CN104464888A - Sulfonated macromolecule/graphene nanocomposite and manufacturing method and application thereof - Google Patents
Sulfonated macromolecule/graphene nanocomposite and manufacturing method and application thereof Download PDFInfo
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- CN104464888A CN104464888A CN201310443373.1A CN201310443373A CN104464888A CN 104464888 A CN104464888 A CN 104464888A CN 201310443373 A CN201310443373 A CN 201310443373A CN 104464888 A CN104464888 A CN 104464888A
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Abstract
The invention discloses a sulfonated macromolecule/graphene nanocomposite and a manufacturing method and application of the sulfonated macromolecule/graphene nanocomposite. The manufacturing method of the sulfonated macromolecule/graphene nanocomposite includes the following steps that oxidized graphene and sulfonated macromolecules are mixed in a solvent, so that a mixed solution is acquired; a reducing agent is added to the mixed solution for a reduction reaction, and the sulfonated macromolecule/graphene nanocomposite is acquired, wherein the sulfonated macromolecule/graphene nanocomposite comprises the graphene and the sulfonated macromolecules evenly dispersed between graphene layers. When the oxidized graphene is reduced to the graphene through hydrazine, due to the fact that the sulfonated macromolecules are evenly inserted into the portions between the oxidized graphene layers in a penetrating mode, when the reduction reaction is conducted, the sulfonated macromolecules cannot be extruded by the graphene, and the proportion of the graphene added to the sulfonated macromolecules can be greatly increased.
Description
Technical field
The present invention relates to graphene composite material, particularly relate to a kind of sulfonated polymer/graphene nanocomposite material and its preparation method and application.
Background technology
The extensive use in the electronic devices such as solar cell, touch-screen, flat-panel monitor of tin indium oxide (ITO) transparent conductive film, but the raw material indium preparing tin indium oxide (ITO) transparency electrode is rare precious metals, and tin indium oxide (ITO) is inorganic oxide film, in fragility, limit its application in flexible touch screen.
After 2004 Univ Manchester UK researchers prepare monoatomic layer Graphene first, the excellent electric property that Graphene shows starts research boom in the whole world.Graphene is the monoatomic layer bidimensional material rearranged in the hexagonal honeycomb lattice plane space of carbon atom formation, be also called monoatomic layer graphite, its existing high tenacity of the structures shape of its uniqueness, has again high rigidity, chemical stability is good, optics and electric property excellence.The visible-light absorptivity of monoatomic layer Graphene is only 2.3%, theoretical surface resistance 20 Ω
-1.The optics of Graphene excellence and electric property, high-flexibility and abundant raw material, become tin indium oxide (ITO) desirable substitution material.When using Graphene to prepare transparent conductive film, need Graphene to mix with macromolecular material.But, often produce the phenomenon of gathering when graphene dispersion is in macromolecule, cause added Graphene ratio all very low.
Summary of the invention
Based on this, be necessary the sulfonated polymer/graphene nanocomposite material providing a kind of Graphene content higher.
A kind of sulfonated polymer/graphene nanocomposite material, comprise Graphene and be dispersed in the sulfonated polymer between described graphene layer, described Graphene forms a conductive network.
Wherein in an embodiment, described sulfonated polymer is the macromolecule with sulfonate radical segment.
Wherein in an embodiment, described sulfonated polymer is selected from the one in poly-(vinyl alcohol) (sulfonated poly (the vinyl alcohol)) of sulfonated polyimide (Sulfonatedpolyimide), sulfonation polydiacetylene (sulfonated poly-diacetylene) and sulfonation.
Wherein in an embodiment, the percentage by weight that described Graphene makes an addition to described sulfonated polymer/graphene nanocomposite material is 0.1% ~ 1%.
A preparation method for sulfonated polymer/graphene nanocomposite material, comprises the steps:
Graphene oxide and sulfonated polymer are mixed to get mixed solution in a solvent; And
In described mixed solution, add reducing agent carry out reduction reaction and obtain sulfonated polymer/graphene nanocomposite material, described sulfonated polymer/graphene nanocomposite material comprises Graphene and is dispersed in the sulfonated polymer between described stone graphene layer.
Wherein in an embodiment, described sulfonated polymer is the macromolecule having sulfonate radical segment.
Wherein in an embodiment, described sulfonated polymer is selected from the one in sulfonated polyimide (Sulfonatedpolyimide), sulfonation polydiacetylene (sulfonated poly-diacetylene), poly-(vinyl alcohol) (sulfonated poly (the vinyl alcohol)) of sulfonation.
Wherein in an embodiment, described Graphene is 0.1% ~ 1% at the percentage by weight of described sulfonated polymer/graphene nanocomposite material.
Wherein in an embodiment, described solvent is selected from the one in deionized water, dimethyl sulfoxide (DMSO), dimethyl formamide, 1-METHYLPYRROLIDONE and ethanol.
Wherein in an embodiment, the described graphene oxide concentration made an addition in described mixed solution is 1mg/ml.
Wherein in an embodiment, described reducing agent is diamine.
Wherein in an embodiment, in described mixed solution, add reducing agent carry out the step that reduction reaction obtains sulfonated polymer/graphene nanocomposite material and be, be that 200mg/mL (diamine of 50% concentration) adds diamine in described mixed solution according to the ratio of graphene oxide and diamine, stirring is added 1 minute the temperature of 25 DEG C, back flow reaction 2 hours at being heated to 100 DEG C afterwards, separation and purification, and then obtain sulfonated polymer/graphene nanocomposite material.
The application of described sulfonated polymer/graphene nanocomposite material on contact panel.
When graphene oxide is reduced into Graphene by reducing agent, because sulfonated polymer is evenly interspersed in the interlayer of graphene oxide, therefore when carrying out reduction reaction, sulfonated polymer can not squeeze by Graphene, therefore significantly can increase Graphene and make an addition to ratio in macromolecule.
Accompanying drawing explanation
Fig. 1 is preparation method's flow chart of the sulfonated polymer/graphene nanocomposite material of an execution mode;
Fig. 2 is preparation method's simulation drawing of the sulfonated polymer/graphene nanocomposite material of an execution mode;
Fig. 3 is that the sulfonated polymer/graphene nanocomposite material of an embodiment and the dispersion situation of pure Graphene contrast photo;
Fig. 4 is the sulfonated polymer/graphene nanocomposite material of an embodiment and the Fourier transform infrared spectrum figure of pure Graphene; And
Fig. 5 is the TEM photo of the sulfonated polymer/graphene nanocomposite material of embodiment 1.
Wherein, description of reference numerals is as follows:
S101, S102 step
Embodiment
Sulfonated polymer/the graphene nanocomposite material of one execution mode, comprise Graphene and be dispersed in the sulfonated polymer between described graphene layer, described Graphene forms a conductive network.
Preferably, sulfonated polymer is the macromolecule with sulfonate radical segment.
Preferably, sulfonated polymer is for being selected from sulfonated polyimide
Sulfonation polydiacetylene
Sulfonated polyethylene alcohol (
) in one.
The ratio of its sulfonation, will have a certain impact for rare being scattered in solution of graphite oxide.Wherein, the ratio of n/m is preferably 4/1; More preferred, n=80; M=20.
Preferably, Graphene is 0.1 ~ 1wt% at the percentage by weight of sulfonated polymer/graphene nanocomposite material.
Please refer to Fig. 1 and Fig. 2, the preparation method of above-mentioned sulfonated polymer/graphene nanocomposite material, comprises the steps:
Step S101, graphene oxide and sulfonated polymer are mixed to get mixed solution in a solvent.
Such as, graphene oxide and sulfonated polymer can be added in different vessels respectively, and add solvent respectively and carry out disperseing and dissolve.The solvent that dissolved oxygen graphite is rare can be selected from the one in deionized water, dimethyl sulfoxide (DMSO) (DMSO), dimethyl formamide (DMF), 1-METHYLPYRROLIDONE (NMP) and ethanol.The solvent dissolving sulfonated polymer can select dimethyl sulfoxide (DMSO) (DMSO) or 1-METHYLPYRROLIDONE (NMP) wherein a kind of.Preferred graphite oxide is rare is adopt ultrasonic oscillation dispersion, rarer for homodisperse graphite oxide progressively instillation in sulfonated polymer is fully mixed.Graphene oxide preferred concentration is in a solvent 1mg/mL, and the preferred concentration of sulfonated polymer is 200mg/mL.The rare ratio making an addition to sulfonated polymer of graphite oxide can from 0.1wt% to 1wt%.On material, graphene oxide can obtain through purchase, or uses the Hummers method of improvement to prepare peeling off after graphite oxidation.
The rare greatest problem faced with macromolecule of graphite is compatibility.The composite material recorded in existing document, the rare ratio of graphite of its blending is often all very low, and graphite under is at high proportion rare, and the phenomenon of gathering can be caused again to produce, therefore how will graphite is rare is at high proportion dispersed in macromolecule, will be a great problem.
Refer to Fig. 3, pure graphite is rare to be scattered in water and to leave standstill 1 hour, can see the generation of the rare sedimentation of graphite.And be scattered in sulfonation pi solution when graphite is rare, under the identical time, do not find the rare sedimentation phenomenon of graphite, this is because the surface of Graphene also exists comparatively multiple polar group (such as-COOH ,-OH etc.), these polar groups can with sulfonate radical (-SO
3h) Hyarogen-bonding is produced.As shown in Figure 4, when graphite rare importing sulfonation pi of 1wt%, its-OH group can toward high wave number direction displacement, the therefore existence of provable its hydrogen mirror active force.And by this active force, the Graphene after reduction can be uniformly dispersed in polymer system.
Step S102, add reducing agent carry out reduction reaction and obtain sulfonated polymer/graphene nanocomposite material in mixed solution, described sulfonated polymer/graphene nanocomposite material comprises single-layer graphene and is dispersed in sulfonated polymer with Multi-layer graphite is rare.
Preferably, reducing agent is diamine (Hydrazine).
Such as, can at the temperature of 25 DEG C, the ratio being 1g:5mL according to graphene oxide and diamine adds the diamine that mass concentration is 50% in mixed solution, stir 1 minute, back flow reaction 2 hours at being heated to 100 DEG C afterwards, separation and purification, and then obtain sulfonated polymer/graphene nanocomposite material.
In said method, when graphene oxide is reduced into Graphene by diamine, because sulfonated polymer is evenly interspersed in the interlayer of graphene oxide, therefore when carrying out reduction reaction, sulfonated polymer can not squeeze by Graphene, therefore significantly can increase Graphene and make an addition to ratio in macromolecule.In addition, the feature of said method is that single step reaction generates nano composite material, but not the Graphene of first making in existing document makes an addition in macromolecule again, and this not only eliminates a step, significantly can also promote Graphene in addition and make an addition to high molecular ratio.
Sulfonated polymer/the graphene nanocomposite material of present embodiment has excellent light transmission and conductivity, therefore can be applied to contact panel to replace tin indium oxide (ITO).
Further illustrate below by way of specific embodiment.
Embodiment 1
For 0.1wt% graphite rare/sulfonation pi composite material, first 10mg graphene oxide is scattered in the deionized water of 10ml, carries out ultrasonic vibration 30 minutes, in addition, sulfonation pi 90mg is added the dimethyl sulfoxide (DMSO) (DMSO) of 0.45ml, and stir 30 minutes.Afterwards by graphite oxide weak solution, slowly instill in sulfonation pi solution, and Keep agitation can obtain mixed solution in 15 minutes.Then join in mixed solution by the diamine of about 0.05ml mass concentration 50%, at the temperature of 100 DEG C, back flow reaction 2 hours, makes graphene oxide be reduced into Graphene, then separation and purification, dries, obtains sulfonation pi/graphene nanocomposite material.
Refer to Fig. 5, be depicted as the TEM(transmission electron microscope of the sulfonation sulfonation pi/graphene nanocomposite material of embodiment 1) photo.As shown in Figure 5, nano level graphene uniform is scattered in sulfonation sulfonation pi interlayer.
Adopt the PGSTAT30 type electric conductivity instrument of Autolab to measure, the conductivity of the sulfonated polymer/graphene nanocomposite material of the present embodiment is 0.145S/cm.
Table one
| Sample | Conductivity (S/cm) |
| SPI | 0.137 |
| SPI/0.1wt% Graphene | 0.145 |
| SPI/0.3wt% Graphene | 0.155 |
| SPI/0.5wt% Graphene | 0.218 |
| SPI/1wt% Graphene | 0.361 |
In table 1, the electrical conductivity of not adding the rare sulfonation pi (SPI) of graphite is 0.137S/cm, and along with the increase that graphite is rare, its conductance also can and then promote.When graphite is rare add 1wt% to time, electrical conductivity can reach 0.361S/cm.Compared to not adding the rare sulfonation pi of graphite, the electrical conductivity of SPI/1wt% Graphene improves the amplitude close to three times, and therefore explanation graphite is clearly rare effectively can promote overall conductivity.
In addition, sulfonation polydiacetylene/graphite is rare, rare with sulfonated polyethylene alcohol/graphite, all can obtain nano composite material with reference to the step of embodiment 1.
The foregoing is only the preferred embodiments of the present invention, be not limited to the present invention, for a person skilled in the art, the present invention can have various modifications and variations.Within the spirit and principles in the present invention all, any amendment done, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (13)
1. sulfonated polymer/graphene nanocomposite material, is characterized in that, comprise Graphene and be dispersed in the sulfonated polymer between described graphene layer, described Graphene forms a conductive network.
2. sulfonated polymer/graphene nanocomposite material according to claim 1, is characterized in that, described sulfonated polymer is the macromolecule with sulfonate radical segment.
3. sulfonated polymer/graphene nanocomposite material according to claim 2, described sulfonated polymer is selected from the one in sulfonated polyimide, sulfonation polydiacetylene, sulfonated polyethylene alcohol.
4. sulfonated polymer/graphene nanocomposite material according to claim 1, is characterized in that, described Graphene is 0.1% ~ 1% at the percentage by weight of described sulfonated polymer/graphene nanocomposite material.
5. a preparation method for sulfonated polymer/graphene nanocomposite material, is characterized in that, comprises the steps:
Graphene oxide and sulfonated polymer are mixed to get mixed solution in a solvent; And
In described mixed solution, add reducing agent carry out reduction reaction and obtain sulfonated polymer/graphene nanocomposite material, described sulfonated polymer/graphene nanocomposite material comprises Graphene and is dispersed in the sulfonated polymer between described graphene layer.
6. the preparation method of sulfonated polymer/graphene nanocomposite material according to claim 5, is characterized in that, described sulfonated polymer is the macromolecule with sulfonate radical segment.
7. the preparation method of sulfonated polymer/graphene nanocomposite material according to claim 6, is characterized in that, described sulfonated polymer is selected from the one in sulfonated polyimide, sulfonation polydiacetylene and sulfonated polyethylene alcohol.
8. the preparation method of sulfonated polymer/graphene nanocomposite material according to claim 5, is characterized in that, described Graphene is 0.1% ~ 1% at the percentage by weight of described sulfonated polymer/graphene nanocomposite material.
9. the preparation method of sulfonated polymer/graphene nanocomposite material according to claim 5, is characterized in that, described solvent is selected from the one in deionized water, dimethyl sulfoxide (DMSO), dimethyl formamide, 1-METHYLPYRROLIDONE and ethanol.
10. the preparation method of sulfonated polymer/graphene nanocomposite material according to claim 5, is characterized in that, the concentration of described graphene oxide in described mixed solution is 1mg/mL.
The preparation method of 11. sulfonated polymer/graphene nanocomposite materials according to claim 5, is characterized in that, described reducing agent is diamine.
The preparation method of 12. sulfonated polymer/graphene nanocomposite materials according to claim 10, it is characterized in that, in described mixed solution, add reducing agent carry out the step that reduction reaction obtains sulfonated polymer/graphene nanocomposite material and be: at the temperature of 25 DEG C, be that the ratio of 1g:5mL adds the diamine that mass concentration is 50% in described mixed solution according to described graphene oxide and described diamine, stir 1 minute, back flow reaction 2 hours at being heated to 100 DEG C afterwards, separation and purification, and then obtain sulfonated polymer/graphene nanocomposite material.
The application of 13. 1 kinds of sulfonated polymer/graphene nanocomposite materials according to claim 1 on contact panel.
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| CN201310443373.1A CN104464888B (en) | 2013-09-25 | 2013-09-25 | Sulfonated macromolecule/graphene nanocomposite and manufacturing method and application thereof |
| TW103129163A TWI568781B (en) | 2013-09-25 | 2014-08-25 | Sulfonated polymer/graphene nano-composite material and its preparation method and application |
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Cited By (3)
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| CN105001581A (en) * | 2015-07-14 | 2015-10-28 | 安徽雄亚塑胶科技有限公司 | TPE composition and high-performance sealing material obtained from same |
| CN105273403A (en) * | 2015-10-13 | 2016-01-27 | 中国科学院宁波材料技术与工程研究所 | High-conductivity polyimides-graphene composite material and preparation method thereof |
| CN113201246A (en) * | 2021-04-24 | 2021-08-03 | 深圳市撒比斯科技有限公司 | High-conductivity photosensitive electronic ink |
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| CN113201246A (en) * | 2021-04-24 | 2021-08-03 | 深圳市撒比斯科技有限公司 | High-conductivity photosensitive electronic ink |
Also Published As
| Publication number | Publication date |
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| TW201512273A (en) | 2015-04-01 |
| TWI568781B (en) | 2017-02-01 |
| CN104464888B (en) | 2017-01-11 |
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