CN1303152C - Carbon nano-pipel poly vinyl imidazole nano-composite material and its preparation method - Google Patents
Carbon nano-pipel poly vinyl imidazole nano-composite material and its preparation method Download PDFInfo
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- CN1303152C CN1303152C CNB2004100890368A CN200410089036A CN1303152C CN 1303152 C CN1303152 C CN 1303152C CN B2004100890368 A CNB2004100890368 A CN B2004100890368A CN 200410089036 A CN200410089036 A CN 200410089036A CN 1303152 C CN1303152 C CN 1303152C
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Abstract
The present invention relates to a carbon nanotube/polyvinyl imidazole nanometer composite material and a preparation method thereof, which belongs to the technical field of an organic / inorganic nanometer composite material. The composite material of the present invention is a carbon nanotube composite modified material which uses a polyvinyl imidazole polymerization monomer as a modifying agent; KH-570, voland or titanate 5S are used as coupling agents, and the composite material is obtained by a chemical etching method and a microemulsion polymerization method. The composite degree and the size dimension of the composite material can be controlled by regulating the reaction conditions of the coupling agents, the polymerization monomer, initiating agents, emulsifying agents, etc. The obtained composite material has the advantages of high thermal stability and chemical stability, good electric property and solubility, and good film forming property and photoelectric property, and can be used for the fields of electric conducting materials, fuel cell materials, photoconductive materials, photoelectric conversion materials, etc.
Description
Technical field
The invention belongs to the Organic technical field, be specifically related to a kind of carbon nano-tube/poly ethene imidazoles nano composite material and preparation method thereof.
Background technology
The research of carbon nanotube composite modification material has become one of focus of present investigation of materials.Up to now, the carbon nanotube composite modifying method of bibliographical information generally is divided into two classes.The first kind is the method that adopts physics to fill and coat, it is compound that carbon nanotube and metal or inorganic semiconductor etc. are carried out physics, though improved character such as the mechanics of carbon nano-tube material and photoelectricity, this method has shortcomings such as the complicated and mechanical property of technology is relatively poor.Another kind of is to obtain carbon nano-tube/polymer composite material with chemically modified or by home position polymerization reaction, though technology is simple, dispersing uniformity and the processability of carbon nanotube in solvent makes moderate progress, and the matrix material size is less, is difficult to control thermally-stabilised than problems such as property differences with matrix material but this method also exists the compound degree.
Summary of the invention
The objective of the invention is to propose that a kind of material property is good, the simple carbon nanotube composite modification material of recombining process and preparation method thereof.
The carbon nanotube composite modification material that the present invention proposes, be a kind of be polymerization single polymerization monomer (properties-correcting agent) with the polyvinyl imidazole, with KH-570, Wo Lan or titanic acid ester 5S is coupling agent, the carbon nano-tube/poly ethene imidazoles nano composite material for preparing through chemical etching method and microemulsion polymerization method.Here the polyvinyl imidazole monomer can be 1-vinyl imidazole, 2-vinyl imidazole, 3-vinyl imidazole or 5-vinyl imidazole etc.
The preparation method of the carbon nano-tube/poly ethene imidazoles nano composite material that the present invention proposes is as follows:
(1) 100～1000mg multi-walled carbon nano-tubes being added the 50ml vitriol oil and concentrated nitric acid is in the mixed strong acids solution of forming at 3: 1 by volume, sonic oscillation was handled 3～12 hours, pour in the deionized water, and leave standstill more than 12 hours, filter and be washed to neutrality, dry again, obtain the carbon nanotube of chemical etching;
(2) carbon nanotube with the above-mentioned chemical etching of 50～500mg is dispersed in the dehydrated alcohol, and under 35 ℃ of water bath condition, Dropwise 5～50ml concentration is the ethanolic soln of the coupling agent of 0.005～0.025g/ml.Successive reaction 10～40 hours, centrifuging and be washed to neutrality, 40 ℃ of following vacuum-dryings of temperature obtained the carbon nanotube through coupling agent treatment more than 12 hours;
(3) in the ethanolic soln of the carbon nanotube of the above-mentioned coupling agent treatment of 50～100mg, add buffer reagent, emulsifying agent and deionized water, under the strong mixer agitation condition, Dropwise 5～25mg polyvinyl imidazol polymerization single polymerization monomer, pre-emulsification 0.5～2 hour, be warming up to 75-85 ℃ then, Dropwise 5～50ml concentration is the aqueous solution of the persulphate of 0.012g/ml, reacts 6～12 hours, obtains the emulsion of carbon nano-tube/poly ethene imidazoles nano composite material; Obtain carbon nano-tube/poly ethene imidazoles nano composite material after the purified processing of this emulsion.
Among the present invention, used coupling agent is KH-570, fertile blue (methacrylate-chromic chloride title complex) or titanate coupling agent 5S, and its chemical structural formula is shown below respectively:
Among the present invention, used comonomer can be 1-vinyl imidazole, 2-vinyl imidazole, 3-vinyl imidazole or 5-vinyl imidazole.
Among the present invention, used buffer reagent can be sodium bicarbonate, yellow soda ash, salt of wormwood, potassiumphosphate, sodium phosphate, calcium phosphate, Tripotassium Citrate, Trisodium Citrate, citrate of lime, potassium primary phosphate, dipotassium hydrogen phosphate, SODIUM PHOSPHATE, MONOBASIC or Sodium phosphate dibasic.
Among the present invention, used emulsifying agent can be Sodium dodecylbenzene sulfonate, sodium lauryl sulphate, palmityl trimethyl ammonium chloride, octadecyl trimethyl ammonium chloride, OP series (as OP-10, OP-15, OP-20), tween (Tween) series (as Tween-20, Tween-40, Tween-60, Tween-80) or department's class's series (as Span-20, Span-60 and Span-80).
Among the present invention, used persulphate can be ammonium persulphate and Potassium Persulphate.
Advantage of the present invention is: 1. mainly be connected with covalent between carbon nanotube and the polyvinyl imidazole material, so the thermostability and the chemical stability of this carbon nano-tube/poly ethene imidazoles nano composite material are very high; 2. in the carbon nano-tube/poly ethene imidazoles nano composite material, the carbon nanotube caliber still keeps nanometer scale and partial order shape, not only keep carbon nanotube special mechanical properties and electric property, had good solubility property, film forming properties and the photoelectric properties etc. of conjugated polymers again; 3. the compound degree of carbon nano-tube/poly ethene imidazoles nano composite material and size can be controlled by regulating reaction conditionss such as coupling agent, polymerization single polymerization monomer, initiator and emulsifying agent.The present invention has important use to electro-conductive material, fuel cell material, photoconductive material and photoelectric conversion material field and is worth.
Description of drawings
Fig. 1 is the synoptic diagram of carbon nano-tube/poly ethene imidazoles nano composite material preparation.
Fig. 2 is the electron microscope picture of carbon nano-tube/poly ethene imidazoles nano composite material.
Fig. 3 is the electron microscope picture of carbon nano-tube material.
Fig. 4 is the state of aggregation figure of carbon nano-tube/poly ethene imidazoles nano composite material.
Embodiment
Above-mentioned carbon nano-tube/poly ethene imidazoles nano composite material, its preparation method is earlier 100～1000mg multi-walled carbon nano-tubes to be added at normal temperatures in the mixed strong acids solution of the 50ml vitriol oil and concentrated nitric acid (volume ratio is 3: 1) composition, sonic oscillation was handled 3～12 hours, pour in the deionized water and standing over night after, filter and be washed to neutrality, obtain the carbon nanotube of chemical etching after the oven dry; The carbon nanotube of the above-mentioned chemical etching of 50～500mg is dispersed in the dehydrated alcohol, and under 35 ℃ of water bath condition, (concentration is 0.005～0.025g/ml) to the ethanolic soln of Dropwise 5～50ml coupling agent.After the successive reaction 10～40 hours, centrifuging and be washed to neutrality after, vacuum-drying is spent the night under 40 ℃ of low temperature, obtains the carbon nanotube of coupling agent treatment; Add buffer reagent, emulsifying agent and deionized water in the ethanolic soln with the carbon nanotube of the above-mentioned coupling agent treatment of 50～100mg, under the strong mixer agitation condition, Dropwise 5～25mg 1-vinyl imidazole monomer, and pre-emulsification 0.5～2 hour.Be warming up to 80 ℃ then, the aqueous solution of Dropwise 5～50ml persulphate (concentration is 0.012g/ml) reacted after 6～12 hours, and stopped reaction obtains the emulsion of carbon nano-tube/poly ethene imidazoles nano composite material.
This emulsion is disperseed again through centrifuging and toluene again, so repeat 2～4 times after, remove by products such as polyvinyl imidazole homopolymer and emulsifying agent.60-70 ℃ of following vacuum-drying obtained carbon nano-tube/poly ethene imidazoles nano composite material more than 12 hours.
Wherein, used coupling agent is KH-570, Wo Lan or titanate coupling agent 5S, and its chemical structural formula is shown below respectively:
Used monomer is 1-vinyl imidazole, 2-vinyl imidazole, 3-vinyl imidazole or 5-vinyl imidazole.Used buffer reagent is sodium bicarbonate, yellow soda ash, salt of wormwood, potassiumphosphate, sodium phosphate, calcium phosphate, Tripotassium Citrate, Trisodium Citrate, citrate of lime, potassium primary phosphate, dipotassium hydrogen phosphate, SODIUM PHOSPHATE, MONOBASIC or Sodium phosphate dibasic.Used emulsifying agent is Sodium dodecylbenzene sulfonate, sodium lauryl sulphate, palmityl trimethyl ammonium chloride, octadecyl trimethyl ammonium chloride, OP-10, OP-15, OP-20, tween 20, Tween-40, Tween-60, tween-80, Span-20, Span-60 or Span-80.Used initiator is ammonium persulphate or Potassium Persulphate.
The present invention will be described in detail below in conjunction with embodiment.Do not violating under the purport of the present invention, the present invention should be not limited to the content that following examples are specifically expressed.
Embodiment 1
The 1g multi-walled carbon nano-tubes is added in the mixed strong acids solution of the 100ml vitriol oil and concentrated nitric acid (volume ratio is 3: 1) composition, sonic oscillation was handled after 6 hours, slowly poured 500ml deionized water (band stirs) into, after the standing over night, filter and wash neutral with deionized water, put into oven for drying.Repeat 3 times, obtain the carbon nano-tube material behind the chemical etching.The good carbon nanotube of weighing 100mg chemical etching is dispersed in the dehydrated alcohol, under 35 ℃ of water bath condition, dropwise drips the ethanolic soln (concentration is 0.067g/ml) of 30mlKH-570.Keep temperature and stirring velocity constant, successive reaction is after 40 hours, centrifuging under 3400 rev/mins of rotating speeds, again disperse with dehydrated alcohol again, after repeating 5 times, vacuum-drying is spent the night under 40 ℃ of low temperature, obtains the double bond containing carbon nanotube after the coupling agent treatment.The carbon nanotube of the above-mentioned coupling agent treatment of 50mg is added 10ml dehydrated alcohol ultra-sonic dispersion 0.5h, add 0.3g sodium bicarbonate, 0.05g Sodium dodecylbenzene sulfonate and 150ml deionized water then, under the strong mixer agitation condition, drip 10ml 1-vinyl imidazole monomer, and pre-emulsification 1h, be warming up to 80 ℃ then, drip 25ml ammonium persulfate aqueous solution (concentration is 0.012g/ml), react after 12 hours, stopped reaction obtains the emulsion of carbon nano-tube/poly ethene imidazoles nano composite material.This emulsion centrifuging and toluene under 3400 rev/mins of rotating speeds disperse again, so repeat 3 times after, remove by products such as polyvinyl imidazole homopolymer and emulsifying agent.Dried overnight in 60 ℃ of vacuum drying ovens obtains carbon nano-tube/poly ethene imidazoles nano composite material at last.
The preparation process of this carbon nano-tube/poly ethene imidazoles nano composite material as shown in Figure 1, its microtexture such as Fig. 2, Fig. 3 and shown in Figure 4.
Embodiment 2
Identical with embodiment 1, fertile blue but KH-570 becomes.
Embodiment 3
Identical with embodiment 1, but KH-570 becomes titanate coupling agent 5S.
Embodiment 4
Identical with embodiment 1, but the concentration of KH-570 becomes 0.201g/ml by 0.067g/ml.
Embodiment 5
Identical with embodiment 1, but the concentration of KH-570 becomes 0.022g/ml by 0.067g/ml.
Embodiment 6
Identical with embodiment 1, but the monomeric consumption of 1-vinyl imidazole becomes 15ml by 10ml.
Embodiment 7
Identical with embodiment 1, but the monomeric consumption of 1-vinyl imidazole becomes 5ml by 10ml.
Embodiment 8
Identical with embodiment 1, but the concentration of ammonium persulfate aqueous solution becomes 0.024g/ml by 0.012g/ml.
Embodiment 9
Identical with embodiment 1, but the concentration of ammonium persulfate aqueous solution becomes 0.006g/ml by 0.012g/ml.Carbon nano-tube/poly ethene imidazoles matrix material that obtains among the embodiment 2-9 and the material of embodiment 1 have similar microstructure and performance.
Claims (8)
1, a kind of carbon nanotube composite modification material, it is characterized in that with the polyvinyl imidazole being polymerization single polymerization monomer, with KH-570, Wo Lan or titanic acid ester 5S is coupling agent, the carbon nano-tube/poly ethene imidazoles nano composite material for preparing through chemical etching method and microemulsion polymerization method; Wherein, polymerization single polymerization monomer is 1-vinyl imidazole, 2-vinyl imidazole, 3-vinyl imidazole or 5-vinyl imidazole; The part by weight of carbon nanotube and polymerization single polymerization monomer is 50-100: 5-25.
2, a kind of preparation method of carbon nano-tube/poly ethene imidazoles nano composite material as claimed in claim 1 is characterized in that concrete steps are:
(1) 100～1000mg multi-walled carbon nano-tubes being added the 50ml vitriol oil and concentrated nitric acid is in the mixed strong acids solution of forming at 3: 1 by volume, sonic oscillation was handled 3～12 hours, pour in the deionized water, and leave standstill more than 12 hours, filter and be washed to neutrality, obtain the carbon nanotube of chemical etching after the oven dry;
(2) carbon nanotube with the above-mentioned chemical etching of 50～500mg is dispersed in the dehydrated alcohol, under 35 ℃ of water bath condition, Dropwise 5～50ml concentration is the ethanolic soln of the coupling agent of 0.005～0.025g/ml, successive reaction 10～40 hours, centrifuging and be washed to neutrality, 40 ℃ of following vacuum-dryings of temperature obtained the carbon nanotube through coupling agent treatment more than 12 hours;
(3) in the ethanolic soln of the carbon nanotube of the above-mentioned coupling agent treatment of 50～100mg, add buffer reagent, emulsifying agent and deionized water, under the agitator agitation condition, Dropwise 5～25mg polyvinyl imidazole polymerization single polymerization monomer, pre-emulsification 0.5～2 hour, be warming up to 75-85 ℃ then, Dropwise 5～50ml concentration is the aqueous solution of the persulphate of 0.012g/ml, reacts 6～12 hours, obtains the emulsion of carbon nano-tube/poly ethene imidazoles nano composite material; The purified processing of this emulsion obtains carbon nano-tube/poly ethene imidazoles nano composite material.
3, preparation method according to claim 2 is characterized in that described coupling agent is KH-570, Wo Lan or titanic acid ester 5S, and its chemical structural formula is shown below respectively:
4, preparation method according to claim 2 is characterized in that said polymerization single polymerization monomer is 1-vinyl imidazole, 2-vinyl imidazole, 3-vinyl imidazole or 5-vinyl imidazole.
5, preparation method according to claim 2 is characterized in that said buffer reagent is sodium bicarbonate, yellow soda ash, salt of wormwood, potassiumphosphate, citrate of lime, potassium primary phosphate, dipotassium hydrogen phosphate, SODIUM PHOSPHATE, MONOBASIC or Sodium phosphate dibasic.
6, preparation method according to claim 2 is characterized in that said emulsifying agent is Sodium dodecylbenzene sulfonate, sodium lauryl sulphate, palmityl trimethyl ammonium chloride, octadecyl trimethyl ammonium chloride, OP-10, OP-15, OP-20, Tween-20, Tween-40, Tween-60, Tween-80, Span-20, Span-60 or Span-80.
7, preparation method according to claim 2 is characterized in that said persulphate is ammonium persulphate or Potassium Persulphate.
8, preparation method according to claim 2, it is characterized in that said purification process, is emulsion to be carried out centrifuging and toluene disperses again, repeats 2～4 times, remove polyvinyl imidazole homopolymer and emulsifying agent by product, then 60-70 ℃ of following vacuum-drying more than 12 hours.
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| US7982130B2 (en) * | 2008-05-01 | 2011-07-19 | The Regents Of The University Of Michigan | Polymer wrapped carbon nanotube near-infrared photovoltaic devices |
| CN102515141B (en) * | 2011-12-02 | 2015-03-25 | 东华理工大学 | Method for synthesizing modified SWCNTs (Single Wall Carbon Nano Tubes) based on Bergman cyclizing reaction |
| CN105597568B (en) * | 2016-02-23 | 2018-07-20 | 天津大学 | Chloromethylation polyether-ether-ketone/imidazoles carbon nano tube hybridized film and preparation and application |
| CN110079759B (en) * | 2019-03-11 | 2020-11-27 | 安徽格斯波纹管有限公司 | Surface treatment method for metal corrugated pipe |
| CN117467226B (en) * | 2023-12-28 | 2024-03-19 | 上海拜安传感技术有限公司 | Composition, sensing film, sensor, preparation method and application |
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| CN1410455A (en) * | 2002-03-14 | 2003-04-16 | 四川大学 | Preparation method of polymer/carbon nano pipe composite emulsion and its in situ emulsion polymerization |
| EP1475407A2 (en) * | 2003-05-08 | 2004-11-10 | Clariant GmbH | Flame retardant nanocomposite combination for thermoplastic polymers |
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| CN1410455A (en) * | 2002-03-14 | 2003-04-16 | 四川大学 | Preparation method of polymer/carbon nano pipe composite emulsion and its in situ emulsion polymerization |
| EP1475407A2 (en) * | 2003-05-08 | 2004-11-10 | Clariant GmbH | Flame retardant nanocomposite combination for thermoplastic polymers |
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