CN106751263A - Stannic oxide/graphene nano lamella strengthens the preparation method of polyvinyl alcohol composite material - Google Patents
Stannic oxide/graphene nano lamella strengthens the preparation method of polyvinyl alcohol composite material Download PDFInfo
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Abstract
The present invention relates to the preparation method that a kind of stannic oxide/graphene nano lamella strengthens polyvinyl alcohol composite material, step is as follows：（1）The 50ml concentrated sulfuric acids and 0.5g graphite powders are added in there-necked flask, is stirred, 0 °C is cooled in ice-water bath, the potassium permanganate of 0.5-1.5g is then slowly added to, 35 °C are slowly warmed up to, after reacting 2 hours, 70 °C are to slowly warm up to again, half an hour is reacted, and obtain low degree of oxidation graphite oxide；（2）By graphite oxide in 10ml deionized waters ultrasonic disperse 1 hour, then it is centrifuged 30 minutes under 4000 revs/min of rotating speed, remove unstripped graphite oxide, obtain the stannic oxide/graphene nano lamella aqueous solution, 1g polyvinyl alcohol is then added in the stannic oxide/graphene nano lamella aqueous solution, then be poured on uniform mixed solution in flat substrate by 90 °C of stirring and dissolvings, dried under 60 °C until constant mass, obtain polyvinyl alcohol/oxidized graphite composite material film.Composite material film physical property prepared by this method is greatly improved.
Description
Technical field
The invention belongs to field of material technology, and in particular to a kind of stannic oxide/graphene nano lamella strengthens the preparation method of polyvinyl alcohol composite material.
Background technology
The preparation of Graphene is always a focus and difficult point problem of scientific circles and industrial quarters.Although many methods are successfully prepared for Graphene, various methods have the advantage of oneself, there is also certain shortcoming.Such as, mechanical stripping method can prepare the most complete graphene sheet layer of structure, but take time and effort very much；Chemical vapour deposition technique（CVD）High-quality graphene film can be prepared, but this method is high to equipment requirement, it is relatively costly；Liquid phase ultrasound is peeled off has simple to operate, convenient advantage, but larger to the selection dependence of solvent.And these methods also have a common shortcoming, exactly can not on a large scale prepare Graphene.The method for most possibly taking the lead in mass producing Graphene at present is redox graphene nanoscale twins（GONS）Method, therefore graphite oxide（GO）The broad interest of researchers is caused again.
GO is a kind of oxidized derivatives of graphite, is aoxidized in strong acid and strong oxidizer by graphite and obtained.After peroxidating, the physical and chemical performance of graphite be there occurs and significantly change, a large amount of hydrophilic radicals, and e.g., the group such as hydroxyl, epoxy, carbonyl, carboxyl is introduced into GO.These groups make GO interlamellar spacings become big, while overcoming the effect of Van der Waals force in graphite, it is the GONS of individual layer or few layer to make GO be easy to peel off in water.Although GO is non-conductive due to the destruction of conjugated structure, by the electric conductivity that can partly recover original graphite after reduction.With mechanical stripping, the method such as CVD compares, and this method has the advantages that low cost, yield are high, therefore, at present the research of GO is mainly to concentrate on and is prepared on Graphene by presoma of GO.In fact, GO is also in itself a kind of widely used nano material, such as in gas absorption, catalysis or the application of fire-retardant aspect.Meanwhile, after GO is peeled off, GONS also can prepare polymer composites as a kind of excellent Nano filling.Recently, GONS is also reported and can serve as dispersant to CNT（CNT）Or fullerene（C60）Disperseed Deng in water.
Preparing GO at present mainly has the several methods such as Brodie methods, Staudenmaier methods and Hummers methods, researchers with this several method when GO is prepared, in order that graphite complete oxidation reaches the purpose being completely exfoliated, and pass through graphite is processed frequently with excessive oxidant.Although can so make GONS be completely exfoliated and disperse in water, the oxidation of excess inevitably causes the defect in structure to Graphene, such as corrugation, crackle, or cavity etc., and these defects will influence the mechanical strength of GONS.Although the Young's modulus of these GONS still can reach 250GPa, want to obtain better performance in high performance polymer composite material etc. is applied it is necessary to prepare defect less, outstanding GONS of performance itself.In addition, high oxidation or the more GONS of defect are also unfavorable for preparing high-quality Graphene, because even oxy radical energy major part is reduced agent removing, the defect in structure but may proceed to stay in the middle of the GONS of reduction.
In sum, if the GO that degree of oxidation is smaller and defect is less can be prepared, high-quality GONS can be just separated, so as to improve GONS performances in actual applications.In fact, in report before this, some seminars have been attempt to adjust the parameter of GO by changing some steps in oxidizing process, such as, Lee et al. Brodie and Staudenmaier change the length of oxidization time when preparing GO, discovery can change the ratio of sp3 carbon and sp2 carbon in GO；Jeong et al. prepares the oxidization time of GO again by regulation Brodie methods, is prepared for the less GO of degree of oxidation.But the peeling behavior of GO is not studied in these reports, also the GONS after stripping is not characterized, while the time that these methods prepare GO is relatively long, be unfavorable for actual production.
The content of the invention
Regarding to the issue above, the present invention is intended to provide a kind of stannic oxide/graphene nano lamella strengthens the preparation method of polyvinyl alcohol composite material.
A kind of stannic oxide/graphene nano lamella strengthens the preparation method of polyvinyl alcohol composite material, and step is as follows：
（1）The 50ml concentrated sulfuric acids and 0.5g graphite powders are added in there-necked flask, stir, 0 °C is cooled in ice-water bath, it is then slowly added to the potassium permanganate of 0.5-1.5g, slowly it is warmed up to 35 °C, after reaction 2 hours, 70 °C are to slowly warm up to again, reaction half an hour, until potassium permanganate consumption is complete, obtain the graphite oxide of suboxides degree, after the completion of reaction, pour into a large amount of frozen water, centrifugal sedimentation, then washed with 10% aqueous hydrochloric acid solution 6 times, deionized water is washed three times, product is collected by centrifugation, 60 °C of drying in last vacuum drying oven, obtain low degree of oxidation graphite oxide；
（2）By graphite oxide in 10ml deionized waters ultrasonic disperse 1 hour, then it is centrifuged 30 minutes under 4000 revs/min of rotating speed, remove unstripped graphite oxide, obtain the stannic oxide/graphene nano lamella aqueous solution, 1g polyvinyl alcohol is then added in the stannic oxide/graphene nano lamella aqueous solution, then be poured on uniform mixed solution in flat substrate by 90 °C of stirrings to dissolving, dried under 60 °C until constant mass, obtain polyvinyl alcohol/oxidized graphite composite material film.
In the present invention, we are prepared for the graphite oxide of suboxides degree with improved Hummers methods, because this method is in hgher efficiency for Brodie methods and Staudenmaier methods, while not having toxic gas releasing in preparation process.Due to potassium permanganate and graphite reaction speed faster, we use the means of the consumption by changing oxidant, make the purpose of graphite oxide suboxides degree to reach, and graphite using the suboxides degree is prepared for strengthening polyvinyl alcohol composite material, the physical property of material is greatly improved.
Specific embodiment
The present invention is described in further details with reference to specific embodiment.
Embodiment 1
（1）A kind of stannic oxide/graphene nano lamella strengthens the preparation method of polyvinyl alcohol composite material, and step is as follows：The 50ml concentrated sulfuric acids and 0.5g graphite powders are added in there-necked flask, stir, 0 °C is cooled in ice-water bath, it is then slowly added to the potassium permanganate of 0.5g, slowly it is warmed up to 35 °C, after reaction 2 hours, 70 °C are to slowly warm up to again, reaction half an hour, until potassium permanganate consumption is complete, obtain the graphite oxide of suboxides degree, after the completion of reaction, pour into a large amount of frozen water, centrifugal sedimentation, then washed with 10% aqueous hydrochloric acid solution 6 times, deionized water is washed three times, product is collected by centrifugation, 60 °C of drying in last vacuum drying oven, obtain low degree of oxidation graphite oxide.
（2）By graphite oxide in 10ml deionized waters ultrasonic disperse 1 hour, then it is centrifuged 30 minutes under 4000 revs/min of rotating speed, remove unstripped graphite oxide, obtain the stannic oxide/graphene nano lamella aqueous solution, 1g polyvinyl alcohol is then added in the stannic oxide/graphene nano lamella aqueous solution, then be poured on uniform mixed solution in flat substrate by 90 °C of stirrings to dissolving, dried under 60 °C until constant mass, obtain polyvinyl alcohol/oxidized graphite composite material film.
Embodiment 2
（1）A kind of stannic oxide/graphene nano lamella strengthens the preparation method of polyvinyl alcohol composite material, and step is as follows：The 50ml concentrated sulfuric acids and 0.5g graphite powders are added in there-necked flask, stir, 0 °C is cooled in ice-water bath, it is then slowly added to the potassium permanganate of 1.0g, slowly it is warmed up to 35 °C, after reaction 2 hours, 70 °C are to slowly warm up to again, reaction half an hour, until potassium permanganate consumption is complete, obtain the graphite oxide of suboxides degree, after the completion of reaction, pour into a large amount of frozen water, centrifugal sedimentation, then washed with 10% aqueous hydrochloric acid solution 6 times, deionized water is washed three times, product is collected by centrifugation, 60 °C of drying in last vacuum drying oven, obtain low degree of oxidation graphite oxide.
（2）By graphite oxide in 10ml deionized waters ultrasonic disperse 1 hour, then it is centrifuged 30 minutes under 4000 revs/min of rotating speed, remove unstripped graphite oxide, obtain the stannic oxide/graphene nano lamella aqueous solution, 1g polyvinyl alcohol is then added in the stannic oxide/graphene nano lamella aqueous solution, then be poured on uniform mixed solution in flat substrate by 90 °C of stirrings to dissolving, dried under 60 °C until constant mass, obtain polyvinyl alcohol/oxidized graphite composite material film.
Embodiment 3
（1）A kind of stannic oxide/graphene nano lamella strengthens the preparation method of polyvinyl alcohol composite material, and step is as follows：The 50ml concentrated sulfuric acids and 0.5g graphite powders are added in there-necked flask, stir, 0 °C is cooled in ice-water bath, it is then slowly added to the potassium permanganate of 1.5g, slowly it is warmed up to 35 °C, after reaction 2 hours, 70 °C are to slowly warm up to again, reaction half an hour, until potassium permanganate consumption is complete, obtain the graphite oxide of suboxides degree, after the completion of reaction, pour into a large amount of frozen water, centrifugal sedimentation, then washed with 10% aqueous hydrochloric acid solution 6 times, deionized water is washed three times, product is collected by centrifugation, 60 °C of drying in last vacuum drying oven, obtain low degree of oxidation graphite oxide.
（2）By graphite oxide in 10ml deionized waters ultrasonic disperse 1 hour, then it is centrifuged 30 minutes under 4000 revs/min of rotating speed, remove unstripped graphite oxide, obtain the stannic oxide/graphene nano lamella aqueous solution, 1g polyvinyl alcohol is then added in the stannic oxide/graphene nano lamella aqueous solution, then be poured on uniform mixed solution in flat substrate by 90 °C of stirrings to dissolving, dried under 60 °C until constant mass, obtain polyvinyl alcohol/oxidized graphite composite material film.
Claims (1)
1. a kind of stannic oxide/graphene nano lamella strengthens the preparation method of polyvinyl alcohol composite material, it is characterised in that step is as follows：（1）The 50ml concentrated sulfuric acids and 0.5g graphite powders are added in there-necked flask, stir, 0 °C is cooled in ice-water bath, it is then slowly added to the potassium permanganate of 0.5-1.5g, slowly it is warmed up to 35 °C, after reaction 2 hours, 70 °C are to slowly warm up to again, reaction half an hour, until potassium permanganate consumption is complete, obtain the graphite oxide of suboxides degree, after the completion of reaction, pour into a large amount of frozen water, centrifugal sedimentation, then washed with 10% aqueous hydrochloric acid solution 6 times, deionized water is washed three times, product is collected by centrifugation, 60 °C of drying in last vacuum drying oven, obtain low degree of oxidation graphite oxide；（2）By graphite oxide in 10ml deionized waters ultrasonic disperse 1 hour, Ran Hou
It is centrifuged 30 minutes under 4000 revs/min of rotating speed, remove unstripped graphite oxide, obtain the stannic oxide/graphene nano lamella aqueous solution, 1g polyvinyl alcohol is then added in the stannic oxide/graphene nano lamella aqueous solution, 90 °C of stirrings are extremely dissolved, then uniform mixed solution is poured in flat substrate, is dried under 60 °C until constant mass, obtain polyvinyl alcohol/oxidized graphite composite material film.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109306143A (en) * | 2017-07-28 | 2019-02-05 | 张家港市六福新材料科技有限公司 | A kind of conductive nano composite material and preparation method thereof based on graphite |
| CN111154207A (en) * | 2018-11-07 | 2020-05-15 | 南京工程学院 | Preparation method of high-tensile-stress self-repairing compound |
| CN114455576A (en) * | 2022-01-24 | 2022-05-10 | 南方电网科学研究院有限责任公司 | Preparation method of graphene composite material for high-sensitivity detection of pressure change |
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2015
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109306143A (en) * | 2017-07-28 | 2019-02-05 | 张家港市六福新材料科技有限公司 | A kind of conductive nano composite material and preparation method thereof based on graphite |
| CN111154207A (en) * | 2018-11-07 | 2020-05-15 | 南京工程学院 | Preparation method of high-tensile-stress self-repairing compound |
| CN114455576A (en) * | 2022-01-24 | 2022-05-10 | 南方电网科学研究院有限责任公司 | Preparation method of graphene composite material for high-sensitivity detection of pressure change |
| CN114455576B (en) * | 2022-01-24 | 2023-11-10 | 南方电网科学研究院有限责任公司 | Preparation method of graphene composite material for detecting pressure change with high sensitivity |
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