring state and cause aniline polymerization, reaction times is 5 ~ 10 hours, by the mixed solution suction filtration, the deionized water wash that obtain after reaction, obtains grapheme/polyaniline composite material;
(2) preparation of graphene/polyaniline/polystyrene compound solid microsphere: by grapheme/polyaniline composite material obtained above, by ultrasonic disperse in certain volume water; The oil phase vinylbenzene (comprising the initiator that massfraction is 0.6 ~ 2% in oil phase) of certain volume will be added in the dispersion liquid of above-mentioned grapheme/polyaniline composite material, and use clarifixator emulsification 1 ~ 5 minute, obtain O/W type emulsion; Emulsion obtained above is placed in 50 ~ 60 DEG C of water-baths, standing and reacting 15 ~ 24 hours; By centrifugal for reacted product with deionized water, washing 3 ~ 5 times, in vacuum drying oven, 30 ~ 40 DEG C of dryings 6 ~ 10 hours, obtain graphene/polyaniline/polystyrene compound solid microsphere;
(3) preparation of graphene/polyaniline compound hollow microballoon: get graphene/polyaniline obtained above/polystyrene compound solid microsphere 1 ~ 3g, add 20 ~ 60mL tetrahydrofuran (THF), stir 2 ~ 4 hours, dissolve completely to polystyrene, by solution centrifugal, tetrahydrofuran (THF) is adopted repeatedly to wash, until wash away polystyrene completely; The solid obtained is placed in vacuum drying oven, and 30 ~ 40 DEG C of dryings 1 ~ 2 hour, obtain graphene/polyaniline compound hollow microballoon.
In step (1), the mass ratio of polystyrolsulfon acid and Graphene is 50: 1 ~ 200: 1, and sonication treatment time is 15 ~ 24 hours; The mass ratio of aniline monomer and Graphene is 0.5: 1 ~ 10: 1, and the mass ratio of aniline monomer and ammonium persulphate is 1: 1 ~ 4: 1; Ultrasonic power is 200 ~ 400W.
In step (2), ultrasonic power is 200 ~ 400W, and ultrasonic time is 10 ~ 30 minutes; The rotating speed of clarifixator is 8000 ~ 30000rpm; The concentration of matrix material dispersion liquid is 1 ~ 10mg/mL; The volume ratio of oil phase and aqueous phase is 1.5: 1 ~ 1: 3; Initiator is the kick off temperature such as 2,2'-Azobis(2,4-dimethylvaleronitrile), Diisopropyl azodicarboxylate at the oil-soluble initiator of 40 ~ 65 DEG C.
In step (3), centrifugal speed is 4000 ~ 8000rpm, and the time is 2 ~ 5 minutes; Get centrifugal rear supernatant liquid to mix with equal-volume dehydrated alcohol, then prove the complete washes clean of polystyrene without precipitation.
Compared with prior art, tool of the present invention has the following advantages:
(1) can by regulating the consumption of emulsifying agent, water oil ratio, the factors such as shearing rate, obtain the emulsion droplets of different size, can the size of hollow regulating microballoon simply and easily.
(2) three-dimensional hollow micro-sphere structure, improves the specific surface area of grapheme/polyaniline composite material effectively, makes full use of the advantage of the large specific surface area of Graphene.
(3) three-dimensional grapheme/polyaniline hollow structure is that electric transmission provides high connductivity network, compare the Graphene-polyaniline of conventional two-dimensional structure, the chemical property of matrix material can effectively improve, and has potential application in sensor, ultracapacitor etc.
(4) utilize the method for Pickering emulsion to prepare graphene/polyaniline compound hollow microballoon in the present invention, method is simple, efficient, and reaction conditions is gentleer, and raw material is easy to get, with low cost.
Embodiment:
Below by embodiment, the present invention is further detailed.
Embodiment 1:
(1) preparation of grapheme/polyaniline composite material: get 30mg graphene oxide, ultrasonic disperse is in 15mL water, the DMF (DMF) adding 100mL in the suspension that this is brown obtains uniform graphene oxide dispersion.In this dispersion liquid, to add at the hydrazine hydrate 80 DEG C of 30 μ L reaction 10 hours, obtain the graphene dispersing solution of black, then mix ultrasonication with 2g polystyrolsulfon acid and within 12 hours, obtain stable black dispersion liquid.Subsequently to the aniline monomer adding 15mg in the Graphene aqueous dispersions that polystyrolsulfon acid is stable, add 15mg ammonium persulphate under vigorous stirring and cause aniline polymerization, react 12 hours at 0 DEG C.The matrix material of graphene/polyaniline is obtained by suction filtration and deionized water wash.
(2) preparation of graphene/polyaniline/polystyrene compound solid microsphere: add the 2,2'-Azobis(2,4-dimethylvaleronitrile) of 0.0273g as oil phase in 3mL vinylbenzene, get graphene/polyaniline aqueous dispersions and vinylbenzene that 3mL mass concentration is 10mg/mL in sample bottle, on high speed dispersor, under 20500rpm rotating speed, homogeneous 2min prepares Pickering emulsion.Sample bottle is placed in 50 DEG C of water-baths, standing and reacting 15 hours.By the product with deionized water washing after polymerization, centrifugal, in vacuum drying oven, 30 DEG C of dryings 8 hours, obtain graphene/polyaniline/polystyrene compound solid microsphere.
(3) preparation of graphene/polyaniline/polystyrene compound hollow microballoon: get 1g solid microsphere, be dissolved in 20mL tetrahydrofuran (THF), stir 4 hours, by solution centrifugal, speed is 4000rpm, time is 3 minutes, repeats for several times, get centrifugal after supernatant liquid, mix with isopyknic ethanol, until without precipitation after mixing, the sample obtained is placed in vacuum drying oven 30 DEG C of dryings 1 hour, namely obtains graphene/polyaniline compound hollow microballoon.
Embodiment 2:
(1) preparation of grapheme/polyaniline composite material: get 15mg graphene oxide, ultrasonic disperse is in 5mL water, and the DMF (DMF) adding 45mL in the dispersion liquid that this is brown obtains uniform graphene oxide dispersion.React 10 hours add the hydrazine hydrate 90 DEG C of 50 μ L in this dispersion liquid at, obtain the graphene dispersing solution of black.Stable black dispersion liquid within 15 hours, is obtained with 2g polystyrolsulfon acid mixing ultrasonication.Subsequently to the aniline monomer adding 45mg in the Graphene aqueous dispersions that polystyrolsulfon acid is stable, add 25mg ammonium persulphate under vigorous stirring and cause aniline polymerization, react 18 hours at 0 DEG C.The matrix material of graphene/polyaniline is obtained by suction filtration and deionized water wash.
(2) preparation of graphene/polyaniline/polystyrene compound solid microsphere: add the 2,2'-Azobis(2,4-dimethylvaleronitrile) of 0.0546g as oil phase in 4mL vinylbenzene, get graphene/polyaniline aqueous dispersions and vinylbenzene that 6mL mass concentration is 5mg/mL in sample bottle, on high speed dispersor, under 8000rpm rotating speed, homogeneous 5min prepares Pickering emulsion.Sample bottle is placed in 55 DEG C of water-baths, standing and reacting 24 hours.By the product with deionized water washing after polymerization, centrifugal, in vacuum drying oven, 35 DEG C of dryings 6 hours, obtain graphene/polyaniline/polystyrene compound solid microsphere.
(3) preparation of graphene/polyaniline/polystyrene compound hollow microballoon: get 2g solid microsphere, be dissolved in 40mL tetrahydrofuran (THF), stir 4 hours, by solution centrifugal, speed is 8000rpm, time is 2 minutes, repeats for several times, get centrifugal after supernatant liquid, mix with isopyknic ethanol, until without precipitation after mixing, the sample obtained is placed in vacuum drying oven 35 DEG C of dryings 1 hour, namely obtains graphene/polyaniline compound hollow microballoon.
Embodiment 3:
(1) preparation of grapheme/polyaniline composite material: get 15mg graphene oxide, ultrasonic disperse is in 5mL water, and the DMF (DMF) adding 45mL in the dispersion liquid that this is brown obtains uniform graphene oxide dispersion.React 6 hours add the hydrazine hydrate 100 DEG C of 50 μ L in this dispersion liquid at, obtain the graphene dispersing solution of black.Mix ultrasonication with 3g polystyrolsulfon acid and within 15 hours, obtain stable black dispersion liquid.Subsequently to the aniline monomer adding 150mg in the Graphene aqueous dispersions that polystyrolsulfon acid is stable, add 40mg ammonium persulphate under vigorous stirring and cause aniline polymerization, react 18 hours at 0 DEG C.The matrix material of graphene/polyaniline is obtained by suction filtration and deionized water wash.
(2) preparation of graphene/polyaniline/polystyrene compound solid microsphere: add the Diisopropyl azodicarboxylate of 0.0546g as oil phase in 4mL vinylbenzene, get graphene/polyaniline aqueous dispersions and vinylbenzene that 6mL mass concentration is 5mg/mL in sample bottle, on high speed dispersor, under 8000rpm rotating speed, homogeneous 5min prepares Pickering emulsion.Sample bottle is placed in 55 DEG C of water-baths, standing and reacting 24 hours.By the product with deionized water washing after polymerization, centrifugal, in vacuum drying oven, 30 DEG C of dryings 8 hours, obtain graphene/polyaniline/polystyrene compound solid microsphere.
(3) preparation of graphene/polyaniline compound hollow microballoon: get 2g solid microsphere, be dissolved in 40mL tetrahydrofuran (THF), stir 4 hours, by solution centrifugal, speed is 8000rpm, time is 2 minutes, repeats for several times, get centrifugal after supernatant liquid, mix with isopyknic ethanol, until without precipitation after mixing, the sample obtained is placed in vacuum drying oven 30 DEG C of dryings 1 hour, namely obtains graphene/polyaniline compound hollow microballoon.
Claims (4)
1. a preparation method for graphene/polyaniline compound hollow microballoon, comprises the steps:
(1) preparation of grapheme/polyaniline composite material: graphene oxide is dispersed in water, adds hydrazine hydrate, at 80 ~ 100 DEG C, reaction obtains Graphene in 6 ~ 12 hours; Above-mentioned graphene dispersing solution is mixed supersound process 12 ~ 24 hours with a certain amount of polystyrolsulfon acid, obtains stable black dispersion liquid; A certain amount of aniline monomer is added in above-mentioned graphene dispersing solution, add oxygenant ammonium persulphate under stirring state and cause aniline polymerization, reaction times is 5 ~ 10 hours, by the mixed solution suction filtration, the deionized water wash that obtain after reaction, obtains grapheme/polyaniline composite material;
(2) preparation of graphene/polyaniline/polystyrene compound solid microsphere: by grapheme/polyaniline composite material obtained above, by ultrasonic disperse in certain volume water; The oil phase vinylbenzene (comprising the initiator that massfraction is 0.6 ~ 2% in oil phase) of certain volume will be added in the dispersion liquid of above-mentioned grapheme/polyaniline composite material, and use clarifixator emulsification 1 ~ 5 minute, obtain O/W type emulsion; Emulsion obtained above is placed in 50 ~ 60 DEG C of water-baths, standing and reacting 15 ~ 24 hours; By centrifugal for reacted product with deionized water, washing 3 ~ 5 times, in vacuum drying oven, 30 ~ 40 DEG C of dryings 6 ~ 10 hours, obtain graphene/polyaniline/polystyrene compound solid microsphere;
(3) preparation of graphene/polyaniline compound hollow microballoon: get graphene/polyaniline obtained above/polystyrene compound solid microsphere 1 ~ 3g, add 20 ~ 60mL tetrahydrofuran (THF), stir 2 ~ 4 hours, dissolve completely to polystyrene, by solution centrifugal, tetrahydrofuran (THF) is adopted repeatedly to wash, until wash away polystyrene completely; The solid obtained is placed in vacuum drying oven, and 30 ~ 40 DEG C of dryings 1 ~ 2 hour, obtain graphene/polyaniline compound hollow microballoon.
2. the preparation method of a kind of graphene/polyaniline compound hollow microballoon according to claim 1, it is characterized in that: in step (1), the mass ratio of polystyrolsulfon acid and Graphene is 50: 1 ~ 200: 1, and sonication treatment time is 15 ~ 24 hours; The mass ratio of aniline monomer and Graphene is 0.5: 1 ~ 10: 1, and the mass ratio of aniline monomer and ammonium persulphate is 1: 1 ~ 4: 1; Ultrasonic power is 200 ~ 400W.
3. the preparation method of a kind of graphene/polyaniline compound hollow microballoon according to claim 1, it is characterized in that: in step (2), ultrasonic power is 200 ~ 400W, and ultrasonic time is 10 ~ 30 minutes; The rotating speed of clarifixator is 8000 ~ 30000rpm; The concentration of matrix material dispersion liquid is 1 ~ 10mg/mL; The volume ratio of oil phase and aqueous phase is 1.5: 1 ~ 1: 3; Initiator is the kick off temperature such as 2,2'-Azobis(2,4-dimethylvaleronitrile), Diisopropyl azodicarboxylate at the oil-soluble initiator of 40 ~ 65 DEG C.
4. the preparation method of a kind of graphene/polyaniline compound hollow microballoon according to claim 1, is characterized in that: in step (3), centrifugal speed is 4000 ~ 8000rpm, and the time is 2 ~ 5 minutes; Get centrifugal rear supernatant liquid to mix with equal-volume dehydrated alcohol, then prove the complete washes clean of polystyrene without precipitation.
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| CN105869903A (en) * | 2016-05-25 | 2016-08-17 | 全球能源互联网研究院 | Preparation method of graphene |
| CN106084775A (en) * | 2016-06-14 | 2016-11-09 | 齐鲁工业大学 | Three layers of vesica shape polyaniline/graphene composite material and preparation method thereof |
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| CN106346019A (en) * | 2016-10-26 | 2017-01-25 | 华中科技大学 | Graphene supported micron-gold core-shell structure and preparation method thereof |
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| CN114558471A (en) * | 2021-12-25 | 2022-05-31 | 福建师范大学 | Application of terpineol modified graphene oxide nanoparticles in Pickering emulsion |
| CN115215334A (en) * | 2022-07-19 | 2022-10-21 | 重庆交通大学 | Preparation method of graphene oxide aerogel hollow microspheres |
| CN117285847A (en) * | 2023-09-08 | 2023-12-26 | 浙江永通新材料股份有限公司 | Coating for coating water-based polypropylene film and preparation method thereof |
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