CN104448167A - Method for preparing core-shell type carbon nanotube conductive fillers by virtue of controllable coating technology - Google Patents
Method for preparing core-shell type carbon nanotube conductive fillers by virtue of controllable coating technology Download PDFInfo
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Abstract
The invention provides a method for preparing core-shell type carbon nanotube conductive fillers by virtue of a controllable coating technology. The method is mainly characterized in that the adsorption of the core-shell type carbon nanotube conductive fillers for multi-wall carbon nanotubes is realized by virtue of the adsorption action of the multi-wall carbon nanotubes for micromolecules, the surfaces of the carbon nanotubes are activated by azodiisobutyronitrile to generate active free radical centres and the polymerization-crosslinking of a divinyl benzene monomer is initiated, thus achieving a coating purpose. The preparation process comprises the following steps: ultrasonically dispersing the multi-wall carbon nanotubes in a solvent at first, and then adding an initiator, heating, reacting and gradually dripping the monomer; finally obtaining a series of core-shell type carbon nanotube conductive fillers with different coating thicknesses by adjusting the ratio among the various reactants. According to the method, the pre-treatment processes of acidification, oxidization and the like for the carbon nanotubes are not required, thus the own structures of the carbon nanotubes are not damaged, and the influence on the performances of the carbon nanotubes is less; the method is an effective way of preparing a core-shell type carbon nanotube compound, and has the advantages of simple process, flexible and wide applicability, wide industrialization prospect and the like.
Description
Technical field
The coated original carbon nanotubes of Vinylstyrene controllable polymerization that the invention relates to polyfunctionality prepares the method for hud typed mixture powder, belongs to technical field prepared by matrix material.
Background technology
Carbon nanotube is another the novel carbonaceous Nano-Materials occurred after soccerballene, curlingly to be formed according to certain helix angle by one deck or Multi-layer graphite synusia from structure carbon nanotube, cylindrical shell carbon nanotube that diameter is nanometer scale is because of the mechanics of its uniqueness, characteristic electron and chemical property, become the focus of research in world wide, achieve in various fields such as Flied emission, molecular electronic device, composite reinforcing material, hydrogen storage material, support of the catalyst and apply widely.
The seamless tubular shaped structure of carbon nanotube and the good degree of graphitization of pipe shaft impart the mechanical property of carbon nanotube excellence, tensile strength reaches 50-200GPa, and be 100 times of steel, density but only has 1/6 of steel, at least high than an ordinary graphite fiber order of magnitude, is thus called as " ultra high strength fiber ".Also have high elasticity, its Young's modulus can reach 1TPa simultaneously, suitable with adamantine Young's modulus, is about five times of steel.Using carbon nanotube as composite material reinforcement body, good intensity, elasticity, fatigue resistance and isotropy can be shown, bring great improvement to the performance of matrix material.Carbon nanotube has similar high molecular structure, and has very high axial strength and rigidity.With macromolecular material compound tense, obtain the matrix material of excellent performance, make carbon nanotube show excellent electric property and mechanical property, this makes carbon nanotube have tempting application prospect in field of compound material.
But carbon nanotube dispersiveness is in a solvent poor, also poor with the consistency of other materials, which limits its application.In the last few years, coating technology is utilized to modify to carbon nanotube running-surface the extensive concern that the method preparing hud typed compounded mix receives people.Carbon nanotube after coated both can be used alone as hybrid material separately, as electrochemical sensor etc., also can prepare polymer matrix composite as filler, as conduction and dielectric composite material etc., therefore realize, to the controlled coated of carbon nanotube, there is very wide application prospect.
Vinylstyrene is the monomer with two vinyl, and structure and styrenic are seemingly.The insoluble polymer of three-dimensional structure can be generated during copolymerization, therefore be a kind of very useful linking agent, be widely used in ion exchange resin, ion-exchange membrane, ABS resin, polystyrene resin, unsaturated polyester resin, synthetic rubber, wood working, carbon processing and other fields.Because it is the by product that ethene and benzene obtain when ethylbenzene is produced in alkylation, abundance of therefore originating, cheap.
Carbon nano-tube modified traditional method is by carbon nanotube acidification under concentrated acid condition, and the carboxyl utilizing acidifying to obtain or other functional groups carry out reacting or initiated polymerization further, thus improves carbon nanotube dispersiveness in the material and consistency.But the structure deteriorate of acidification to carbon nanotube is serious, its performance is caused to be subject to great impact, there are many workers to attempt utilizing the conjugated double bond of carbon nano tube surface or physical adsorption to carry out modified carbon nano-tube in recent years for this reason, but it is not coated even not for obtaining result, be exactly that cost is too high, be difficult to the production carried out on a large scale.Not modified carbon nanotube dispersiveness is in organic solvent not good, and most polymer compatibility is also poor, thus has a strong impact on the performance of matrix material.Therefore the method has coated closely controlled, the plurality of advantages such as experimentation is simple to operate, material controllability is good.
Summary of the invention
The object of the present invention is to provide a kind of short-cut method prepared Vinylstyrene enveloped carbon nanometer tube and prepare hud typed carbon nanotube compounded mix.In preparation process, first multi-walled carbon nano-tubes abundant ultrasonic solution in a small amount of solvent is reunited, then add initiator by ultrasonication at carbon nano tube surface activation generation free radical activity center.Then logical nitrogen protection oxygen under certain rotating speed in stirring at room temperature eliminating system, raises temperature of reaction and progressively drips monomer and makes it be polymerized, and obtains final hud typed carbon mano-tube composite.
Poly ion liquid enveloped carbon nanometer tube provided by the invention prepares the preparation process of hud typed carbon nanotube filler, and concrete steps are:
A) be the suspension of concentration 1-5mg/mL by original carbon nanotubes, DMF mixed preparing, ultrasonic more than 45min;
B) by quality 0.25 doubly in a) Diisopropyl azodicarboxylate of carbon nanotube add in above-mentioned suspension, continue ultrasonic 10min with abundant activated carbon nano-tube, obtain homogeneous system;
C) in above-mentioned system, pass into nitrogen and be warming up to 80 DEG C, dripping carbon nanotube mass 1-10 monomer Vinylstyrene doubly gradually, and with this conditioned response 12h;
D), after reaction stops, suction filtration obtains product, obtains final product successively with methyl alcohol, deionized water wash.
Further, step c) in adopt the Vinylstyrene of technical grade purity.
Further, step c) in change the consumption of Vinylstyrene and can control the thickness of coating layer between 5-60nm.
The feature that polyfunctionality vinyl monomer enveloped carbon nanometer tube provided by the invention prepares the method for hud typed carbon nanotube filler is:
1. utilize radical initiator Diisopropyl azodicarboxylate to the activation of carbon nanotube tube wall, under homogeneous system, directly cause the polymerization of multi-vinyl monomer and to realize carbon nanotube with this coated.Do not need to carry out acidifying to carbon nanotube, the process such as oxidation, the structure of carbon nanotube is not damaged, thus retain the original performance of carbon nanotube to the full extent.
2. coating layer is crosslinking structure, therefore firmly coated in carbon nano tube surface, difficult drop-off.
3. what achieve carbon nanotube is entirely coated, and cladding ratio is comparatively even, and the thickness of coating layer is controlled, significantly improves the dispersiveness of carbon nanotube in organic solution.
4. operation is relatively simple and direct, and cost is low.
Accompanying drawing explanation
Fig. 1: the coated multi-walled carbon nano-tubes of divinyl benzene polymers provided by the invention prepares the process flow sheet of hud typed compounded mix.
Fig. 2: the transmission electron microscope photo of the hud typed compounded mix of the coated multi-walled carbon nano-tubes of divinyl benzene polymers.
A) carbon nanotube and monomer weight ratio are 1:1
B) carbon nanotube and monomer weight ratio are 1:3
C) carbon nanotube and monomer weight ratio are 1:5
D) carbon nanotube and monomer weight ratio are 1:10
Fig. 3: the thermogravimetric curve of the hud typed compounded mix of the coated multi-walled carbon nano-tubes of divinyl benzene polymers.
A) carbon nanotube and monomer weight ratio are 1:1
B) carbon nanotube and monomer weight ratio are 1:3
C) carbon nanotube and monomer weight ratio are 1:5
D) carbon nanotube and monomer weight ratio are 1:10
Embodiment
Carbon nano tube surface can be caught polymer chain grafting that the free radical produced in polyreaction makes to be polymerized and be become entangled in carbon nano tube surface, but this can make polymer chain lose the activity of polymerization further equally, molecular weight has been controlled in very low scope, does not reach said covered effect.And adopt the divinylbenzene monomers of polyfunctionality to address this problem, improve coated thickness and controllability.Vinylstyrene is industrial conventional a kind of linking agent, and itself is cheap, and its similar, in the monomer of conventional poly styrene polymer, therefore has good consistency with polystyrene and other multiple polymers.But this monomer reaction activity is very high, easy autohemagglutination becomes crosslinked insoluble not molten polymkeric substance, wants to control it and carries out cross-linking reaction and the auto-polymerization reaction reduced as far as possible in solvent system is a technical barrier needing to solve in carbon nano tube surface.We reduce by the monomer concentration that reduces system and the method that drips reactive monomer gradually the generation that auto-polymerization reacts as much as possible.Consider simultaneously the too low generation of monomer concentration the situation that rate of polymerization is not high and coated thickness is too low we have employed following consumption and working method.
Embodiment 1
Weigh carbon nanotube 150mg, be placed in there-necked flask, add the DMF (DMF) of 150ml as solvent, ultrasonic disperse 45min, adds the initiator Diisopropyl azodicarboxylate of 25mg and continues ultrasonic 10min.Measure Vinylstyrene (DVB) monomer of 0.15g, and add in dropper after dilution.There-necked flask is moved in oil bath, under nitrogen protection, stirring at room temperature 1h.Be warming up to 80 DEG C, Vinylstyrene (DVB) monomer dripped in dropper carries out polyreaction gradually.Heating is stopped to terminate reaction after 12h.Suction filtration obtains product, uses water, methanol wash 30min respectively, and last suction filtration obtains target product.Fig. 2 (a) is the transmission electron microscope photo of the hud typed mixture (particular flow sheet as shown in Figure 1) of Vinylstyrene enveloped carbon nanometer tube prepared by the present embodiment.As can be seen from the figure have the uniform coating of thin layer at multi-walled carbon nano-tubes outer wall, thickness is greatly about below 5nm.Can find out through thermogravimetric curve, due to divinyl benzene polymers on coated outside carbon nanotube, so contrast the mass loss that pure carbon pipe has occurred about 35%, as shown in (a) in Fig. 3.Can prove that Vinylstyrene is successfully coated on carbon nano tube surface in conjunction with this two point data.
Embodiment 2
Weigh carbon nanotube 150mg, be placed in there-necked flask, add the DMF (DMF) of 150ml as solvent, ultrasonic disperse 45min.Add the initiator Diisopropyl azodicarboxylate of 25mg and continue ultrasonic 10min.Measure Vinylstyrene (DVB) monomer of 0.45g, and add in dropper after dilution.There-necked flask is moved in oil bath, under nitrogen protection, stirring at room temperature 1h.Be warming up to 80 DEG C, drip monomer gradually and carry out polyreaction.Heating is stopped to terminate reaction after 12h.Suction filtration obtains product, uses water, methanol wash 30min respectively, and last suction filtration obtains target product.Fig. 2 (b) is the transmission electron microscope photo of the hud typed mixture of Vinylstyrene enveloped carbon nanometer tube prepared by the present embodiment.As can be seen from the figure have the uniform coating of thin layer at multi-walled carbon nano-tubes outer wall, thickness is greatly about about 20nm.Can find out through thermogravimetric curve, due to divinyl benzene polymers on coated outside carbon nanotube, so contrast the mass loss that pure carbon pipe has occurred about 45%, as shown in (b) in Fig. 3.Can prove that divinyl benzene polymers is successfully coated on carbon nano tube surface in conjunction with this two point data.
Embodiment 3
Weigh carbon nanotube 150mg, be placed in there-necked flask, add the DMF (DMF) of 150ml as solvent, ultrasonic disperse 45min, adds the initiator Diisopropyl azodicarboxylate of 25mg and continues ultrasonic 10min.Measure Vinylstyrene (DVB) monomer of 0.75g, add in dropper after dilution.There-necked flask is moved in oil bath, under nitrogen protection, stirring at room temperature 1h.Be warming up to 80 DEG C, drip monomer gradually and carry out polyreaction.Heating is stopped to terminate reaction after 12h.Suction filtration obtains product, uses water, methanol wash 30min respectively, and last suction filtration obtains target product.Fig. 2 (c) is the transmission electron microscope photo of the hud typed mixture of Vinylstyrene enveloped carbon nanometer tube prepared by the present embodiment.As can be seen from the figure have the uniform coating of thin layer at multi-walled carbon nano-tubes outer wall, thickness is greatly about below 40nm.Can find out through thermogravimetric curve, due to polymkeric substance on coated outside carbon nanotube, so contrast the mass loss that pure carbon pipe has occurred about 55%, as shown in (c) in Fig. 3.Can prove that divinyl benzene polymers is successfully coated on carbon nano tube surface in conjunction with this two point data.
Embodiment 4
Weigh carbon nanotube 150mg, be placed in there-necked flask, add the DMF (DMF) of 150ml as solvent, ultrasonic disperse 45min, adds the initiator Diisopropyl azodicarboxylate of 25mg and continues ultrasonic 10min.Measure Vinylstyrene (DVB) monomer of 1.5g, add after dilution in dropper, there-necked flask is moved in oil bath, under nitrogen protection, stirring at room temperature 1h.Be warming up to 80 DEG C, drip monomer gradually and carry out polyreaction.Heating is stopped to terminate reaction after 12h.Suction filtration obtains product, uses water, methanol wash 30min respectively, and last suction filtration obtains target product.Fig. 2 (d) is the transmission electron microscope photo of the hud typed mixture (particular flow sheet as shown in Figure 1) of Vinylstyrene enveloped carbon nanometer tube prepared by the present embodiment.As can be seen from the figure have the uniform coating of thin layer at multi-walled carbon nano-tubes outer wall, thickness is greatly about about 60nm.Can find out through thermogravimetric curve, due to polymkeric substance on coated outside carbon nanotube, so contrast the mass loss that pure carbon pipe has occurred about 70%, as shown in (d) in Fig. 3.Can prove that divinyl benzene polymers is successfully coated on carbon nano tube surface in conjunction with this two point data.
Claims (3)
1. utilize controlled coating technology to prepare a method for hud typed carbon nanotube conducting filler, it is characterized in that step is as follows:
A) be the suspension of concentration 1-5mg/mL by original carbon nanotubes, DMF mixed preparing, ultrasonic more than 45min;
B) by quality 0.25 doubly in a) Diisopropyl azodicarboxylate of carbon nanotube add in above-mentioned suspension, continue ultrasonic 10min with abundant activated carbon nano-tube, after dissolving, obtain homogeneous system;
C) in above-mentioned system, pass into nitrogen and be warming up to 80 DEG C, dripping the divinylbenzene monomers of 1-10 times of carbon nanotube mass gradually, and with this conditioned response 12h;
D), after reaction stops, suction filtration obtains product, obtains final product successively with methyl alcohol, deionized water wash.
2., by a kind of method utilizing controlled coating technology to prepare hud typed carbon nanotube conducting filler according to claim 1, it is characterized in that step c) the middle Vinylstyrene adopting technical grade purity.
3., by a kind of method utilizing controlled coating technology to prepare hud typed carbon nanotube conducting filler according to claim 1, it is characterized in that step c) in control the thickness of coating layer between 5-60nm by changing the consumption of Vinylstyrene.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104927404A (en) * | 2015-06-15 | 2015-09-23 | 北京化工大学 | Method for preparing core-shell type carbon nano tube dielectric packing through in-situ copolymerization technology |
| CN105385196A (en) * | 2015-11-15 | 2016-03-09 | 北京化工大学 | Preparation method of core-shell carbon nano-tube hybridization packing with epoxy group |
| CN105609732A (en) * | 2016-01-11 | 2016-05-25 | 华南师范大学 | Carbon-coated zinc ferrite electrode material and preparation method and application thereof |
| CN110534384A (en) * | 2019-07-26 | 2019-12-03 | 宁波工程学院 | A kind of nano-particle modified dendritic TiO of Au2Application of the nanometer stick array as filed emission cathode material |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103146231A (en) * | 2013-03-15 | 2013-06-12 | 北京化工大学 | Method for preparing core-shell type carbon nano-tube filling by coating carbon nano-tube through polyionic liquid |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103146231A (en) * | 2013-03-15 | 2013-06-12 | 北京化工大学 | Method for preparing core-shell type carbon nano-tube filling by coating carbon nano-tube through polyionic liquid |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104927404A (en) * | 2015-06-15 | 2015-09-23 | 北京化工大学 | Method for preparing core-shell type carbon nano tube dielectric packing through in-situ copolymerization technology |
| CN104927404B (en) * | 2015-06-15 | 2017-08-11 | 北京化工大学 | A kind of method that in-situ copolymerization technology prepares hud typed CNT dielectric filler |
| CN105385196A (en) * | 2015-11-15 | 2016-03-09 | 北京化工大学 | Preparation method of core-shell carbon nano-tube hybridization packing with epoxy group |
| CN105385196B (en) * | 2015-11-15 | 2018-03-30 | 北京化工大学 | A kind of preparation method of the hud typed carbon nano-tube hybridization filler with epoxide group |
| CN105609732A (en) * | 2016-01-11 | 2016-05-25 | 华南师范大学 | Carbon-coated zinc ferrite electrode material and preparation method and application thereof |
| CN110534384A (en) * | 2019-07-26 | 2019-12-03 | 宁波工程学院 | A kind of nano-particle modified dendritic TiO of Au2Application of the nanometer stick array as filed emission cathode material |
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