CN105439134A - Stripping agent for preparing graphene through mechanical exfoliation - Google Patents
Stripping agent for preparing graphene through mechanical exfoliation Download PDFInfo
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- CN105439134A CN105439134A CN201511007071.5A CN201511007071A CN105439134A CN 105439134 A CN105439134 A CN 105439134A CN 201511007071 A CN201511007071 A CN 201511007071A CN 105439134 A CN105439134 A CN 105439134A
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Abstract
The invention discloses a stripping agent for preparing graphene through mechanical exfoliation. The stripping agent is characterized in that amide organic matters and deionized water are prepared into a solution, wherein the amide organic matters are formed by amidation reaction of phthalic anhydride and hydrophilic polymer units, graphite is added into the solution, and the mixed solution is subjected to ultrasonic treatment and centrifugal separation, so that graphene is obtained. The stripping agent is prepared from phthalic anhydride and non-toxic and harmless amino organic acid which are commonly used in the industry and used as raw materials, therefore the toxicity of the raw materials is lower, the preparation process is simple, the cost is low, and the stripping agent is suitable for large-scale industrial production.
Description
Technical field
The present invention relates to technical field of nanometer material preparation, particularly a kind of stripper preparing Graphene for mechanically peel.
Background technology
Within 2004, grapheme material is successfully prepared, and has caused the upsurge of a new ripple carbon materials research since then.The planar carbon nano material that Graphene is made up of one deck carbon atom, be the thinnest known two-dimensional material at present, its thickness is only 0.335nm, and it is made up of the lattice of six sides.Connected by σ key between carbon atom in Graphene, impart the extremely excellent mechanical property of Graphene and structure rigidity.And in Graphene, each carbon atom has the p electronics of a non-Cheng Jian, and these p electronics can move freely in crystal, and movement velocity is up to 1/300 of the light velocity, impart the electroconductibility that Graphene is good.In optics, Graphene is almost completely transparent, only absorbs the light of 2.3%.Graphene has peculiar mechanics, electrical and optical properties, and Graphene has very vast potential for future development.
In order to allow outstanding grapheme material realize suitability for industrialized production and application, a kind of can be mass-produced and the number of plies and the controlled preparation method of size just must be developed.The preparation method of current Graphene has mechanical stripping method, epitaxial growth method, oxidation reduction process, organic synthesis method, solvent-thermal method, chemical Vapor deposition process etc.In these methods, because mechanically peel method can preserve the character of Graphene best, and preparation method is simple, and preparation process is environment friendly and pollution-free, in the production of reality, enjoy favor.In order to improve the efficiency of mechanically peel, multiple stripper and stripping means are developed.
China Patent Publication No. 105110326A provides a kind of method utilizing liquid phase stripping method to prepare Graphene, the method comprises: first prepare certain density Sodium dodecylbenzene sulfonate ethanolic soln, and expanded graphite is sieved, then by magnetic agitation, the expanded graphite after sieving is dissolved in Sodium dodecylbenzene sulfonate ethanolic soln, the expanded graphite microwave treatment 5min again prepared by previous step, ultrasonic stripping under solution condition of ice bath after microwave treatment, obtains Graphene.Program graphene sheet layer is thinner, and the number of plies is within ten layers, and textural defect is little, conducts electricity very well.But the method is only limitted to adopt Sodium dodecylbenzene sulfonate, and Sodium dodecylbenzene sulfonate can stimulate eyes, stimulate respiratory system, to human injury.
China Patent Publication No. 103623741A provides a kind of graphene dispersion agent and stripper, is made up of naphthalenetetracarbimidec imidec unit, anionic group and alkyl chain three parts.The present invention has excellent graphene dispersion ability.Use Graphene that described graphite dispersing agent is prepared by ultrasonic method not through the process of oxidation-reduction, defect content is low, and preparation cost is low.Although this dispersion agent is water miscible, still there is naphthalenetetracarbacidic acidic dicarboxylic anhydride unit, expensive raw material price, cost is still very high.
In sum, also do not have in present existing method a kind of pollution-free, can be recycled, the water miscible Graphene stripper of good stability.
Summary of the invention
In order to solve deficiency and the defect of aforesaid method, the present invention develops a kind of stripper preparing Graphene for mechanically peel, the Tetra hydro Phthalic anhydride adopting industry conventional and nontoxic amino organic acid are as raw material, Tetra hydro Phthalic anhydride provides the benzene ring units of π key in addition, this unit can form π-π with graphite and act on, be adsorbed on graphite layers, and the bridge that the amino in amino organic acid provides acid amides to react, organic acid provides water soluble group, and, after organic acid ionizes in water, self is charged, form electrostatic force, mutual repulsion, dispersed graphite alkene, prevent from reuniting.Both suitably heat up and can react in its aqueous solution, and be prepared into water miscible stripper, technique is simple, with low cost, is applicable to large-scale industrial production.
The invention provides a kind of stripper preparing Graphene for mechanically peel, it is characterized in that, described stripper makes solution by amides organism and deionized water, described amides organism reacts chemical combination by Tetra hydro Phthalic anhydride and hydrophilic polymer unit by acid amides and forms, graphite is added in this solution, after carrying out supersound process, centrifugation, obtains Graphene.
Preferably, described hydrophilic polymer unit is the organism containing at least one group in carboxylic acid group, sulfonic group and guanidine nitric acid hydrophilic radical.
Preferably, described stripper is made in accordance with the following steps:
A. mixed with deionized water by Tetra hydro Phthalic anhydride, the concentration obtaining phthalic acid anhydride solution is 0.1-1mol/L, and add acid amides catalysts, heated solution is to 80-100 DEG C;
B. in the solution prepared in a step, drip the amino organic acid solution that hydrophilic polymer unit is provided, stir, obtain stripper.
Preferably, described amino organic acid solution is at least one in amino acid, thionamic acid and aminoguanidine salpeter solution.
Preferably, the concentration of described amino organic acid solution is 0.2-3mol/L.
Preferably, the volume ratio of described phthalic acid anhydride solution and amino organic acid solution is 1:1-5.
Preferably, described acid amides catalysts is N, N, N, N-tetramethyl-urea phosphofluoric acid ester, benzotriazole-N, N, one or more in N, N-tetramethyl-urea phosphofluoric acid ester, phosphoric acid salt or phosphofluoric acid salts solution, the concentration of acid amides catalysts is 0.1-0.5mmol/L.
Above-mentioned one or more technical scheme in the embodiment of the present application, at least has one or more technique effects following:
1, the present invention adopts industrial conventional Tetra hydro Phthalic anhydride and nontoxic amino organic acid as raw material, and material toxicity is lower, and preparation technology is simple, with low cost, is applicable to large-scale industrial production.
2, the present invention adopts Tetra hydro Phthalic anhydride and amino organic acid suitably to heat up in aqueous can to react, and Tetra hydro Phthalic anhydride provides the benzene ring units of in addition π key, and this unit can form π-π with graphite and act on, be adsorbed on graphite layers, and the bridge that the amino in amino organic acid provides acid amides to react, organic acid provides water soluble group, and, after organic acid ionizes in water, self is charged, forms electrostatic force, mutually repels, dispersed graphite alkene, prevents from reuniting.
3, this kind of water miscible stripper of the present invention's acquisition, after stripping Graphene completes, only need evaporate water, amides organism still stable existence, and can continue proportioning after concentrated as required and obtain stripper, be convenient to recycling, environmental pollution is little.
Embodiment
By embodiment, the present invention is described in further detail, but this should be interpreted as scope of the present invention is only limitted to following example.When not departing from aforesaid method thought of the present invention, the various replacement made according to ordinary skill knowledge and customary means or change, all should be within the scope of the present invention.
Embodiment one
The present embodiment comprises the steps:
Tetra hydro Phthalic anhydride is mixed with deionized water, acquisition concentration is 0.1mol/L phthalic acid anhydride solution, get this solution of 1L, add the acid amides catalysts N that concentration is 0.1mmol/L, N, N, N-tetramethyl-urea phosphofluoric acid ester 50mL, be heated to 80 DEG C, next, the amino acid solution containing hydrophilic polymer unit is slowly dripped in above-mentioned solution, amino acid in the present embodiment can be leucine, Isoleucine, L-glutamic acid, Methionin, arginine, glycine, Serine, Threonine, one or more in L-Ala, for leucine, get the leucine solution 1.5L that concentration is 0.2mol/L, amino acid solution content supersaturation during acid amides is reacted, slowly add in the phthalic acid anhydride solution containing catalyzer, stir, after abundant acid amides reaction, be down to room temperature and obtain stripper.
Added by 100g graphite in 1L stripper solution, after carrying out supersound process 12h, centrifugation, obtains graphene dispersing solution after the throw out in removing solution.By the Graphene in graphene dispersing solution by after Centrifugical extraction, after testing, the Graphene prepared is of a size of 1.39 μm (selected area sizes), and thickness is 0.83nm, and productive rate is 5.7%.Remaining dispersion liquid is heated to the moisture in 90 DEG C of removing dispersion liquids, obtains organism concentrated solution, deposit in container for storing liquid, add appropriate amount of deionized water through proportioning and can be prepared into stripper recycle.
Embodiment two
The present embodiment comprises the steps:
Tetra hydro Phthalic anhydride is mixed with deionized water, acquisition concentration is 0.5mol/L phthalic acid anhydride solution, get this solution of 1L, add the acid amides catalysts N that concentration is 0.1mmol/L, N, N, N-tetramethyl-urea phosphofluoric acid ester 30mL, be heated to 80 DEG C, next, the amino acid solution containing hydrophilic polymer unit is slowly dripped in above-mentioned solution, amino acid in the present embodiment can be leucine, Isoleucine, L-glutamic acid, Methionin, arginine, glycine, Serine, Threonine, one or more in L-Ala, for leucine, get the leucine solution 2L that concentration is 1.5mol/L, amino acid solution content supersaturation during acid amides is reacted, slowly add in the phthalic acid anhydride solution containing catalyzer, stir, after abundant acid amides reaction, be down to room temperature and obtain stripper.
Added by 100g graphite in 1L stripper solution, after carrying out supersound process 12h, centrifugation, obtains graphene dispersing solution after the throw out in removing solution.By the Graphene in graphene dispersing solution by after Centrifugical extraction, after testing, the Graphene prepared is of a size of 1.42 μm (selected area sizes), and thickness is 0.97nm, and productive rate is 6.2%.Remaining dispersion liquid is heated to 85 DEG C, by the moisture evaporation in dispersion liquid, obtains organism concentrated solution, deposit in container for storing liquid, add appropriate amount of deionized water through proportioning and can be prepared into stripper recycle.
Embodiment three
The present embodiment comprises the steps:
Tetra hydro Phthalic anhydride is mixed with deionized water, acquisition concentration is 0.5mol/L phthalic acid anhydride solution, get this solution of 1L, add the acid amides catalysts N that concentration is 0.1mmol/L, N, N, N-tetramethyl-urea phosphofluoric acid ester 30mL, is heated to 90 DEG C, next, get the sulfamic acid solution 3L that concentration is 1.5mol/L, slowly drip in above-mentioned solution, sulfamic acid solution content supersaturation during acid amides is reacted, slowly add in the phthalic acid anhydride solution containing catalyzer, stir, after abundant acid amides reaction, be down to room temperature and obtain stripper.
Added by 100g graphite in 1L stripper solution, after carrying out supersound process 12h, centrifugation, obtains graphene dispersing solution after the throw out in removing solution.By the Graphene in graphene dispersing solution by after Centrifugical extraction, after testing, the Graphene prepared is of a size of 1.31 μm (selected area sizes), and thickness is 0.87nm, and productive rate is 7.4%.Remaining dispersion liquid is heated to 85 DEG C, by the moisture evaporation in dispersion liquid, obtains organism concentrated solution, deposit in container for storing liquid, add appropriate amount of deionized water through proportioning and can be prepared into stripper recycle.
Embodiment four
The present embodiment comprises the steps:
Tetra hydro Phthalic anhydride is mixed with deionized water, acquisition concentration is 0.5mol/L phthalic acid anhydride solution, get this solution of 1L, add the acid amides catalysts phosphofluoric acid salts solution 30mL that concentration is 0.3mmol/L, be heated to 100 DEG C, next, get the sulfamic acid solution 3L that concentration is 2.0mol/L, slow dropping is in above-mentioned solution, sulfamic acid solution content supersaturation during acid amides is reacted, slowly adds in the phthalic acid anhydride solution containing catalyzer, stirs, after abundant acid amides reaction, be down to room temperature and obtain stripper.
Added by 100g graphite in 1L stripper solution, after carrying out supersound process 12h, centrifugation, obtains graphene dispersing solution after the throw out in removing solution.By the Graphene in graphene dispersing solution by after Centrifugical extraction, after testing, the Graphene prepared is of a size of 1.16 μm (selected area sizes), and thickness is 1.07nm, and productive rate is 8.3%.Remaining dispersion liquid is heated to 85 DEG C, by the moisture evaporation in dispersion liquid, obtains organism concentrated solution, deposit in container for storing liquid, add appropriate amount of deionized water through proportioning and can be prepared into stripper recycle.
Embodiment five
The present embodiment comprises the steps:
Tetra hydro Phthalic anhydride is mixed with deionized water, acquisition concentration is 1mol/L phthalic acid anhydride solution, get this solution of 1L, add the acid amides catalysts phosphofluoric acid salts solution 50mL that concentration is 0.5mmol/L, be heated to 100 DEG C, next, get the aminoguanidine salpeter solution 5L that concentration is 2.0mol/L, slow dropping is in above-mentioned solution, aminoguanidine nitric acid content supersaturation during acid amides is reacted, slowly adds in the phthalic acid anhydride solution containing catalyzer, stirs, after abundant acid amides reaction, be down to room temperature and obtain stripper.
Added by 100g graphite in 1L stripper solution, after carrying out supersound process 12h, centrifugation, obtains graphene dispersing solution after the throw out in removing solution.By the Graphene in graphene dispersing solution by after Centrifugical extraction, after testing, the Graphene prepared is of a size of 1.02 μm (selected area sizes), and thickness is 0.97nm, and productive rate is 5.3%.Remaining dispersion liquid is heated to 85 DEG C, by the moisture evaporation in dispersion liquid, obtains organism concentrated solution, deposit in container for storing liquid, add appropriate amount of deionized water through proportioning and can be prepared into stripper recycle.
Although describe the preferred embodiments of the present invention, those skilled in the art once obtain the basic creative concept of cicada, then can make other change and amendment to these embodiments.So claims are intended to be interpreted as comprising preferred embodiment and falling into all changes and the amendment of the scope of the invention.
Obviously, those skilled in the art can carry out various change and modification to the present invention and not depart from the spirit and scope of the present invention.Like this, if these amendments of the present invention and modification belong within the scope of the claims in the present invention and equivalent technologies thereof, then the present invention is also intended to comprise these change and modification.
Claims (7)
1. prepare the stripper of Graphene for mechanically peel for one kind, it is characterized in that, described stripper makes solution by amides organism and deionized water, described amides organism reacts chemical combination by Tetra hydro Phthalic anhydride and hydrophilic polymer unit by acid amides and forms, graphite is added in this solution, after carrying out supersound process, centrifugation, obtains Graphene.
2. a kind of stripper preparing Graphene for mechanically peel according to claim 1, is characterized in that, described hydrophilic polymer unit is the organism containing at least one group in carboxylic acid group, sulfonic group and guanidine nitroxyl hydrophilic radical.
3. a kind of stripper preparing Graphene for mechanically peel according to claim 1, it is characterized in that, described stripper is made in accordance with the following steps:
A. mixed with deionized water by Tetra hydro Phthalic anhydride, the concentration obtaining phthalic acid anhydride solution is 0.1-1mol/L, and add acid amides catalysts, heated solution is to 80-100 DEG C;
B. in the solution prepared in a step, drip the amino organic acid solution that hydrophilic polymer unit is provided, stir, obtain stripper.
4. a kind of stripper preparing Graphene for mechanically peel according to claim 3, is characterized in that, described amino organic acid solution is at least one in amino acid, thionamic acid and aminoguanidine salpeter solution.
5. a kind of stripper preparing Graphene for mechanically peel according to claim 3, is characterized in that, the concentration of described amino organic acid solution is 0.2-3mol/L.
6. a kind of stripper preparing Graphene for mechanically peel according to claim 3, is characterized in that, the volume ratio of described phthalic acid anhydride solution and amino organic acid solution is 1:1-5.
7. a kind of stripper preparing Graphene for mechanically peel according to claim 3, it is characterized in that, described acid amides catalysts is N, N, N, N-tetramethyl-urea phosphofluoric acid ester, benzotriazole-N, N, one or more in N, N-tetramethyl-urea phosphofluoric acid ester, phosphoric acid salt or phosphofluoric acid salts solution, the concentration of acid amides catalysts is 0.1-0.5mmol/L.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106744870A (en) * | 2016-10-25 | 2017-05-31 | 成都新柯力化工科技有限公司 | A kind of abrasive media that Graphene is peeled off for slurry grinding |
| CN107723828A (en) * | 2017-10-13 | 2018-02-23 | 江苏双良低碳产业技术研究院有限公司 | The preparation method and spinning process of a kind of polymolecularity graphene/composite fibre of nylon 6 |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102530932A (en) * | 2011-12-21 | 2012-07-04 | 青岛大学 | Green and environmentally-friendly preparation method of graphene with low defect and large size |
| CN102702039A (en) * | 2012-05-14 | 2012-10-03 | 河南农业大学 | Process for synthesizing beta-alanyl-taurine |
| CN103253659A (en) * | 2013-05-23 | 2013-08-21 | 渤海大学 | Method for preparing graphene through carrying out ultrasonic stripping on graphite |
| KR20130133433A (en) * | 2012-05-29 | 2013-12-09 | 이혜경 | Pure graphene mass production method i |
-
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102530932A (en) * | 2011-12-21 | 2012-07-04 | 青岛大学 | Green and environmentally-friendly preparation method of graphene with low defect and large size |
| CN102702039A (en) * | 2012-05-14 | 2012-10-03 | 河南农业大学 | Process for synthesizing beta-alanyl-taurine |
| KR20130133433A (en) * | 2012-05-29 | 2013-12-09 | 이혜경 | Pure graphene mass production method i |
| CN103253659A (en) * | 2013-05-23 | 2013-08-21 | 渤海大学 | Method for preparing graphene through carrying out ultrasonic stripping on graphite |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106744870A (en) * | 2016-10-25 | 2017-05-31 | 成都新柯力化工科技有限公司 | A kind of abrasive media that Graphene is peeled off for slurry grinding |
| CN106744870B (en) * | 2016-10-25 | 2019-01-04 | 成都新柯力化工科技有限公司 | A kind of abrasive media grinding removing graphene for slurry |
| CN107723828A (en) * | 2017-10-13 | 2018-02-23 | 江苏双良低碳产业技术研究院有限公司 | The preparation method and spinning process of a kind of polymolecularity graphene/composite fibre of nylon 6 |
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