CN105085907A - Method for preparing polyaniline grafted carbon material - Google Patents
Method for preparing polyaniline grafted carbon material Download PDFInfo
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- CN105085907A CN105085907A CN201510604549.6A CN201510604549A CN105085907A CN 105085907 A CN105085907 A CN 105085907A CN 201510604549 A CN201510604549 A CN 201510604549A CN 105085907 A CN105085907 A CN 105085907A
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- carbonaceous material
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Abstract
The invention relates to a method for preparing a polyaniline grafted carbon material. The method comprises the steps that a carbon material firstly oxidized, and an epoxy group is introduced to the surface of the carbon material; then the carbon material reacts with p-phenylenediamine, and an anilino group is introduced to the surface of the oxidized carbon material; finally, polyaniline is grafted to the surface of the material. According to the method, grafted polyaniline and the carbon material are directly and electronically conjugated, conductivity and stability higher than those of other methods are achieved, and the prepared polyaniline grafted carbon material has great application potential in the fields of conductive coating, static prevention, radiation protection, wave absorption, composites and the like.
Description
Technical field
The present invention relates to a kind of preparation method of polyaniline grafted carbonaceous material, specifically belong to macromolecule organic material technical field.
Background technology
The carbonaceous materials such as Graphite Powder 99, Graphene, carbon black, carbon fiber, carbon nanotube are at conductive devices, absorbing material, electrically conducting coating, and aviation field, the field such as antistatic is widely used.But material exists, and particle is little, specific surface area is large, interparticle reactive force is strong, very easily reunites, not easily disperse, electric conductivity be low, with the shortcoming such as resin boundary surface compatibility performance difference, constrain it and apply more widely.
Polyaniline has the antiseptic property of good thermostability, chemical stability, electrochemical reversibility, microwave absorption performance and uniqueness, has a wide range of applications in electrical condenser, anticorrosion, the field such as solar cell, electromagnetic shielding.In order to improve carbonaceous material dispersiveness, consistency and specific conductivity, be a kind of good method at its Surface coating or Polyaniline Grafted, and done a lot of research.In patent CN103337377A, describe the method utilizing the direct coating graphite alkene of polyaniline, and be applied on electrical condenser; Patent CN103613755A describes at graphenic surface first grafted silane coupling agent, then utilizes silane coupling agent to cause the polymerization of polyaniline, thus at graphenic surface Polyaniline Grafted; First oxide/carbon nanometer tube in patent CN104465110A, then utilizes carboxyl and Ursol D to react, and is middlely connected with carbon nanotube by aniline by an amido linkage, finally utilizes the polymerization of the anilino initiation polyaniline in grafting; Describe the process utilizing liquefied ammonia and oxide/carbon nanometer tube to react in patent CN104098944A, amido has been directly grafted on carbonaceous material, has then caused the preparation process of polyaniline.Researched and analysed by current, we find that Polyaniline Grafted has had a lot of method on carbonaceous material, but the polyaniline of grafting does not directly link with carbon atom, centre is isolated by the group of non-conjugated property, have a strong impact on the fluency of electric transmission, thus affect the performance such as conduction, suction ripple of material.And the method for the direct introducing amido introduced in patent CN104098944A, condition is very harsh, is unfavorable for large-scale production.
The present invention is carbonoxide based material first, epoxy group(ing) is introduced on surface, then the reaction of Ursol D and epoxy group(ing) anilino on its surface grafting is utilized, anilino is finally utilized to cause polyaniline reaction, thus in material surface grafting electrically conductive polyaniline, and polyaniline is connected with the direct conjugation of carbonaceous material, there is higher electronics and move fluency.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of polyaniline grafted carbonaceous material, to achieve these goals, preparation method's step of the present invention is as follows:
(1) 10g carbonaceous material, the dense H of 100 ~ 300ml
2sO
4, 3 ~ 7gNaNO
3after mixing, under condition of ice bath in 1 hour, slowly add wherein by 15 ~ 40g potassium permanganate, after adding, temperature of reaction system is elevated to 35 DEG C gradually, then is incubated 1 hour; Then after slowly adding 150 ~ 300ml distilled water in reaction system, temperature of reaction system is elevated to 90 DEG C, after at the uniform velocity stirring 30min, slowly adds 15 ~ 40mlH
2o
2, be cooled to room temperature, after filtration, vacuum-drying, obtain carbonoxide based material.
(2) after the mixing of 3g carbonoxide based material, 5 ~ 10ml Ursol D and 20ml toluene, after 70 DEG C of reaction 10h, after filtration, after washing, drying treatment, again with the aqueous solution of 2 ~ 5g Sodium dodecylbenzene sulfonate, 1 ~ 15g aniline, 10 ~ 25ml Virahol, and after the sonic oscillation of 30min stirring and emulsifying 10min, then the hydrochloric acid soln that 10 ~ 25ml concentration is 2mol/L is added wherein, system temperature is controlled in the ice-water bath of 0 ~ 5 DEG C, drip the 1mol/L ammonium persulfate aqueous solution of 0.8 ~ 1.5 times of aniline moles, stirring reaction 6h; After completion of the reaction, product carries out washing suction filtration successively with the hydrochloric acid of 0.33mol/L, dehydrated alcohol, distilled water respectively, then through vacuum-drying, obtains polyaniline grafted carbonaceous material.
Described carbonaceous material can be Graphite Powder 99, Graphene, carbon black, short carbon fiber or carbon nanotube.
In the aqueous solution of described Virahol, the volume ratio of Virahol and water is 1:5.
advantage of the present invention:
The present invention passes through carbonaceous material surface directly conjugation Polyaniline Grafted, make the carbonaceous material of polyaniline grafted modification have higher electronics and move fluency, improve the electroconductibility of material monolithic, overcome the interrupted situation of electroconductibility after current most material surface Polyaniline Grafted.Preparation method of the present invention is easy, and reaction conditions is gentle, and raw material is easy to get, and is applicable to large-scale production.
Embodiment
Illustrate the present invention is detailed further below in conjunction with embodiment, but content of the present invention is not only confined to the following examples.
embodiment 1
(1) 10g Graphite Powder 99 (particle diameter 16um ~ 20um) and the dense H of 150ml is taken
2sO
4, 6gNaNO
3join in beaker, slowly 30g potassium permanganate was added wherein in 1 hour under condition of ice bath, after adding, temperature is elevated to 35 DEG C gradually, be incubated 1 hour.Then after slowly adding 200ml distilled water in system, temperature is elevated to 90 DEG C, at the uniform velocity stirs 30min, slowly add 30mlH
2o
2, be cooled to room temperature, filter, vacuum-drying.
(2) above-mentioned modified graphite powder 3g is got, add 6ml Ursol D and 20mL toluene, under 70 DEG C of conditions, react 10h, filter, washing, after drying, add the Sodium dodecylbenzene sulfonate of 4g, 1g aniline with and 15ml Virahol and water mixing solutions in, stirring and emulsifying after sonic oscillation 30min, then the hydrochloric acid soln that 15mL concentration is 2mol/L is added, system temperature is controlled in the ice-water bath of 0 DEG C, drip the 1mol/L ammonium persulfate aqueous solution of 0.8 times of aniline moles, stirring reaction 6h.After completion of the reaction, washing suction filtration is carried out successively, then vacuum-drying with the hydrochloric acid of 0.33mol/L, dehydrated alcohol, distilled water respectively.
embodiment 2
Other reactions are identical with embodiment 1, just Graphite Powder 99 is changed to Graphene (diameter 0.5-3um), and oxidising process change: the dense H of 200ml into
2sO
4, 5gNaNO
3join in beaker, slowly 20g potassium permanganate was added wherein in 1 hour under condition of ice bath, after adding, temperature is elevated to 35 DEG C gradually, be incubated 1 hour.Then after slowly adding 200ml distilled water in system, temperature is elevated to 90 DEG C, at the uniform velocity stirs 30min, slowly add 30mlH
2o
2, be cooled to room temperature, filter, vacuum-drying.
embodiment 3
Other reactions are identical with embodiment 1, just Graphite Powder 99 are changed to short carbon fiber (mean length 230um), and Ursol D, the add-on of Sodium dodecylbenzene sulfonate changes 7ml and 3g into respectively.
embodiment 4
Other reactions are identical with embodiment 2, just Graphene is changed to multi-walled carbon nano-tubes (length 10 ~ 30um, caliber 10 ~ 20nm), and Ursol D, the add-on of Sodium dodecylbenzene sulfonate change 7ml and 3g into respectively.
embodiment 5
Other reactions are identical with embodiment 3, just short carbon fiber is changed to graphitized carbon black (median size 18nm), and the add-on of ammonium persulfate aqueous solution change the 1mol/L ammonium persulfate aqueous solution of dropping 1.5 times of aniline moles into
Get the sample of preparation, at 20MPa condition lower sheeting, utilize four point probe conductivitimeter to test its conductivity.
embodiment 1-embodiment 5 performance test
The performance test data table look-up of the carbonaceous material after graft modification
| Specific conductivity (S/cm) | |
| Embodiment 1 | 2.6 |
| Embodiment 2 | 1.5 |
| Embodiment 3 | 17.8 |
| Embodiment 4 | 1.3 |
| Embodiment 5 | 0.9 |
Claims (3)
1. a preparation method for polyaniline grafted carbonaceous material, is characterized in that, described preparation method's step is as follows:
(1) 10g carbonaceous material, the dense H of 100 ~ 300ml
2sO
4, 3 ~ 7gNaNO
3after mixing, under condition of ice bath in 1 hour, slowly add wherein by 15 ~ 40g potassium permanganate, after adding, temperature of reaction system is elevated to 35 DEG C gradually, then is incubated 1 hour; Then after slowly adding 150 ~ 300ml distilled water in reaction system, temperature of reaction system is elevated to 90 DEG C, after at the uniform velocity stirring 30min, slowly adds 15 ~ 40mlH
2o
2, be cooled to room temperature, after filtration, vacuum-drying, obtain carbonoxide based material;
(2) after the mixing of 3g carbonoxide based material, 5 ~ 10ml Ursol D and 20ml toluene, after 70 DEG C of reaction 10h, after filtration, after washing, drying treatment, again with the aqueous solution of 2 ~ 5g Sodium dodecylbenzene sulfonate, 1 ~ 15g aniline, 10 ~ 25ml Virahol, and after the sonic oscillation of 30min stirring and emulsifying 10min, then the hydrochloric acid soln that 10 ~ 25ml concentration is 2mol/L is added wherein, system temperature is controlled in the ice-water bath of 0 ~ 5 DEG C, drip the 1mol/L ammonium persulfate aqueous solution of 0.8 ~ 1.5 times of aniline moles, stirring reaction 6h; After completion of the reaction, product carries out washing suction filtration successively with the hydrochloric acid of 0.33mol/L, dehydrated alcohol, distilled water respectively, then through vacuum-drying, obtains polyaniline grafted carbonaceous material.
2. the preparation method of a kind of polyaniline grafted carbonaceous material according to claim 1, is characterized in that, described carbonaceous material can be Graphite Powder 99, Graphene, carbon black, short carbon fiber or carbon nanotube.
3. the preparation method of a kind of polyaniline grafted carbonaceous material according to claim 1, is characterized in that, in the aqueous solution of described Virahol, the volume ratio of Virahol and water is 1:5.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108642968A (en) * | 2018-07-11 | 2018-10-12 | 佛山腾鲤新能源科技有限公司 | A kind of preparation method of carbon nano tube conductive paper |
| CN108642885A (en) * | 2018-05-25 | 2018-10-12 | 晋江瑞碧科技有限公司 | The Preparation method and use of activated carbon/polyaniline-p-phenylenediamine copolymer composite nano fiber |
| CN108659422A (en) * | 2018-04-26 | 2018-10-16 | 武汉工程大学 | A kind of polyaniline/graphene/polyvinyl alcohol plural gel and preparation method thereof |
| CN109535737A (en) * | 2018-11-14 | 2019-03-29 | 湖南湘贤科技有限公司 | A kind of preparation method of electric-conductivity heat-conductivity high graphene composite material |
| CN110289176A (en) * | 2019-02-25 | 2019-09-27 | 常州大学 | A kind of preparation method for the polyaniline grafted redox graphene/multi-wall carbon nano-tube composite material can be used for electrochemical energy storage |
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| CN104098944A (en) * | 2013-05-31 | 2014-10-15 | 江西省电力科学研究院 | Method for preparing high-performance fluoro-carbon anticorrosive coating through grafting of conducting polymer onto carbon nanotube |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108659422A (en) * | 2018-04-26 | 2018-10-16 | 武汉工程大学 | A kind of polyaniline/graphene/polyvinyl alcohol plural gel and preparation method thereof |
| CN108659422B (en) * | 2018-04-26 | 2021-02-12 | 武汉工程大学 | Polyaniline/graphene/polyvinyl alcohol composite gel and preparation method thereof |
| CN108642885A (en) * | 2018-05-25 | 2018-10-12 | 晋江瑞碧科技有限公司 | The Preparation method and use of activated carbon/polyaniline-p-phenylenediamine copolymer composite nano fiber |
| CN108642885B (en) * | 2018-05-25 | 2020-12-01 | 晋江瑞碧科技有限公司 | Preparation method and application of activated carbon/polyaniline-p-phenylenediamine copolymer composite nanofiber |
| CN108642968A (en) * | 2018-07-11 | 2018-10-12 | 佛山腾鲤新能源科技有限公司 | A kind of preparation method of carbon nano tube conductive paper |
| CN108642968B (en) * | 2018-07-11 | 2020-12-01 | 深圳市宏途创嘉科技有限公司 | Preparation method of carbon nanotube conductive paper |
| CN109535737A (en) * | 2018-11-14 | 2019-03-29 | 湖南湘贤科技有限公司 | A kind of preparation method of electric-conductivity heat-conductivity high graphene composite material |
| CN110289176A (en) * | 2019-02-25 | 2019-09-27 | 常州大学 | A kind of preparation method for the polyaniline grafted redox graphene/multi-wall carbon nano-tube composite material can be used for electrochemical energy storage |
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Application publication date: 20151125 |