CN104448167B - 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 present invention be with regard to polyfunctionality divinylbenzene controllable polymerization cladding original carbon nanotubes prepare hud typed multiple
The method of compound powder body, belongs to the technical field of composite preparation.
Background technology
CNT is another the new carbonaceous Nano-Materials occurring after fullerene, carbon nanometer from structure
Pipe is cylindrical shell carbon that crimped according to certain helical angle by one layer or Multi-layer graphite synusia, a diameter of nanometer scale
Nanotube, because of its unique mechanics, characteristic electron and chemical characteristic, becomes the focus of research in world wide, in Flied emission, divides
The various fields such as sub- electronic device, composite reinforcing material, hydrogen storage material, catalyst carrier achieve and are widely applied.
The seamless tubular shaped structure of CNT and the good degree of graphitization of pipe shaft impart the excellent mechanical property of CNT
Can, tensile strength reaches 50-200gpa, is 100 times of steel, density but only have steel 1/6, high one at least than ordinary graphite fiber
The order of magnitude, thus it is referred to as " ultra high strength fiber ".Also there is high elasticity simultaneously, its elastic modelling quantity up to 1tpa, with Buddha's warrior attendant
The elastic modelling quantity of stone is suitable, about the five of steel times.Using CNT as composite material reinforcement body, can show good strong
Degree, elasticity, fatigue resistance and isotropism, bring great improvement to the performance of composite.CNT has similar height
The structure of molecule, and have very high axial strength and rigidity.With macromolecular material compound tense, obtain the composite wood of excellent performance
Material, makes CNT show excellent electric property and mechanical property, this makes CNT have in field of compound material
Tempting application prospect.
But CNT dispersibility in a solvent is poor, also poor with the compatibility of other materials, which limits it
Application.In the last few years, it was subject to using the method that coating technology prepares hud typed compounded mix to the modification of CNT running-surface
Arrive the extensive concern of people.CNT after cladding both can be used alone separately as hybrid material, such as electrochemical sensing
Device etc. it is also possible to prepare polymer matrix composite as filler, such as conductive and dielectric composite material etc., therefore realize carbon is received
The controlled cladding of mitron has very wide application prospect.
Divinylbenzene is that have the monomer of two vinyls, and structure is with phenylethylene seemingly.Three-dimensional knot can be generated during copolymerization
The insoluble polymer of structure, is therefore a kind of particularly useful cross-linking agent, be widely used in ion exchange resin, ion exchange membrane,
Abs resin, polystyrene resins, unsaturated polyester resin, synthetic rubber, timber processing, carbon processing and other fields.Because it is second
Alkene and benzene produce obtained by-product during ethylbenzene through alkylation, therefore originate sufficient, cheap.
Carbon nano-tube modified traditional method be by CNT under the conditions of concentrated acid acidification, obtained using acidifying
Carboxyl or other functional groups reacted further or caused polymerization, thus improve CNT dispersibility in the material and
The compatibility.But acidification is serious to the structural deterioration of CNT, its performance is caused to be subject to strong influence, for this in recent years
Many workers are had to attempt using the conjugated double bond of carbon nano tube surface or physical absorption come modified carbon nano-tube, but
To result be not coat not uniformly it is simply that cost too high it is difficult to the production that carries out on a large scale.Not modified CNT exists
Dispersibility in organic solvent is not good, and most polymer compatibility is also poor, thus having a strong impact on composite
Performance.Therefore the method has many advantages, such as cladding is closely controlled, experimentation is simple to operate, material controllability is good.
Content of the invention
It is an object of the invention to provide one kind prepares divinylbenzene enveloped carbon nanometer tube prepares hud typed CNT
The short-cut method of compounded mix.In preparation process, first by multi-walled carbon nano-tubes in a small amount of solvent fully ultrasonic de-agglomerated, then
Add initiator to pass through ultrasonication and activate generation free radical active center in carbon nano tube surface.Then lead to nitrogen protection and
Oxygen in exclusion system is stirred at room temperature, liter high reaction temperature progressively Deca monomer make it be polymerized, obtain under certain rotating speed
Whole hud typed carbon mano-tube composite.
The poly ion liquid enveloped carbon nanometer tube that the present invention provides prepares the preparation technology mistake of hud typed carbon nanotube filler
Journey, comprises the concrete steps that:
A) by original carbon nanotubes, n, n dimethylformamide mixed preparing is the suspension of concentration 1-5mg/ml, ultrasonic
More than 45min；
B) by 0.25 times of quality a) in the azodiisobutyronitrile of CNT add in above-mentioned suspension, continue ultrasonic
10min, with abundant activated carbon nano-tube, obtains homogeneous system；
C) it is passed through nitrogen into above-mentioned system and be warming up to 80 DEG C, the gradually monomer two of 1-10 times of Deca carbon nanotube mass
Vinyl benzene, and with this conditioned response 12h；
D), after reaction stops, sucking filtration obtains product, obtains final product with methanol, deionized water wash successively.
Further, in step c) middle employing technical grade purity divinylbenzene.
Further, the consumption changing divinylbenzene in step c) can control the thickness of clad between 5-60nm.
The polyfunctionality vinyl monomer enveloped carbon nanometer tube that the present invention provides prepares the side of hud typed carbon nanotube filler
The feature of method is:
1. utilize the activation to CNT tube wall for the radical initiator azodiisobutyronitrile, straight under homogeneous system
Connect the polymerization causing multi-vinyl monomer and the cladding to CNT is realized with this.Do not need CNT is acidified,
Oxidation etc. is processed, and the structure of CNT is not damaged, thus retains the original performance of CNT to the full extent.
2. clad is cross-linked structure, therefore in carbon nano tube surface cladding firmly, difficult for drop-off.
3. achieve the full cladding to CNT, and cladding ratio is more uniform, the thickness of clad is controlled, greatly improves
Dispersibility in organic solution for the CNT.
4. operate relatively simple and direct, low cost.
Brief description
The divinyl benzene polymers cladding multi-walled carbon nano-tubes that Fig. 1: the present invention provides prepares hud typed compounded mix
Process chart.
Fig. 2: divinyl benzene polymers coat the transmission electron microscope photo of the hud typed compounded mix of multi-walled carbon nano-tubes.
A) CNT and monomer weight ratio are 1:1
B) CNT and monomer weight ratio are 1:3
C) CNT and monomer weight ratio are 1:5
D) CNT and monomer weight ratio are 1:10
Fig. 3: divinyl benzene polymers coat the thermogravimetric curve of the hud typed compounded mix of multi-walled carbon nano-tubes.
A) CNT and monomer weight ratio are 1:1
B) CNT and monomer weight ratio are 1:3
C) CNT and monomer weight ratio are 1:5
D) CNT and monomer weight ratio are 1:10
Specific embodiment
Carbon nano tube surface can capture the free radical producing in polyreaction makes the polymer chain of polymerization be grafted and twine
Knot is in carbon nano tube surface, but this equally can make the activity that polymer chain forfeiture is polymerized further, and molecular weight has been controlled in very
Low scope, does not reach described covered effect.And can be very good to solve this using the divinylbenzene monomers of polyfunctionality
One problem, improves thickness and the controllability of cladding.Divinylbenzene is a kind of industrial conventional cross-linking agent, and price itself is low
Honest and clean, it is similar to that the monomer of conventional poly styrene polymer, therefore has very with polystyrene and other multiple polymers
The good compatibility.But this monomer reaction activity is very high, easy autohemagglutination becomes the insoluble insoluble polymer of crosslinking it is desirable to control it
The auto polymerization reaction carrying out cross-linking reaction in carbon nano tube surface and reducing as far as possible in dicyandiamide solution is one needs solution
Technical barrier.We reduce autohemagglutination as far as possible at the method for the monomer concentration and gradually Deca activated monomer by reducing system
Close the generation of reaction.Consider the feelings that rate of polymerization is not high and cladding thickness is too low of the too low generation of monomer concentration simultaneously
Condition we employ following consumption and operational approach.
Embodiment 1
Weigh CNT 150mg, be placed in there-necked flask, add the n of 150ml, n dimethylformamide (dmf) conduct
Solvent, ultrasonic disperse 45min, add the initiator azodiisobutyronitrile of 25mg and continue ultrasonic 10min.Measure the two of 0.15g
Vinyl benzene (dvb) monomer, and add in dropper after diluting.There-necked flask is moved in oil bath, under nitrogen protection, room
Temperature stirring 1h.It is warming up to 80 DEG C, gradually divinylbenzene (dvb) monomer in Deca dropper carries out polyreaction.After 12h
Stop heating and terminate reaction.Sucking filtration obtains product, washs 30min with water, methanol respectively, last sucking filtration obtains target product.Fig. 2
A () is the hud typed complex (particular flow sheet is as shown in Figure 1) of divinylbenzene enveloped carbon nanometer tube manufactured in the present embodiment
Transmission electron microscope photo.As can be seen from the figure there are the uniform coating of thin layer, thickness in multi-wall carbon nano-tube pipe outer wall
About in below 5nm.Through thermogravimetric curve as can be seen that due to divinyl benzene polymer in cladding outside the CNT
Thing, so contrasting the mass loss that pure carbon pipe occurs in that about 35%, in such as Fig. 3 shown in (a).Can in conjunction with this two point data
Carbon nano tube surface is successfully coated on proof divinylbenzene.
Embodiment 2
Weigh CNT 150mg, be placed in there-necked flask, add the n of 150ml, n dimethylformamide (dmf) conduct
Solvent, ultrasonic disperse 45min.Add the initiator azodiisobutyronitrile of 25mg and continue ultrasonic 10min.Measure the two of 0.45g
Vinyl benzene (dvb) monomer, and add in dropper after diluting.There-necked flask is moved in oil bath, under nitrogen protection, room
Temperature stirring 1h.It is warming up to 80 DEG C, gradually Deca monomer carries out polyreaction.Stop heating after 12h and terminate reaction.Sucking filtration is produced
Thing, washs 30min with water, methanol, last sucking filtration obtains target product respectively.Fig. 2 (b) is divinyl manufactured in the present embodiment
The transmission electron microscope photo of the hud typed complex of benzene enveloped carbon nanometer tube.As can be seen from the figure in multi-wall carbon nano-tube pipe outer wall
There is the uniform coating of thin layer, thickness is about in 20nm.Through thermogravimetric curve as can be seen that due to receiving in carbon
Outside mitron, cladding has gone up divinyl benzene polymers, so contrasting the mass loss that pure carbon pipe occurs in that about 45%,
As shown in (b) in Fig. 3.May certify that divinyl benzene polymers are successfully coated on carbon nano tube surface in conjunction with this two point data.
Embodiment 3
Weigh CNT 150mg, be placed in there-necked flask, add the n of 150ml, n dimethylformamide (dmf) conduct
Solvent, ultrasonic disperse 45min, add the initiator azodiisobutyronitrile of 25mg and continue ultrasonic 10min.Measure the two of 0.75g
Vinyl benzene (dvb) monomer, adds in dropper after dilution.There-necked flask is moved in oil bath, under nitrogen protection, room temperature
Stirring 1h.It is warming up to 80 DEG C, gradually Deca monomer carries out polyreaction.Stop heating after 12h and terminate reaction.Sucking filtration is produced
Thing, washs 30min with water, methanol, last sucking filtration obtains target product respectively.Fig. 2 (c) is divinyl manufactured in the present embodiment
The transmission electron microscope photo of the hud typed complex of benzene enveloped carbon nanometer tube.As can be seen from the figure have in multi-wall carbon nano-tube pipe outer wall
The uniform coating of thin layer, thickness is about in below 40nm.Through thermogravimetric curve as can be seen that due in carbon nanometer
Outside pipe, cladding has gone up polymer, so contrasting the mass loss that pure carbon pipe occurs in that about 55%, as (c) institute in Fig. 3
Show.May certify that divinyl benzene polymers are successfully coated on carbon nano tube surface in conjunction with this two point data.
Embodiment 4
Weigh CNT 150mg, be placed in there-necked flask, add the n of 150ml, n dimethylformamide (dmf) conduct
Solvent, ultrasonic disperse 45min, add the initiator azodiisobutyronitrile of 25mg and continue ultrasonic 10min.Measure the diethyl of 1.5g
Alkenyl benzene (dvb) monomer, adds after dilution in dropper, there-necked flask is moved in oil bath, under nitrogen protection, room temperature is stirred
Mix 1h.It is warming up to 80 DEG C, gradually Deca monomer carries out polyreaction.Stop heating after 12h and terminate reaction.Sucking filtration obtains product,
Wash 30min with water, methanol respectively, last sucking filtration obtains target product.Fig. 2 (d) is divinylbenzene manufactured in the present embodiment
The transmission electron microscope photo of the hud typed complex (particular flow sheet is as shown in Figure 1) of enveloped carbon nanometer tube.As can be seen from the figure
There is the uniform coating of thin layer in multi-wall carbon nano-tube pipe outer wall, thickness is about in 60nm.Through thermogravimetric curve
As can be seen that due to having coated polymer outside CNT, so contrast pure carbon pipe to occur in that one about 70%
In mass loss, such as Fig. 3 shown in (d).May certify that divinyl benzene polymers are successfully coated on carbon and receive in conjunction with this two point data
Nanotube surface.
Claims (3)
1. a kind of using controlled coating technology prepare hud typed carbon nanotube conducting filler method it is characterised in that step such as
Under:
A) by original carbon nanotubes, n, n dimethylformamide mixed preparing is the suspension of concentration 1-5mg/ml, ultrasonic 45min
More than；
B) by 0.25 times of quality a) in the azodiisobutyronitrile of CNT add in above-mentioned suspension, continue ultrasonic 10min
With abundant activated carbon nano-tube, after dissolving, obtain homogeneous system；
C) it is passed through nitrogen into above-mentioned system and be warming up to 80 DEG C, the gradually divinylbenzene of Deca 1-10 times carbon nanotube mass
Monomer, and with this conditioned response 12h；
D), after reaction stops, sucking filtration obtains product, obtains final product with methanol, deionized water wash successively.
2. a kind of method preparing hud typed carbon nanotube conducting filler using controlled coating technology as described in claim 1,
It is characterized in that adopting the divinylbenzene of technical grade purity in step c).
3. a kind of method preparing hud typed carbon nanotube conducting filler using controlled coating technology as described in claim 1,
It is characterized in that controlling the thickness of clad between 5-60nm by changing the consumption of divinylbenzene in step c).
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| 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 |
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