CN106633667B - A kind of preparation method of carbon nanotube and polymer composites - Google Patents
A kind of preparation method of carbon nanotube and polymer composites Download PDFInfo
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- CN106633667B CN106633667B CN201611254998.3A CN201611254998A CN106633667B CN 106633667 B CN106633667 B CN 106633667B CN 201611254998 A CN201611254998 A CN 201611254998A CN 106633667 B CN106633667 B CN 106633667B
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 86
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 79
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 74
- 239000002131 composite material Substances 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- 229920000642 polymer Chemical class 0.000 title claims abstract description 28
- 239000000203 mixture Substances 0.000 claims abstract description 45
- 239000003054 catalyst Substances 0.000 claims abstract description 31
- 229920005989 resin Polymers 0.000 claims abstract description 30
- 239000011347 resin Substances 0.000 claims abstract description 30
- 238000010438 heat treatment Methods 0.000 claims abstract description 26
- 230000006698 induction Effects 0.000 claims abstract description 26
- 239000000843 powder Substances 0.000 claims abstract description 25
- 238000011065 in-situ storage Methods 0.000 claims abstract description 21
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 21
- 150000003624 transition metals Chemical class 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 20
- 230000005291 magnetic effect Effects 0.000 claims abstract description 15
- 238000000465 moulding Methods 0.000 claims abstract description 15
- 239000002861 polymer material Substances 0.000 claims abstract description 15
- 206010020843 Hyperthermia Diseases 0.000 claims abstract description 5
- 230000036031 hyperthermia Effects 0.000 claims abstract description 5
- 230000015572 biosynthetic process Effects 0.000 claims abstract 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 239000004593 Epoxy Substances 0.000 claims 1
- 239000011159 matrix material Substances 0.000 abstract description 11
- 239000000463 material Substances 0.000 description 19
- 229910052799 carbon Inorganic materials 0.000 description 13
- 238000003756 stirring Methods 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 6
- 239000003822 epoxy resin Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 229920000647 polyepoxide Polymers 0.000 description 5
- 239000004215 Carbon black (E152) Substances 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- 239000002086 nanomaterial Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000004411 aluminium Substances 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 230000005674 electromagnetic induction Effects 0.000 description 3
- 230000002708 enhancing effect Effects 0.000 description 3
- 229920002521 macromolecule Polymers 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000000197 pyrolysis Methods 0.000 description 3
- 238000007711 solidification Methods 0.000 description 3
- 230000008023 solidification Effects 0.000 description 3
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000002048 multi walled nanotube Substances 0.000 description 2
- 239000002071 nanotube Substances 0.000 description 2
- 229920000620 organic polymer Polymers 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000002787 reinforcement Effects 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- 229920005992 thermoplastic resin Polymers 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000004471 Glycine Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- 239000007868 Raney catalyst Substances 0.000 description 1
- 229910000564 Raney nickel Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 150000001722 carbon compounds Chemical class 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- -1 ethylene, propylene Chemical group 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 229910000939 field's metal Inorganic materials 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000003760 hair shine Effects 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000012994 industrial processing Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 239000003863 metallic catalyst Substances 0.000 description 1
- 239000011859 microparticle Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 229920013657 polymer matrix composite Polymers 0.000 description 1
- 239000011160 polymer matrix composite Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Abstract
The present invention provides a kind of preparation method of carbon nanotube and polymer composites, the method includes being uniformly mixed to obtain mixture with organic high molecular polymer material by catalyst transition metal powders, by mixture curing molding, the mixture of curing molding is placed in magnetic induction heating equipment again and is heated, on transition metal powders surface, formation localized hyperthermia so that polymer material growth in situ forms carbon nanotube at catalyst position in mixture, and products obtained therefrom is the composite material of carbon nanotube and polymer.The method of the invention not only solves the problem of CNTs is difficult to disperse in a polymer matrix, also solves the problems, such as polymer and the bonding tightness of CNTs；Resin quality is high in the composite material being prepared simultaneously, and gained composite material is greatly enhanced compared with polymeric matrix mechanical property, heat conductivility and electric property.
Description
Technical field
The invention belongs to the preparing technical fields of composite material, and in particular to a kind of carbon nanotube and polymer composites
Preparation method.
Background technology
The spacing of carbon nanotube between layers is about 0.34nm, and generally in nano-scale range, length has diameter
Tens nanometers, longest can reach several microns.The C=C covalent bonds that 2sp hydridization is formed are one of strongest valence links in nature, this
Just the excellent mechanical property of carbon nanotube is imparted；Meanwhile on the π tracks of vertical graphite synusia, due to not matching there are more
To electronics, carbon nanotube have excellent electric property.In addition, carbon nanotube also has excellent heat conductivility, magnetics, light
Learn characteristic and unique absorbing property.Carbon nanotube relies on its unique electronic structure and physicochemical characteristics, it is considered to be one
The new structural material and functional material that kind is had excellent performance, can be used as the fibrous material of high intensity, and carbon nanotube unimolecule shines
Element, hydrogen storage material, feds material etc..In aerospace field, carbon nanotube is as a kind of emerging nano wave-absorption
Material can obtain large-scale application in military stealth, energy storage, suction wave etc..
The preparation method for the carbon nanotube having disclosed at present mainly has following several：1, chemical vapour deposition technique：Or
For hydrocarbon gas pyrolysismethod.This method is to allow gaseous hydrocarbon by being attached with the templates of catalyst particles, at 800~1200 DEG C
Under the conditions of, gaseous hydrocarbon, which decomposes, generates carbon nanotube.The advantage that this method protrudes is that Residual reactants are gas, be may exit off anti-
System is answered, obtains the relatively high carbon nanotube of purity, while temperature also need not be very high, in contrast saves energy.But
Carbon nanotube caliber obtained is irregular, in irregular shape, and has in preparation process to use catalyst.This method
Main direction of studying be desirable to control the structure of the carbon nanotube of generation by controlling the arrangement mode of catalyst in template,
It has been achieved for centainly being in progress.2, polymerisation synthetic method：In preparation method of carbon nano-tube, polymerisation synthetic method refers generally to
The method expanded using template duplicating.Scientist has found that under strong acid, ul-trasonic irradiation, carbon nanotube can first be fractured into several
Section, then certain nano-scale catalyst particles effect under be proliferated extend, and extend after gained carbon nanotube and template volume
Bent mode is identical.3, catalystic pyrolysis：Catalystic pyrolysis is to make to contain under the action of 600~1000 DEG C of temperature and catalyst
Carbon feedstock gas (such as carbon monoxide, methane, ethylene, propylene and benzene) decomposes to prepare a kind of method of carbon nanotube.This side
Method makes carbon compound be cracked into carbon atom to be attached to and urge under carbon atom is acted at Transition metal-catalyzed dose at relatively high temperatures
Be formed as carbon nanotube on agent microparticle surfaces.Catalyst activity component used in catalystic pyrolysis is mostly the 8th race's transition
Metal or its alloy are added the adjustable activities metal energy states such as Cu, Zn, Mg, change its chemisorption and contain with decomposition on a small quantity
The ability of carbon gas.
Based on many excellent properties of carbon nanotube, as reinforcement can increase substantially composite material electricity and
The performances such as mechanics.Therefore carbon nanotube has broad application prospects in the composite, is the hot issue of Recent study.
Wherein carbon nano-tube/polymer based composites, scholars are more to its research, and technique is most ripe, has been widely used for
In actual production.For polymer matrix composite, since the main component of carbon nanotube is carbon, structure and polymer
Similar, size also on the same order of magnitude, can be seen as the polymer of single element, when carbon nanotube is as composite wood
When the reinforcement of material, the stress transfer ability between polymeric matrix is 10 times of fiber or more.But due to carbon nanotube
Caliber is small, and surface energy is big, easily tangles, reunites together, this phenomenon has seriously affected carbon nanotube in the polymer equal
Even dispersion causes the performance of composite material by a degree of influence.Therefore, to prepare carbon nano-tube/polymer base compound
In materials process, carbon nanotube dispersibility in a polymer matrix and its become with the interface cohesion of matrix has to be solved
Critical issue.As Chinese invention patent CN201480002453.6 discloses a kind of resin combination and uses the resin combination
Shaped article made from object.The method for wherein preparing resin combination includes：A) based on 100 parts by weight in following melting mixings
It is middle carry out melting mixing thermoplastic resin, by with mechanical mixer stir 0.1 to 20 parts by weight carbon nanomaterial, 0.1
To the solvent of the polycyclic aromatic hydrocarbons (PAH) derivative and 60 to 99.8 parts by weight of 20 parts by weight, polycyclic fragrance is coated on carbon nanomaterial
Hydrocarbon derivative；And the thermoplastic resin melting mixing for the product and 100 parts by weight for b) making 0.1 to 5 parts by weight coated,
Wherein, the weight ratio of carbon nanomaterial and polycyclic aromatic hydrocarbons (PAH) derivative is 1:0.2 to 1:0.9, the polycyclic aromatic hydrocarbons (PAH) derivative
Selected from least one of 1- pyrenes-BuCh and 1- pyrenes-butyric acid, carbon nanomaterial is that mean outside diameter is 5 to 30nm and is averaged
The multi-walled carbon nanotube that length is 1 to 25 μm.In addition, disclosing a kind of carbon in Chinese invention patent application CN201510073672.X
The preparation method of nanotube network/polymer composites, including：The carbon nanotube of network structure is provided；By the network knot
Structure layer by layer deposition obtains carbon nanotube network film precast body；High polymer monomer precursor solution is provided, the carbon is received
Nanotube networks structural membrane precast body is infiltrated with the high polymer monomer precursor solution before obtaining carbon nano tube network/macromolecule
Drive body mixture；Carbon nano tube network described in stretch processing/macromolecule presoma mixture；By the carbon nanotube after stretching
Network/macromolecule presoma mixture carries out hot-pressing densification curing process and obtains carbon nano tube network/polymer composites.
It is composite material to be prepared by carbon nanotube product, thus can not thoroughly be solved in such scheme above-mentioned in the above method
The dispersibility of carbon nanotube in a polymer matrix and its interface cohesion problem with matrix.
A kind of carbon nanotube of Chinese invention patent CN201410337996.5 offers and the enhancing of alumina whisker In-situ reaction
It is (0.005~0.1) ︰ that the preparation method of resin material, which includes by the mass ratio of transition-metal catalyst Fen Ti ︰ Lv Fen ︰ resins,
(0.005~0.1) ︰ 1 carry out dispensing, and transition-metal catalyst powder and aluminium powder are first dispersed in same organic solution respectively
In, 1~5min of ultrasonic disperse obtains the mixture and aluminium powder and organic solution of transition-metal catalyst powder and organic solution
Mixture, then by the mixing of the transition-metal catalyst powder and the mixture and the aluminium powder and organic solution of organic solution
Object is added in 50~100 DEG C of resin, 1~2h of mechanical agitation；Then cure 20~28h under the conditions of 200~300 DEG C,
It buries and is heat-treated 1~5h under the conditions of carbon atmosphere and 600~1500 DEG C, carbon nanotube and alumina whisker In-situ reaction enhancing tree is made
Fat material.In addition, disclosing a kind of nitrogen doped corrugated carbon nanotube in Chinese invention patent application 201610269954.1
Preparation method, it is that carbon matrix precursor is prepared nitrogen as nitrogen source using glycine and mixes using transition metal as catalyst to take macroreticular resin
Miscellaneous Bamboo-shaped multi-walled carbon nanotube.Composite wood is prepared in the method that carbon nano-tube in situ is all made of in above-mentioned preparation method
Material, but the resin in the composite material obtained using above-mentioned preparation method is at a high temperature of forming 1000 DEG C or so of carbon nanotube
After being kept for a period of time, resin therein substantially all decomposed by carbonization, there is no polymer presence in composite material, makes
It is substantially unavailable to obtain the composite material so prepared.
Therefore, this field needs a kind of preparation method of the composite material of new carbon nanotube and polymer.
Invention content
Therefore, the present invention provides a kind of preparation method of carbon nanotube and polymer composites, and the method includes will
Catalyst transition metal powders are uniformly mixed to obtain mixture with organic high molecular polymer material, by mixture curing molding,
The mixture of curing molding is placed in magnetic induction heating equipment again and is heated, forming localized hyperthermia on transition metal powders surface makes
Polymer material growth in situ forms carbon nanotube at catalyst position in mixture, products obtained therefrom be carbon nanotube with
The composite material of polymer.
In a kind of specific embodiment, the bulk temperature of mixture maintains when magnetic induction is heated in the present invention
Lower temperature makes in mixture most resins not be carbonized, thus product macroshape after magnetic induction heat treatment and
The macroshape of the mixture of curing molding and size are consistent substantially before size heats with magnetic induction.
In a kind of specific embodiment, the organic high molecular polymer material includes resin, and in curing molding
It is additionally added resin curing agent in preceding mixture；It is preferred that including epoxy resin in the organic high molecular polymer material.
In a kind of specific embodiment, comprising one or more in iron, nickel and cobalt in the transition metal powders.
In a kind of specific embodiment, the average grain diameter of the transition metal powders is 10nm~10um, preferably
10~500nm.
In a kind of specific embodiment, transition metal powders account for 0.01~20wt%, preferably 0.1 in the mixture
~10wt%.In the dosage of curing agent in being not counted in mixture, corresponding organic high molecular polymer material accounts for the matter of mixture
It is 80~99.99%, preferably 90~99.9% to measure percentage composition.
In a kind of specific embodiment, the power of the magnetic induction heating equipment is 0.1~30kw, preferably 1~
10kw, more preferable 1.5~5kw.
In a kind of specific embodiment, the organic high molecular polymer material in situ grows to form carbon nanotube
Time is 0.1s or more, preferably 0.2~600s, more preferable 0.5~300s.
In a kind of specific embodiment, the organic high molecular polymer material in situ grows to form carbon nanotube
Local temperature is 500~1000 DEG C, and the bulk temperature of the mixture of curing molding described in magnetic induction heating process maintains
300 DEG C hereinafter, it is preferred that 200 DEG C hereinafter, more preferable 120 DEG C or less.
In a kind of specific embodiment, the forming temperature during the mixture curing molding is 120~180
℃。
In the present invention, the mixture is placed in magnetic induction heating equipment, such as by the mixture block after curing molding
Body is placed in heating in induction heating equipment, since organic polymer will not be by electromagnetic induction heating, in powerful sensing heating
In the process, the nano metal powder catalyst speed heating in organic polymer, forms localized hyperthermia, is wrapped in around catalyst
Polymer temperature and catalysis collective effect under in-situ preparation carbon nanotube.
Method treatment conditions provided by the invention mitigate, are easy to operate and easily controllable.Carbon nanotube and polymer simultaneously
Matrix is well combined, and is evenly distributed in polymeric inner carbon nanotube CNTs, is fine and close, loading capacity and distribution density are controllable.This hair
In bright, the induction heating equipment and magnetic induction heating equipment each mean electromagnetic induction heating device, electromagnetic induction heating device
An example being most widely used in our daily lifes is electromagnetic oven.And in field of industrial processing, magnetic induction heating is set
Standby such as coreless induction furnace or intermediate frequency furnace, which have also been obtained, to be widely applied.
Curing molding in the present invention can be fabricated to corresponding shape according to the follow-up requirement of the composite material.
In the present invention, because workpiece is put into induction heating equipment, inductor usually input intermediate frequency or high-frequency alternating current (300~
300000Hz or higher) hollow copper tubing.Generate the induction that alternating magnetic field metal powder surface in workpiece produces same frequency
Electric current, this induced current being unevenly distributed on metal powder, it is strong on surface, and internal very weak, it is connect to center portion
It is bordering on 0, using this kelvin effect, metal powder surface can be made to heat rapidly, surface temperature rises to 800- in seconds
1000 DEG C, and other spot temperatures increase very little.It is poly- around metal surface under the catalytic action of localized hyperthermia and catalyst
It closes object growth in situ and goes out carbon nanotube, and other non-temperature distortions of position composite material, do not interfere with workpiece overall structure.
The method of the invention not only solves the problem of CNTs is difficult to disperse in a polymer matrix, also solves polymerization
The bonding tightness problem of object and CNTs；Resin quality is high in the composite material being prepared simultaneously, and gained composite material is relatively poly-
It closes object matrix mechanical property, heat conductivility and electric property to be greatly enhanced, and its enhancing ratio can be by adjusting catalyst powder
The factors such as the heating time of body ratio in the mixture, the grain size of catalyst and in-situ preparation carbon nanotube and be adjusted.
Specific implementation mode
The preparation method of the present invention specifically comprises the following steps：
1, it is uniformly distributed the preparation of the resin material of catalyst
The transition-metal catalysts powder such as iron, nickel, cobalt, average grain diameter are 10nm~10um, are added in epoxy resin, stir
10~60min of dispersion is mixed, curing agent is added, after stirring evenly, pours into and prepares in advance and in preheated mold, selected
Cured under condition of cure, the equally distributed resin material of metallic catalyst is made.
2, in-situ growing carbon nano tube in resin material
Molding mixing material prepared by step 1 is placed in induction heater, open induction heater power be 0.1~
30kw, the transition metal particles in material are inductively heated, and part generates 500~1000 DEG C in 0.1~600s at catalyst
High temperature, at temperature and catalyst collective effect, catalyst and resin contact site growth in situ go out carbon nanotube, and due to
Heating speed is fast, and material bulk temperature does not rise to the softening temperature of polymer because of the overall structure without destroying resin.It is raw
It grows strong bonded and is dispersed in the carbon nanotube inside resin material, when to solve conventional composite materials preparation
The problem of being difficult to be evenly distributed to composite inner due to carbon nanotube easily tangles and reunites.Also solves conventional electricity simultaneously
It is up to 1000 DEG C of temperature under mode of heating and makes heated the problem of the decomposing that be carbonized of the resin in composite material.
Embodiment 1
1, it is uniformly distributed the preparation of the resin material of iron catalyst
The iron powder and 49g epoxy resin E-51 that 6g average grain diameters are 100nm are weighed respectively, are dispersed with stirring uniformly, then weigh
45g nylon 651 is added thereto to form mixture, after stirring evenly, pours the mixture into and is coated in the plastic mould of releasing agent.Add
Heat obtains cured mixture to 150 DEG C of solidification 2h.
2, in-situ growing carbon nano tube in resin
Cured mixture prepared by step 1 is placed in induction heater, the induction heating power of 2kw is opened, is heated
2s.About 800 DEG C of high temperature is generated at catalyst part, growth in situ goes out carbon nanotube, obtains the carbon nanotube and polymerize
Object composite material.
Embodiment 2
1, it is uniformly distributed the preparation of the resin material of Co catalysts
The cobalt powder and 63g epoxy resin E-51 that 2g average grain diameters are 15nm are weighed respectively, are dispersed with stirring uniformly, then weigh
35g nylon66 fibers are added thereto to form mixture, after stirring evenly, pour the mixture into and are coated in the plastic mould of releasing agent.Add
Heat obtains cured mixture to 170 DEG C of solidification 3h.
2, in-situ growing carbon nano tube in resin
Cured mixture prepared by step 1 is placed in induction heater, the induction heating power of 3kw is opened, is heated
5s.About 900 DEG C of high temperature is generated at catalyst part, growth in situ goes out carbon nanotube, obtains the carbon nanotube and polymerize
Object composite material.
Embodiment 3
1, it is uniformly distributed the preparation of the resin material of Raney nickel
Weigh respectively 10g average grain diameters be 300nm nickel powder and 90g epoxy resin E-51, be dispersed with stirring be formed uniformly it is mixed
Object is closed, the mixture after stirring evenly is poured into and is coated in the plastic mould of releasing agent.140 DEG C of solidification 3h are heated to, consolidate
The mixture of change.
2, in-situ growing carbon nano tube in resin
Cured mixture prepared by step 1 is placed in induction heater, the induction heating power of 1.5kw is opened, adds
Hot 6s.About 1000 DEG C of high temperature is generated at catalyst part, growth in situ goes out carbon nanotube, obtains the carbon nanotube and gathers
Compound composite material.
The foregoing is only a preferred embodiment of the present invention, is not intended to restrict the invention, for the skill of this field
For art personnel, the invention may be variously modified and varied.All within the spirits and principles of the present invention, any made by repair
Change, equivalent replacement, improvement etc., should all be included in the protection scope of the present invention.
Claims (11)
1. the preparation method of a kind of carbon nanotube and polymer composites, the method includes by catalyst transition metal powders
It is uniformly mixed to obtain mixture with organic high molecular polymer material, by mixture curing molding, then by the mixing of curing molding
Object is placed in magnetic induction heating equipment and heats, and on transition metal powders surface, formation localized hyperthermia makes in mixture in catalyst
Polymer material growth in situ forms carbon nanotube at position, and products obtained therefrom is the composite material of carbon nanotube and polymer.
2. preparation method according to claim 1, which is characterized in that the organic high molecular polymer material includes resin,
And it is additionally added resin curing agent in the mixture before curing molding.
3. preparation method according to claim 2, which is characterized in that include epoxy in the organic high molecular polymer material
Resin.
4. preparation method according to claim 1, which is characterized in that comprising in iron, nickel and cobalt in the transition metal powders
It is one or more.
5. preparation method according to claim 1, which is characterized in that the average grain diameter of the transition metal powders be 10nm~
10μm。
6. preparation method according to claim 5, which is characterized in that the average grain diameter of the transition metal powders be 10~
500nm。
7. according to any one of claim 1~6 preparation method, which is characterized in that transition metal in the mixture
Powder accounts for 0.1~10wt%.
8. according to any one of claim 1~6 preparation method, which is characterized in that the magnetic induction heating equipment
Power is 1.5~5kw.
9. according to any one of claim 1~6 preparation method, which is characterized in that the organic high molecular polymer
Material in situ grows to form the time of carbon nanotube as 0.5~300s.
10. according to any one of claim 1~6 preparation method, which is characterized in that the organic high molecular polymer
Material in situ grows that form the local temperature of carbon nanotube be 500~1000 DEG C, and is solidified into described in magnetic induction heating process
The bulk temperature of the mixture of type maintains 120 DEG C or less.
11. according to any one of claim 1~6 preparation method, which is characterized in that the mixture curing molding mistake
Forming temperature in journey is 120~180 DEG C.
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