CN104927404B - A kind of method that in-situ copolymerization technology prepares hud typed CNT dielectric filler - Google Patents
A kind of method that in-situ copolymerization technology prepares hud typed CNT dielectric filler Download PDFInfo
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Abstract
The present invention discloses a kind of method that in-situ copolymerization technology prepares hud typed CNT dielectric filler.It is easy to produce the characteristic of physical absorption with carbon nano tube surface by the pi-conjugated effects of π using small molecule containing phenyl ring (divinylbenzene), second comonomer maleic anhydride is added using this small molecule monomer as bridge, living radical center is produced with BPO activated carbon nano-tubes surface and triggers divinyl benzene polymer, further trigger the copolymerization of maleic anhydride and divinylbenzene, so as to form copolymer clad on original carbon nanotubes surface.By CNT ultrasonic disperse in solvent, initiator is then added, temperature reaction, by adjusting the ratio between initiator and two monomers, obtains a series of different hud typed CNT dielectric filler of cladding thickness.This method need not carry out the preprocessing process such as acidifying oxidation to carbon nano tube surface, and technique is simple, can largely prepare the controllable dielectric filler of clad, and nontoxic solvent, there is good industrial prospect.
Description
Technical field
The present invention is divinylbenzene and maleic anhydride controllable polymerization the cladding original carbon nanotubes system on polyfunctionality
The method of standby hud typed compound dielectric filler, belongs to the technical field of composite preparation.
Background technology
CNT has excellent unique mechanics, electricity, heat conductivility, and recent decades have obtained extensive concern.Carbon
The seamless tubular shaped structure of nanotube and the good degree of graphitization of pipe shaft impart the excellent mechanical property of CNT, tensile strength
It is 100 times of steel up to 50-200GPa, density but only has the 1/6 of steel, an order of magnitude at least higher than ordinary graphite fiber, thus
It is referred to as " ultra high strength fiber ".Again because by graphene develop and Lai CNT its carbon atom in possess substantial amounts of p electronics, p
The presence of electronics results in large-scale delocalized pi-bond, and unpaired electron can be moved freely along tube wall, result in carbon nanometer
Also there is the property of semiconductor while pipe is with metallic conduction performance, thus again should with good on functional composite material
Use prospect.
There is great specific surface area yet with CNT so that there is extremely strong van der Waals interaction between pipe,
Thus CNT exists in the form of reuniting and is difficult to disperse under normal circumstances, while water and various organic solvents are insoluble in,
It is more difficult to be dispersed in polymeric matrix, thus needs to carry out CNT surface modification, can be readily dispersed in each
Plant in matrix and solvent.In the last few years, prepared by hud typed compounded mix to carbon nano tube surface modification using coating technology
Method receives the extensive concern of people.CNT after cladding can both be used alone separately as hybrid material, such as electrification
Sensor etc. is learned, polymer matrix composite can also be prepared as filler, such as conductive and dielectric composite material, therefore is realized
There is very wide application prospect to the controllable cladding of CNT.
Divinylbenzene is the monomer with two vinyl, and structure and phenylethylene are seemingly.Three-dimensional knot can be generated during copolymerization
The insoluble polymer of structure, therefore be a kind of particularly useful crosslinking agent, be widely used in ion exchange resin, amberplex,
ABS resin, polystyrene resin, unsaturated polyester resin, synthetic rubber, timber processing, carbon processing and other fields.Also, due to
π-πconjugation between divinylbenzene and CNT so that it is easy to physical absorption in carbon nano tube surface, therefore
The probability of homopolymerization between monomer can be effectively reduced during polymerization, so as to be easy in carbon nano tube surface formation clad.Further, since
It is accessory substance resulting when ethene and benzene produce ethylbenzene through being alkylated, therefore source is sufficient, cheap.
Maleic anhydride industrially has a wide range of applications as a kind of conventional copolymeric material.Such as styrene-Malaysia
Acid anhydride copolymer is exactly that one kind is commonly used on the market at present, and function admirable, cheap novel high polymer material is widely used
In water treatment agent, adhesive modifying agent, latex paint, floor polishing emulsifying agent, farm chemical emulgent, pigment dispersing agent, asphalt mixtures modified by epoxy resin
The fields such as fat curing agent.Anhydride group is incorporated into the surface of CNT, CNT and various kinds of resin can be effectively improved
The compatibility of matrix (PVC, nylon), so as to improve dispersiveness of the CNT in resin matrix, improves the property of composite
Can, therefore have good application prospect.
Carbon nano-tube modified traditional method be by CNT under the conditions of concentrated acid acidification, obtained using acidifying
Carboxyl or other functional groups further reacted or trigger polymerization so that improve CNT in the material dispersiveness and
Compatibility.But acidification destroys serious to the structure of CNT, causes its performance by strong influence, be this in recent years
To there is many workers to attempt conjugated double bond or physical absorption using carbon nano tube surface come modified carbon nano-tube, but this
Kind physics coats the active force between carbon pipe and insecure, clad can be come off under the change of some external conditions,
So as to have influence on the performance of composite.Therefore closely controllable, experimentation is simple to operate, material is adjustable with cladding for this method
Many advantages, such as section property is good.
The content of the invention
Prepared it is an object of the invention to provide a kind of divinylbenzene-maleic anhydride enveloped carbon nanometer tube hud typed
The short-cut method of CNT compounded mix.CNT is divided under certain supersonic frequency and power first in preparation process
Dissipate in a certain amount of solvent, then by adding initiator in N2It is set to be lived in carbon nano tube surface formation free radical under atmosphere
Property center, and then trigger the copolymerization of divinylbenzene monomers and maleic anhydride, finally obtain hud typed CNT compounded mix.
Divinylbenzene-copolymer-maleic anhydride that the present invention is provided prepares the specific step of CNT nucleocapsid dielectric filler
Suddenly it is：
A) CNT, butyl acetate are mixed, ultrasonic more than 1h is configured to concentration 1-1.5mg/mL suspension；
B) by 0.2-0.8 times of quality a) in the dibenzoyl peroxide of CNT add in above-mentioned suspension, in N2
Protection is lower to continue ultrasound 10min with abundant activated carbon nano-tube, and homogeneous system is obtained after dissolving；
C) system is warming up to 80 DEG C, the divinylbenzene monomers (purity of 2-10 times of carbon nanotube mass is added dropwise
80%), after reaction 2h, the disposable maleic anhydride (purity 95%) for adding divinylbenzene mass fraction 10%-80% and with
This conditioned response 12h；
D) centrifugation, suction filtration obtain product after reaction stops, and are washed successively with toluene, ethyl acetate, and vacuum drying is obtained most
End-product.
Further, in step a) ultrasonic power between 300-600W.
Further, the thickness of the consumption control clad of divinylbenzene and maleic anhydride is changed in step c)；Maleic acid
The increase of acid anhydride ingredient proportion can reduce coating thickness, so that coating thickness control is between 5-20nm.
The polyfunctionality vinyl monomer and anhydride copolymers enveloped carbon nanometer tube that the present invention is provided prepare hud typed dielectric and filled out
The characteristics of method of material is：
1. using activation of the radical initiator dibenzoyl peroxide to CNT tube wall, under homogeneous system
Directly trigger the polymerization of multi-vinyl monomer, and then trigger the copolymerzation with cross-linking of maleic anhydride and polyenic monomer, realize to carbon nanometer
The cladding of pipe.The method need not be acidified to CNT, the processing such as oxidation, to the structure destructiveness of CNT
It is low, thus retain the original performance of CNT to the full extent.
2. clad is cross-linked structure, therefore firm in carbon nano tube surface cladding, difficult for drop-off.
3. the full cladding to CNT is realized, and cladding ratio is more uniform, the thickness of clad is controllable, greatly improves
Dispersiveness of the CNT in organic solution.
4. operation is relatively simple and direct, cost is low, harmless using nontoxic solvent.
Brief description of the drawings
Fig. 1：The divinylbenzene that the present invention is provided-copolymer-maleic anhydride cladding multi-walled carbon nanotube prepares hud typed multiple
Close the process chart of filler.
Fig. 2：Divinylbenzene-copolymer-maleic anhydride thing coats the INFRARED SPECTRUM of the hud typed compounded mix of multi-walled carbon nanotube
Figure.
A) CNT, divinylbenzene, the mass ratio of maleic anhydride are 1:10:1
B) CNT, divinylbenzene, the mass ratio of maleic anhydride are 1:8:2
C) CNT, divinylbenzene, the mass ratio of maleic anhydride are 1:5:2.5
D) CNT, divinylbenzene, the mass ratio of maleic anhydride are 1:2:1.6
Fig. 3：Divinylbenzene-copolymer-maleic anhydride coats the transmission electron microscope of the hud typed compounded mix of multi-walled carbon nanotube
Photo
A) CNT, divinylbenzene, the mass ratio of maleic anhydride are 1:10:1
B) CNT, divinylbenzene, the mass ratio of maleic anhydride are 1:8:2
C) CNT, divinylbenzene, the mass ratio of maleic anhydride are 1:5:2.5
D) CNT, divinylbenzene, the mass ratio of maleic anhydride are 1:2:1.6
Embodiment
Carbon nano tube surface can capture the free radical produced in polymerisation and then trigger the monomer with double bond to enter one
Step polymerization causes heavy polymer grafting or is coated on carbon nano tube surface.But this mode is the problem of have certain.
Due to there is the free based component of a variety of small molecules in solution system, such as carbon pipe free radical, initiator free radical, monomer are certainly
Autohemagglutination between monomer in base, therefore course of reaction is inclined to and its serious, causes CNT covered effect to be deteriorated.And use many
The divinylbenzene monomers containing conjugated structure of degree of functionality can be very good to solve this problem, and the phenyl ring with conjugated structure inclines
To in physical absorption in carbon nano tube surface so that CNT free radical preferentially with the monomer reaction, in CNT
Surface triggers polymerization, forms cross-linked network structure.While thickness and controllability in order to further improve cladding, Wo Mentong
Cross the monomer concentration of reduction system and the method for activated monomer is gradually added dropwise to reduce the generation of auto polymerization reaction as far as possible.Together
When consider the too low generation of monomer concentration rate of polymerization is not high and the too low situation of cladding thickness we employ with
Under consumption and operating method.
Embodiment 1
CNT 500mg is weighed, is placed in three-necked flask, the butyl acetate for adding 500ml is used as solvent, ultrasonic disperse
1h, the initiator dibenzoyl peroxide for adding 400mg continues ultrasound 10min.5g divinylbenzene (DVB) monomer is measured,
And added after diluting in dropper.Three-necked flask is moved into oil bath, under nitrogen protection, 10min is stirred at room temperature.It is warming up to
80 DEG C, divinylbenzene (DVB) monomer being gradually added dropwise in dropper carries out polymerisation, it is disposable after 2h to add 0.5g
Stop heating after maleic anhydride, 12h and terminate reaction.Suction filtration obtains product, is respectively washed twice with toluene, butyl acetate respectively, most
Centrifugation, suction filtration, vacuum drying obtain target product afterwards.Fig. 2 (a) is divinylbenzene enveloped carbon nanometer tube manufactured in the present embodiment
Hud typed compound (particular flow sheet is as shown in Figure 1) infrared spectrum, by characteristic peak analysis can be with preliminary proof diethyl
Alkenyl benzene-maleic anhydride cross-linked copolymer is coated on CNT.Fig. 3 (a) is divinylbenzene manufactured in the present embodiment
The transmission electron microscope photo of the hud typed compound of enveloped carbon nanometer tube, as can be seen from the figure has one in multi-wall carbon nano-tube pipe outer wall
The thicker uniform coating of layer, thickness about in 20nm illustrates that thicker clad can be obtained in this formula.With reference to this
Two point datas can prove that divinylbenzene-maleic anhydride cross-linked copolymer is successfully coated on carbon nano tube surface.Using such a
The dielectric filler of thickness is mixed with polystyrene systems, and when addition is 12wt%, prepared composite is 104Hz is surveyed
Try under frequency, dielectric constant, respectively up to 30, is 7 times of pure polystyrene systems, and dielectric loss is no more than 0.02.Such a material
Material has very big potential using value on microelectronic component is prepared.
Embodiment 2
CNT 500mg is weighed, is placed in three-necked flask, the butyl acetate for adding 450ml is used as solvent, ultrasonic disperse
1h, the initiator dibenzoyl peroxide for adding 300mg continues ultrasound 10min.4g divinylbenzene (DVB) monomer is measured,
And added after diluting in dropper.Three-necked flask is moved into oil bath, under nitrogen protection, 10min is stirred at room temperature.It is warming up to
80 DEG C, divinylbenzene (DVB) monomer being gradually added dropwise in dropper carries out polymerisation, it is disposable after 2h to add 1g horses
Carry out after acid anhydrides, 12h to stop heating terminating to react.Suction filtration obtains product, is respectively washed twice with butyl acetate, toluene respectively, finally
Centrifugation, suction filtration, vacuum drying obtain target product.Fig. 2 (b) is divinylbenzene enveloped carbon nanometer tube manufactured in the present embodiment
The infrared spectrum of hud typed compound (particular flow sheet is as shown in Figure 1), can be with preliminary proof divinyl by characteristic peak analysis
Base benzene-maleic anhydride cross-linked copolymer is coated on CNT.Fig. 3 (b) is divinylbenzene bag manufactured in the present embodiment
The transmission electron microscope photo of the hud typed compound of CNT is covered, as can be seen from the figure has one layer in multi-wall carbon nano-tube pipe outer wall
The uniform coating more relatively thin than embodiment 1, thickness is about in 10nm.Divinylbenzene-horse can be proved with reference to this two point data
Carry out acid anhydrides cross-linked copolymer and be successfully coated on carbon nano tube surface.Using the dielectric filler and epoxy resin, polyphenyl of such a thickness
The systems such as ethene are mixed, and when addition is respectively 10wt% and 30wt%, prepared composite is 104Hz test frequencies
Under, dielectric constant, respectively up to 180 and 112, is 60 times of pure epoxy resin system, 30 times of pure polystyrene systems, and is situated between
Electrical loss is no more than 0.02.Such a composite has very big potential using value on microelectronic component is prepared.
Embodiment 3
CNT 500mg is weighed, is placed in three-necked flask, the butyl acetate for adding 400ml is used as solvent, ultrasonic disperse
1h, the initiator dibenzoyl peroxide for adding 187.5mg continues ultrasound 10min.The divinylbenzene (DVB) for measuring 2.5g is single
Added after body, and dilution in dropper.Three-necked flask is moved into oil bath, under nitrogen protection, 10min is stirred at room temperature.Rise
Divinylbenzene (DVB) monomer that temperature is added dropwise to 80 DEG C, gradually in dropper carries out polymerisation, disposably added after 2h
Stop heating after 1.25g maleic anhydrides, 12h and terminate reaction, suction filtration obtains product.Respectively two are respectively washed with butyl acetate, toluene
Time, finally centrifugation, suction filtration, vacuum drying obtains target product.Fig. 2 (c) is divinylbenzene carbon coated manufactured in the present embodiment
The infrared spectrum of the hud typed compound (particular flow sheet is as shown in Figure 1) of nanotube, can tentatively be demonstrate,proved by characteristic peak analysis
Bright divinylbenzene-maleic anhydride cross-linked copolymer is coated on CNT.Fig. 3 (c) is diethyl manufactured in the present embodiment
The transmission electron microscope photo of the hud typed compound of alkenyl benzene enveloped carbon nanometer tube, as can be seen from the figure outside multi-walled carbon nanotube
Wall coating thickness is thinner, and uniformity has declined, and thickness is about in 8nm.Divinyl can be proved with reference to this two point data
Base benzene-maleic anhydride cross-linked copolymer is successfully coated on carbon nano tube surface.
Embodiment 4
CNT 500mg is weighed, is placed in three-necked flask, the butyl acetate for adding 350ml is used as solvent, ultrasonic disperse
1h, the initiator dibenzoyl peroxide for adding 100mg continues ultrasound 10min.1g divinylbenzene (DVB) monomer is measured,
And added after diluting in dropper.Three-necked flask is moved into oil bath, under nitrogen protection, 10min is stirred at room temperature.It is warming up to
80 DEG C, divinylbenzene (DVB) monomer being gradually added dropwise in dropper carries out polymerisation, it is disposable after 2h to add 0.8g
Stop heating after maleic anhydride, 12h and terminate reaction.Suction filtration obtains product, is respectively washed twice with butyl acetate, toluene respectively, most
Centrifugation, suction filtration, vacuum drying obtain target product afterwards.Fig. 2 (d) is divinylbenzene enveloped carbon nanometer tube manufactured in the present embodiment
Hud typed compound (particular flow sheet is as shown in Figure 1) infrared spectrum, as can be seen from the figure：Divinylbenzene-Malaysia
Acid anhydride copolymer feature peak intensity is markedly less than above example.Fig. 3 (d) is divinylbenzene carbon coated manufactured in the present embodiment
The transmission electron microscope photo of the hud typed compound of nanotube, as can be seen from the figure has very thin in multi-wall carbon nano-tube pipe outer wall
Clad, thickness is about in 5nm.It can prove that divinylbenzene-maleic anhydride cross-linked copolymer is a small amount of with reference to this two point data
Ground is coated on carbon nano tube surface, and can form very thin clad, demonstrates again that by controlling maleic anhydride addition can
To regulate and control coating thickness.It is combined using the dielectric filler and thermoplastic polyurethane (TPU) system of such a thickness, is in addition
During 15wt%, prepared composite is 104Under Hz test frequencies, dielectric constant, up to 32, is the 4 of pure TPU resin systems
Times, dielectric loss is no more than 0.1.Obtained composite has very big potential application valency on high dielectric elastomer is prepared
Value.
Claims (1)
1. a kind of method that in-situ copolymerization technology prepares hud typed CNT dielectric filler, it is characterised in that step is：
A) CNT and butyl acetate are mixed, ultrasonic more than 1h is configured to concentration 1-1.5mg/mL suspension；
B) by 0.2-0.8 times of quality a) in the dibenzoyl peroxide of CNT add in above-mentioned suspension, in N2Under protection
Continue ultrasound 10min with abundant activated carbon nano-tube, homogeneous system is obtained after dissolving；
C) system is warming up to 80 DEG C, be added dropwise after the divinylbenzene monomers of 2-10 times of carbon nanotube mass, reaction 2h, one
Secondary property adds divinylbenzene mass fraction 10%-80% maleic anhydride and with this conditioned response 12h；
D) centrifugation, suction filtration obtain product after reaction stops, and are washed successively with toluene, ethyl acetate, and vacuum drying obtains final production
Thing；
Ultrasonic power is between 300-600W in step a)；
Change the thickness of the consumption control clad of divinylbenzene and maleic anhydride in step c)；Maleic anhydride ingredient proportion
Increase can reduce coating thickness, so that coating thickness control is between 5-20nm.
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| CN112480602B (en) * | 2020-10-30 | 2022-07-01 | 西南科技大学 | High-dielectric low-loss carbon nanotube-coated epoxy resin composite material and preparation method thereof |
| CN112480639B (en) * | 2020-12-09 | 2023-03-24 | 金旸（厦门）新材料科技有限公司 | Efficient super-tough conductive PC material and preparation method thereof |
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