CN107674421A - A kind of preparation method and applications of graphene/carbon nano-tube aerogel polymer conducing composite material - Google Patents
A kind of preparation method and applications of graphene/carbon nano-tube aerogel polymer conducing composite material Download PDFInfo
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/08—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino-carboxylic acids
- C08G69/14—Lactams
- C08G69/16—Preparatory processes
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- 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
- C08K2201/001—Conductive additives
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- 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 invention belongs to the invention belongs to the field of chemical synthesis, more particularly to a kind of preparation method and applications of graphene/carbon nano-tube aerogel polymer conducing composite material.A kind of preparation method of graphene/carbon nano-tube aerogel polymer conducing composite material, comprises the following steps：After graphene/carbon nano-tube aeroge mixes with high molecular polymer presoma, reaction mixture is formed, reaction mixture is formed to graphene/carbon nano-tube aeroge high molecular polymer precursor mixture after microwave or ultraviolet irradiation；Heat graphene/carbon nano-tube aeroge high molecular polymer precursor mixture, then curing process is carried out, the temperature of heating is 48~85 DEG C, hardening time is 1.5~6h, solidification temperature is 85~155 DEG C, obtain graphene/carbon nano-tube aerogel polymer conducing composite material, conductive capability 2~7 orders of magnitude higher than conventional graphite alkenyl composite of composite.
Description
Technical field
The invention belongs to the invention belongs to the field of chemical synthesis, more particularly to a kind of polymerization of graphene/carbon nano-tube aeroge
The preparation method and applications of thing conducing composite material.
Background technology
Graphene (Graphene) be one kind by carbon atom with sp2Hydridization connects the list with hexagonal lattice structure to be formed
Atomic layer two dimensional crystal, carbon atom are regularly arranged among honeycomb lattice construction unit.The special atomic structure of graphene
Make it have the performance of many uniquenesses：Its tensile strength reaches 130GPa, and modulus of elasticity reaches 1.1TPa, and hardness reaches 4.5 ×
108NmKg-1, it is intensity and hardness highest material in known materials for tens times of steel.It, which has, greatly compares surface
Product, the specific surface area of single-layer graphene are up to 2.6 × 103m2g-1；At room temperature, its carrier is in SiO2Mobility on substrate is
104m2v-1s-1, electrical conductivity 104S/cm, it is the material that electric conductivity is best at room temperature；Its room temperature thermal conductivity is 4.40 × 103Wm- 1k-1~5.78 × 103Wm-1k-1In the range of, it is thermal conductivity highest material so far.Graphene also there is good gas to hinder
Every property, passing through for minimum gas molecule helium can be obstructed with its manufactured film.Further, since its zigzag edge possesses
Lone pair electrons, make it have potential magnetic property, such as magnetic switch and ferromagnetism.
At present, the research for graphene conductive nano composite material is more, although graphene has realized large-scale industry
Metaplasia is produced, but by production technology and equipment are limited, the oxygen-containing functional group on its surface is difficult to remove completely, causes on its lamella
Sp2Hybrid structure existing defects, π-pi-conjugated structure are affected, so as to reduce electronics in its nanoscale twins
Transmission speed, cause the electric conductivity by graphene conductive nano composite material to decrease, how to improve graphene conductive nanometer
The problem of electric conductivity of composite is current graphene conductive nano composite material development urgent need to resolve.
The content of the invention
The defects of it is an object of the invention to overcome the electric conductivity of prior art graphene conductive nano composite material low, carry
For a kind of preparation method and applications of graphene/carbon nano-tube aerogel polymer conducing composite material.
The invention provides a kind of preparation method of graphene/carbon nano-tube aerogel polymer conducing composite material, bag
Include following steps：
(1) graphene/carbon nano-tube aeroge mixes with high molecular polymer presoma, forms reaction mixture, will be anti-
Mixed liquor is answered to form graphene/carbon nano-tube aeroge high molecular polymer precursor mixture after microwave or ultraviolet irradiation.
High molecular polymer presoma refers to the high molecular polymer presoma of liquid, and the high molecular polymer liquid is pre-
In network mould of the aggressiveness injection equipped with graphene/carbon nano-tube aeroge, it is set to be fully infiltrated into graphene/carbon nano-tube airsetting
Glue network.During admixed graphite alkene/carbon nanotube aerogel and high molecular polymer presoma, it is not necessary to carry out machinery and stir
Mix, it is only necessary to simple dipping filling processing, and be not in local the problem of reuniting, the reaction mixture uniformity of formation
It is high.
The present invention is to utilize microwave or ultraviolet reduced graphene/carbon nanotube aerogel high molecular polymer presoma mixing
Thing, it is not necessary to add reducing agent.Because it can be easy to destroy the sp of graphene oxide layer when adding reducing agent2Hybrid structure,
π-pi-conjugated structure is affected, and so as to reduce transmission speed of the electronics in nanoscale twins, reduces electric conductivity.
(2) graphene/carbon nano-tube aeroge high molecular polymer precursor mixture is heated, is then carried out at solidification
Reason, the temperature of heating is 48~85 DEG C, and hardening time is 1.5~6h, and solidification temperature is 85~155 DEG C, obtains graphene/carbon nanometer
Pipe aerogel polymer conducing composite material.Conductive additive of the graphene/carbon nano-tube aeroge as composite so that
The conductive capability of composite 2~7 orders of magnitude higher than conventional graphite alkenyl composite.
Specifically, in step (1), after graphene/carbon nano-tube aeroge mixes with high molecular polymer presoma, so
After carry out application of vacuum.0.06~0.1atm of vacuum, vacuum processing time are 5~60min.Application of vacuum can remove reaction
Bubble in mixed liquor, so that reaction mixture is fully infiltrated into graphene/carbon nano-tube aeroge network.
Specifically, in the reaction mixture of step (1), the mass content of graphene/carbon nano-tube aeroge is 0.005
~20%, the mass content of high molecular polymer presoma is 80~99.995%.
Specifically, in step (1), graphene/carbon nano-tube aeroge is that three-dimensional mutually lapping network structure, density are
0.05mg/cm3~10mg/cm3, porosity is 50%~99.99%, and specific surface area is 100m2/ g~3000m2/ g, electrical conductivity
It is 0.1S/cm~50S/cm.Graphene/carbon nano-tube aeroge is the three-dimensional phase that graphene and CNT are formed with covalent bond
Mutually overlap joint network structure, this structure further enhance the pliability of graphene/carbon nano-tube aeroge, therefore, prepared
Graphene/carbon nano-tube aerogel polymer conducing composite material can bear more bendings and stretcher strain, be a kind of soft
The good composite of good toughness, elasticity.
Specifically, in step (1), high molecular polymer presoma is silicon rubber presoma, polyurethane presoma, epoxy
It is resin precursor, paraffin presoma, nylon monomer-cast nylon presoma, polymethyl methacrylate presoma, polyimide precursor, poly-
Styrene presoma, natural emulsion presoma or polypropylene presoma.
Specifically, the preparation method of the graphene/carbon nano-tube aeroge in step (1) is as follows：
First step：Finely dispersed graphene oxide (GO) solution is first prepared, then aminated carbon nano tube is added
Enter in graphene oxide solution, ultrasonic disperse is uniform, obtains mixed liquor；
, can be to the three-dimensional phase of graphene/carbon nano-tube aeroge because aminated carbon nano tube has huge draw ratio
Mutually overlap joint network structure creates favorable conditions.Meanwhile the excellent electric conductivity of aminated carbon nano tube is graphene/carbon nano-tube
Aeroge electric conductivity creates favorable conditions.Further, since amination carbon pipe has certain reduction to graphene oxide,
Therefore the electric conductivity of graphene three-dimensional network can be improved.
Second step：After mixed liquor obtained by second step is carried out microwave or ultraviolet irradiation, then at 70 DEG C~96 DEG C
At a temperature of react 2h~20h, obtain hydrogel；
Third step：Supercritical carbon dioxide drying or freeze-drying are carried out to the hydrogel obtained by third step, obtains stone
Black alkene/carbon nanotube aerogel.Freeze-drying is orientation freeze-drying or non-directional freeze-drying, and freeze-drying is in order that institute
Hydrogel structure hold its shape looks.
Specifically, in the mixed liquor obtained by first step, graphene oxide and aminated carbon nano tube mass ratio are 1：
0.1~5.
Specifically, in the second step, the microwave frequency is 20~20000MHZ, microwave output power be 50W~
50000W, microwave treatment time are 0.1~400min, and the wavelength of the ultraviolet light is 100~400nm, uv power 50W
~5000W, ultraviolet processing time are 0.1~400min.
Specifically, in the first step, in ultrasound, temperature is 40~90 DEG C, and ultrasonic time is 0.5~4h；In the 3rd step
In rapid, in freeze-drying, cryogenic temperature is -196~2 DEG C, and drying temperature is 0~50 DEG C, dry vacuum be 3~
30000Pa, drying time are 4~72h.
In addition, a kind of graphene/carbon nano-tube aerogel polymer conducing composite material is additionally provided in conductive composite wood
Application in material or elastic conductor field.
Beneficial effects of the present invention：(1) in the present invention, graphene/carbon nano-tube aeroge is graphene and carbon nanometer
The three-dimensional that pipe is formed with covalent bond mutually lapping network structure, this structure can strengthen the electric conductivity of composite.In addition, stone
Conductive additive of the black alkene/carbon nanotube aerogel as composite, plus aminated carbon nano tube to graphene oxide
With certain reduction so that the conductive energy of obtained graphene/carbon nano-tube aerogel polymer conducing composite material
Power 2~7 orders of magnitude higher than conventional graphite alkenyl composite；(2) graphene/carbon nano-tube aeroge is that graphene and carbon are received
The three-dimensional that mitron is formed with covalent bond mutually lapping network structure, this structure further enhance graphene/carbon nano-tube airsetting
The pliability of glue, more bendings and stretcher strain can be born.So graphene/carbon nano-tube aeroge and polyphosphazene polymer
Composite made of compound is the composite that a kind of pliability is good, elasticity is good；(3) present invention be using microwave or it is ultraviolet also
Former graphene/carbon nano-tube aeroge high polymer mixtures, also have to graphene oxide plus aminated carbon nano tube
There is certain reduction, it is not necessary to add reducing agent, reduce the use of chemicals, reduce to a certain extent to environment
Pollution；(4) present invention has the characteristics of easy to operate, cost is low and is easy to structure regulating, is expected to turn into large-scale production height
The universal method of the graphene-based composite of performance, can be widely applied to conducing composite material and elastic conductor field.
Embodiment
With reference to specific embodiment, the present invention is further illustrated.
The preparation method of graphene/carbon nano-tube aeroge, it is specifically shown in embodiment 1~4：
Embodiment 1
The 100ml 2mg/ml prepared in beaker graphite oxide (GO) solution, is put into power 500w, frequency 10000HZ
Ultrasound Instrument in ultrasound, in ultrasound, temperature is 40 DEG C, and ultrasonic time is 4h, obtains scattered uniform graphene oxide solution.To oxygen
20mg aminated carbon nano tubes are added in graphite alkene solution, being then placed in continuation ultrasonic disperse 30min in Ultrasound Instrument fills it
Divide reaction, mixed liquor is obtained after ultrasound；Irradiation reduction is carried out by microwave in mixed liquor, microwave frequency is
20000MHZ, power 50000W.Then beaker sealing being put into thermostat water bath with preservative film, temperature is set as 96 DEG C,
2h is reacted, after reaction terminates, water unnecessary in beaker is poured out, is soaked after products therefrom is cleaned with distilled water, and freeze
It is dried to obtain graphene/carbon nano-tube aeroge.It is freeze-dried and is freeze-dried for orientation, cryogenic temperature is -196 DEG C, dries temperature
Spend for 0 DEG C, it is 3Pa, drying time 4h to dry vacuum.
It is 0.05mg/cm that graphene/carbon nano-tube aeroge density prepared by the present embodiment 1, which is,3, porosity is
97.40%, specific surface area 500m2/ g, electrical conductivity 4S/cm.
Embodiment 2
10ml 3mg/ml graphite oxide (GO) solution is prepared in beaker, is put into power 2000w, frequency 1000HZ surpasses
Ultrasonic in sound instrument, in ultrasound, temperature is 65 DEG C, and ultrasonic time is 2.5h, obtains scattered uniform graphene oxide solution.In ultrasound
90mg aminated carbon nano tubes are added in the graphene oxide solution finished, being put into continuation ultrasonic disperse 60min in Ultrasound Instrument makes
It fully reacts.The solution of gained carries out irradiation reduction by microwave in the mixed solution that ultrasound finishes, and microwave frequency is
20MHZ, power 50W.Hereafter, beaker sealing is put into thermostat water bath with preservative film, temperature is set as 90 DEG C, reaction
10h.After reaction terminates, water unnecessary in beaker is poured out, products therefrom is cleaned with distilled water, soaked, and carbon dioxide
Supercritical drying obtains graphene/carbon nano-tube aeroge.
It is 10mg/cm that graphene/carbon nano-tube aeroge density prepared by the present embodiment 2, which is,3, porosity 99.10%,
Specific surface area is 800m2/ g, electrical conductivity 0.1S/cm.
Embodiment 3
10ml 3mg/ml graphite oxide (GO) solution is prepared in beaker, is put into power 2000w, frequency 1000HZ surpasses
Ultrasonic in sound instrument, in ultrasound, temperature is 90 DEG C, and ultrasonic time is 30min, obtains scattered uniform graphene oxide solution.In ultrasound
30mg aminated carbon nano tubes are added in the graphene oxide solution finished, being put into continuation ultrasonic disperse 60min in Ultrasound Instrument makes
It fully reacts.The solution of gained carries out irradiation reduction, the ripple of ultraviolet light by ultraviolet light in the mixed solution that ultrasound finishes
A length of 100nm, uv power 50W.Hereafter, beaker sealing is put into thermostat water bath with preservative film, temperature is set as
80 DEG C, 15h is reacted, after reaction terminates, water unnecessary in beaker is poured out, products therefrom is cleaned with distilled water, soaked, and
Freeze-drying obtains graphene/carbon nano-tube aeroge.It is freeze-dried and is freeze-dried for non-directional, cryogenic temperature is~100 DEG C,
Drying temperature is 20 DEG C, and it is 10000Pa, drying time 35h to dry vacuum.
It is 0.14mg/cm that graphene/carbon nano-tube aeroge density prepared by the present embodiment 3, which is,3, porosity is
99.56%, specific surface area 1000m2/ g, electrical conductivity 50S/cm.
Embodiment 4
10ml 3mg/ml graphite oxide (GO) solution is prepared in beaker, is put into power 2000w, frequency 1000HZ surpasses
Ultrasonic in sound instrument, in ultrasound, temperature is 90 DEG C, and ultrasonic time is 30min, obtains scattered uniform graphene oxide solution.In ultrasound
150mg aminated carbon nano tubes are added in the graphene oxide solution finished, being put into continuation ultrasonic disperse 60min in Ultrasound Instrument makes
It fully reacts.The solution of gained carries out irradiation reduction, the ripple of ultraviolet light by ultraviolet light in the mixed solution that ultrasound finishes
A length of 400nm, uv power 5000W.Hereafter, beaker sealing is put into thermostat water bath with preservative film, temperature setting
For 70 DEG C, 20h is reacted.After reaction terminates, water unnecessary in beaker is poured out, products therefrom is cleaned with distilled water, soaked,
And CO 2 supercritical is dried to obtain graphene/carbon nano-tube aeroge.
It is 10mg/cm that graphene/carbon nano-tube aeroge density prepared by the present embodiment 4, which is,3, porosity 99.10%,
Specific surface area is 800m2/ g, electrical conductivity 20S/cm.
The preparation method of graphene/carbon nano-tube aeroge silicon rubber composite material, is specifically shown in embodiment 5~10：
When high molecular polymer presoma is polyurethane presoma, the preparation method of polyurethane presoma, specific steps
It is as follows：By polyurethane presoma and curing agent by weight 2~20：1 mix simultaneously be stirred vigorously, and 100~5000w of power,
Disperse 10~100min under 10000~500000HZ of frequency ultrasonication, it is uniformly dispersed, then vacuum degassing is steeped
5min, obtain polyurethane presoma presoma.
When high molecular polymer presoma is polystyrene presoma or polypropylene presoma, high molecular polymer forerunner
The preparation method of body, is comprised the following steps that：
By high molecular polymer and acetone and other organic solvent by weight 0.01~2：It is stirred vigorously after 1 mixing to polymer
It is completely dissolved and forms a thick solution, and in 100~5000w of power, 10000~500000HZ of frequency ultrasonication
Disperse 10~100min down, it is uniformly dispersed, then vacuum de-soak 5min, obtains polymer precursor.
Embodiment 5
(1) the high molecular polymer presoma of the present embodiment is silicon rubber presoma, its model Dowcorning's
Sylgard-184 (contains curing agent).Silicon rubber：α, ω-hydroxyl dimethyl silicone polymer (PDMS) technical grade, are by Jinan state
Chemical Co., Ltd. of nation produces；Crosslinking agent (tetraethyl orthosilicate, analysis are pure) and catalyst (dibutyltindilaurylmercaptide cinnamic acid, analysis are pure)
It is to be produced by Co., Ltd of Shanghai Resin Factory.
(2) preparation method of silicon rubber presoma is as follows：Silicon rubber is 100 with crosslinking agent, the mass ratio of catalyst：4：
1, using petroleum ether as solvent, about 5 minutes are stirred vigorously after mixing to full and uniform, and power 600w, frequency 10000HZ it is super
The lower scattered 10min of sound effect makes it be uniformly dispersed, then vacuum degassing is steeped 10 minutes, obtains silicon rubber presoma.
(3) preparation method of graphene/carbon nano-tube aeroge silicon rubber composite material：First prepared by embodiment 1
Graphene/carbon nano-tube aeroge is placed in a mould, is then injected into silicon rubber presoma, is permeated it and is fully infiltrated graphite
Alkene/carbon nanotube aerogel, form reaction mixture.In reaction mixture, the quality of graphene/carbon nano-tube aeroge contains
Amount is 0.005%, and the mass content of high molecular polymer presoma is 99.995%.Reaction mixture is subjected to spoke by microwave
According to formation graphene/carbon nano-tube aeroge high polymer mixtures after reduction.Microwave frequency is 1000MHZ, power is
800W.Hereafter application of vacuum, vacuum 0.1atm used, vacuum processing time 60 minutes are carried out again.Application of vacuum mixes reaction
Close liquid in air bubble expansion and emersion liquid level and remove, reaction mixture is more fully penetrated into graphene/carbon nano-tube gas
In the space of gel.The homogeneous mixture of graphene/carbon nano-tube aeroge and silicon rubber precursor solution is heated to 85 DEG C,
And heat preservation solidification 6 hours, obtain graphene/carbon nano-tube aeroge silicon rubber composite material.
In graphene/carbon nano-tube aeroge silicon rubber composite material manufactured in the present embodiment, graphene mass content is about
For 0.1%, electrical conductivity is about 1.5S/cm, basically identical with the electrical conductivity of original graphite alkene/carbon nanotube aerogel, than tradition
High six orders of magnitude of the graphene-based composite of chemical stripping method.In addition, the tensile strength of pure silicone rubber is 0.32MPa, pass through
The method of the present invention is modified, and tensile strength is promoted to 0.39MPa, and the tensile strength of composite is higher than pure silicone rubber
20%.
Graphene/carbon nano-tube aeroge silicon rubber composite material has very excellent electricity as a kind of elastic conductor
With mechanical property and very high mechanical stability, when bending to 2.8mm radius of curvature, the resistance of composite only rises 1%,
And resistance does not also change significantly after being subjected to the alternating bending of 5,000 times.When composite is subjected to bigger change shaped like bending
Resistance is also only risen less than 15% under to 0.6mm radius of curvature and 60% tensile deformation, and can continue to bear height
The stretcher strain reached.
Embodiment 6
(1) the present embodiment high molecular polymer presoma is epoxy resin presoma, and epoxy resin is epoxy resin 828,
It is to be produced by Shanghai City Hongxin Chemical trade Co., Ltd, curing agent is diethylenetriamine, is had by Chinese medicines group chemical reagent
Limit company produces.
(2) preparation method of epoxy resin presoma is as follows：Epoxy resin 828 presses 2 with diethylenetriamine：1 mass ratio
About 10 minutes are stirred vigorously after mixing to full and uniform, and power 400w, frequency 10000HZ ultrasonication under disperse
20min makes it be uniformly dispersed.Vacuum de-soak 20 minutes again, obtain epoxy resin presoma.
(3) preparation method of graphene/carbon nano-tube aeroge epoxy resin composite material：First prepared by embodiment 2
Graphene/carbon nano-tube aeroge be placed in a mould, be then injected into epoxy resin presoma, make its permeate and fully infiltrate
Graphene/carbon nano-tube aeroge, form reaction mixture.In reaction mixture, the matter of graphene/carbon nano-tube aeroge
It is 20% to measure content, and the mass content of high molecular polymer presoma is 80%.Reaction mixture is reduced through microwave irradiation, it is micro-
Wave frequency rate is 1000MHZ, power 800W.Hereafter application of vacuum, vacuum 0.06atm used, vacuum processing time are carried out again
30 minutes.Application of vacuum make the air bubble expansion in reaction mixture and emersion liquid level and remove, make reaction mixture more fully
Penetrate into the space of graphene/carbon nano-tube aeroge.Graphene/carbon nano-tube aeroge and epoxy resin presoma is molten
The homogeneous mixture of liquid is heated to 100 DEG C, and heat preservation solidification 1.5 hours, obtains graphene/carbon nano-tube aeroge epoxy resin
Composite.
Graphene mass content in graphene/carbon nano-tube aeroge epoxy resin composite material prepared by the present embodiment
About 0.4%, electrical conductivity is about 8.0S/cm, basically identical with the electrical conductivity of original graphite alkene/carbon nanotube aerogel, than passing
System high six orders of magnitude of the graphene-based composite of chemical stripping method.The tensile strength of pure epoxy resin is 24.68MPa, this reality
The tensile strength for applying the graphene/carbon nano-tube aeroge epoxy resin composite material prepared by example is 32.11MPa, therefore, and
And the tensile strength of the graphene/carbon nano-tube aeroge epoxy resin composite material prepared by the present embodiment compares pure epoxy resin
It is high by 30%.
Embodiment 7
(1) the present embodiment high molecular polymer presoma is polymethyl methacrylate presoma, poly-methyl methacrylate
The preparation method of ester presoma is as follows：Acetone is with polymethyl methacrylate according to mass ratio 1：After 2 mixing, about 15 are stirred vigorously
Hour to full and uniform, and power 600w, frequency 10000HZ ultrasonication under disperse 40min, it is uniformly dispersed.So
Vacuum de-soak 30 minutes afterwards, obtain polymethyl methacrylate presoma.
(2) preparation method of graphene/carbon nano-tube aeroge composite material of polymethyl methacrylate：By embodiment 3
The graphene/carbon nano-tube aeroge of preparation is placed in a mould, and injects polymethyl methacrylate presoma, makes its infiltration
And fully infiltrate graphene/carbon nano-tube aeroge.Graphene/carbon nano-tube aeroge and polymethyl methacrylate presoma
Irradiation reduction, microwave frequency 1000MHZ, power 800W are further carried out by microwave after being sufficiently mixed uniformly.Hereafter again
Carry out application of vacuum, vacuum 0.06atm used, vacuum processing time 30 minutes.Application of vacuum makes the gas in polymer solution
Bubble expands simultaneously emersion liquid level and removed, and polymer solution is more fully penetrated into the space of graphene/carbon nano-tube aeroge
In.The homogeneous mixture of graphene/carbon nano-tube aeroge and polymethyl methacrylate precursor solution is heated to 48 DEG C,
Acetone is fully volatilized, be again heated to 155 DEG C of simultaneously heat preservation solidification 1.5 hours, obtain the poly- methyl of graphene/carbon nano-tube aeroge
Methyl acrylate composite.
Graphene in graphene/carbon nano-tube aeroge composite material of polymethyl methacrylate prepared by the present embodiment
Mass content is about 0.2%, and electrical conductivity is about 25.0S/cm, basic with the electrical conductivity of original graphite alkene/carbon nanotube aerogel
Unanimously, high six orders of magnitude of composite more graphene-based than traditional chemical stripping method.In addition, the drawing of pure polymethyl methacrylate
It is 30.20MPa to stretch intensity, the stretching of the graphene/carbon nano-tube aeroge epoxy resin composite material prepared by the present embodiment
Intensity is 34.75MPa, therefore the drawing of the graphene/carbon nano-tube aeroge epoxy resin composite material prepared by the present embodiment
It is higher than pure polymethyl methacrylate by 15.0% to stretch intensity.
Embodiment 8
(1) the present embodiment high molecular polymer presoma is the presoma of nylon monomer-cast nylon 6, and the presoma of nylon monomer-cast nylon 6 is in
The caprolactam of Ba Ling branch companies of petrochemical industry limited company of state production.
(2) preparation method of graphene/carbon nano-tube aeroge cast nylon composite material：Stone prepared by embodiment 4
Black alkene/carbon nanotube aerogel is put into the toluene solution of toluene di-isocyanate(TDI), is heated to 40 DEG C of stirring 4h, then in power
400w, frequency 10000HZ ultrasonication under disperse 20min it is uniformly dispersed, irradiation reduction is then carried out by microwave, it is micro-
Wave frequency rate is 1000MHZ, power 800W.Caprolactam in reactor is warming up to 130 DEG C, is evaporated under reduced pressure and removes moisture,
0.20g sodium hydroxides are added in reactor, carry out vacuum distillation water removal again, are warming up to 140 DEG C, remove vacuum, rapid note
Enter to be put into the mould of graphene/carbon nano-tube aeroge (mold temperature is 170 DEG C), form graphene/carbon nano-tube gas
Gel caprolactam mixture.Hereafter application of vacuum, vacuum 0.06atm used, vacuum processing time 30 minutes are carried out again.Very
Vacancy reason make air bubble expansion in caprolactam and emersion liquid level and remove, make caprolactam more fully penetrate into graphene/
In the space of carbon nanotube aerogel.Polymerisation 60 minutes, is stripped after natural cooling.Obtain graphene/carbon nano-tube airsetting
Glue cast nylon composite material.
Graphene mass content in graphene/carbon nano-tube aeroge cast nylon composite material prepared by the present embodiment
About 0.4%, electrical conductivity mass content is about 14.0S/cm, basic with the electrical conductivity of original graphite alkene/carbon nanotube aerogel
Unanimously (electrical conductivity of original graphite alkene/carbon nanotube aerogel is i.e. 8.5S/cm)；It is more graphene-based than traditional chemical stripping method multiple
(order of magnitude of the graphene-based composite of traditional chemical stripping method is 10 to high six orders of magnitude of condensation material-4-10-5S/cm)；And
The tensile strength of composite is higher than pure nylon monomer-cast nylon by 10%, (tensile strength of pure nylon monomer-cast nylon is 80.5MPa).
Embodiment 9
(1) the present embodiment high molecular polymer presoma is the presoma of nylon monomer-cast nylon 6, and the presoma of nylon monomer-cast nylon 6 is in
The caprolactam of Ba Ling branch companies of petrochemical industry limited company of state production.
(2) preparation method of graphene/carbon nano-tube aeroge cast nylon composite material：Stone prepared by embodiment 4
Black alkene/carbon nanotube aerogel is put into the toluene solution of toluene di-isocyanate(TDI), is heated to 40 DEG C of stirring 4h, then in power
400w, frequency 10000HZ ultrasonication under disperse 20min it is uniformly dispersed；And further irradiate also by microwave
Original, microwave frequency 1000MHZ, power 800W.Caprolactam in reactor is warming up to 130 DEG C, is evaporated under reduced pressure and removes
Moisture；Then 0.20g sodium hydroxides are added in reactor, carries out vacuum distillation water removal again, be warming up to 140 DEG C, removal is true
Sky, and 0.8g toluene di-isocyanate(TDI) activators are rapidly added, stir, rapid injection has been put into graphene/carbon and received in advance
In 170 DEG C of mould of mitron aeroge, graphene/carbon nano-tube aeroge caprolactam mixture is formed, makes its infiltration simultaneously
Fully infiltration graphene/carbon nano-tube aeroge.Hereafter application of vacuum is carried out again, vacuum 0.06atm used, during application of vacuum
Between 5 minutes.Application of vacuum make the air bubble expansion in caprolactam and emersion liquid level and remove, caprolactam is more fully permeated
Enter in the space of graphene/carbon nano-tube aeroge.Polymerisation 60 minutes, is stripped after natural cooling.Graphene/carbon is obtained to receive
Mitron aeroge cast nylon composite material.
Graphene content quality in graphene/carbon nano-tube aeroge cast nylon composite material prepared by the present embodiment
About 0.4%, electrical conductivity quality is about 18.0S/cm, the electrical conductivity (original graphite with original graphite alkene/carbon nanotube aerogel
The electrical conductivity of alkene/carbon nanotube aerogel is 12.0S/cm) basically identical, composite more graphene-based than traditional chemical stripping method
High six orders of magnitude.And the tensile strength of composite is higher than pure nylon monomer-cast nylon by 15%, (tensile strength of pure nylon monomer-cast nylon is
80.5MPa)。
Embodiment 10
(1) the present embodiment high molecular polymer presoma is 60% natural emulsion presoma, and natural emulsion is natural rubber
Glue, natural rubber come from Xishuangbanna Jing Yang limited rubbers responsible company, and its solid content is 60%.
(2) (i.e. graphene/carbon nano-tube aeroge is modified graphene/carbon nano-tube aeroge natural emulsion composite
Natural emulsion condom products) preparation method：Graphene/carbon nano-tube aeroge grinds prepared by embodiment 1, grinding
Shi Caiyong milling apparatus is ground 6 hours, is then mixed with natural emulsion, forms graphene/carbon nano-tube aeroge natural emulsion
Mixture, permeate it and fully infiltrate graphene/carbon nano-tube aeroge.Add 1% dispersion stabilizer, 0.2%
Surfactant, 1% accelerator, 0.8% age resistor, 2% vulcanizing agent and 0.5% vulcanizing activator, disperse steady
It is sodium laurate or F108 to determine agent, and surfactant is cetyl benzenesulfonic acid, and accelerator is diethyldithiocar bamic acid
Zinc, age resistor 2,6- di-tert-butyl-4-methy phenols, vulcanizing agent are sulphur, and vulcanizing activator is zinc oxide.Graphene/carbon
Nanotube aeroge and natural emulsion be sufficiently mixed uniformly after power 400w, frequency 10000HZ ultrasonication under disperse
20min makes it be uniformly dispersed.And irradiation reduction, microwave frequency 1000MHZ, power 800W are further carried out by microwave.
Hereafter application of vacuum, vacuum 0.06atm used, vacuum processing time 30 minutes are carried out again.Application of vacuum makes in natural emulsion
Air bubble expansion and emersion liquid level and remove, natural emulsion is more fully penetrated into the sky of graphene/carbon nano-tube aeroge
In gap, viscosity is 8mPas or so.Glue after will be compound stands 24 hours or so, it is fully cured, and then adds dipping
Carried out in machine with condom mold dipping three times after heat drying solidified to 100 DEG C, obtain graphene/carbon nano-tube airsetting
Glue modified natural emulsion condom products.
Graphene matter in graphene/carbon nano-tube aeroge modified natural emulsion condom products prepared by the present embodiment
It is about 0.4% to measure content, and the tensile strength of graphene/carbon nano-tube aeroge modified natural emulsion condom products is than pure
Natural emulsion is high by 10%, (tensile strength of pure natural latex is 2.25MPa)；Elongation at break than pure natural latex is high
30%, the elongation at break of pure natural latex is 275%.Meanwhile the compound action of graphene/carbon nano-tube aeroge and latex
Make micropore less, substantially reduce AIDS virus, hepatitis B, hepatitis C virus, the transmission probability of human papilloma virus, graphite
Alkene/carbon nanotube aerogel modified natural emulsion condom products condom thickness can reach one micron, disclosure satisfy that condom
Requirement.
The above is only the section Example of the present invention, any formal limitation not done to the present invention, it is every according to
Any simple modification made according to the technical spirit of the present invention to above-described embodiment, equivalent variations and modification, belong to the present invention
In the range of technical scheme.
Claims (10)
- A kind of 1. preparation method of graphene/carbon nano-tube aerogel polymer conducing composite material, it is characterised in that including with Lower step：(1) after graphene/carbon nano-tube aeroge mixes with high molecular polymer presoma, reaction mixture is formed, will be reacted Mixed liquor forms graphene/carbon nano-tube aeroge high molecular polymer precursor mixture after microwave or ultraviolet irradiation；(2) graphene/carbon nano-tube aeroge high molecular polymer precursor mixture is heated, curing process is then carried out, adds The temperature of heat is 48~85 DEG C, and hardening time is 1.5~6h, and solidification temperature is 85~155 DEG C, obtains graphene/carbon nano-tube gas Gelatin polymer conducing composite material.
- 2. the preparation method of graphene/carbon nano-tube aerogel polymer conducing composite material according to claim 1, its It is characterised by：In step (1), graphene/carbon nano-tube aeroge carries out vacuum after being mixed with high molecular polymer presoma Processing, vacuum is 0.06~0.1atm, and vacuum processing time is 5~60min.
- 3. the preparation side of graphene/carbon nano-tube aerogel polymer conducing composite material according to claim 1 or 2 Method, it is characterised in that：In the reaction mixture of step (1), the mass content of graphene/carbon nano-tube aeroge is 0.005 ~20%, the mass content of high molecular polymer presoma is 80~99.995%.
- 4. the preparation side of graphene/carbon nano-tube aerogel polymer conducing composite material according to claim 1 or 2 Method, it is characterised in that：In step (1), graphene/carbon nano-tube aeroge is that three-dimensional mutually lapping network structure, density are 0.05mg/cm3~10mg/cm3, porosity is 50%~99.99%, and specific surface area is 100m2/ g~3000m2/ g, electrical conductivity It is 0.1S/cm~50S/cm.
- 5. the preparation method of graphene/carbon nano-tube aerogel polymer conducing composite material according to claim 1, its It is characterised by：In step (1), before high molecular polymer presoma is silicon rubber presoma, polyurethane presoma, epoxy resin Drive body, paraffin presoma, nylon monomer-cast nylon presoma, polymethyl methacrylate presoma, polyimide precursor, polystyrene Presoma, natural emulsion presoma or polypropylene presoma.
- 6. the preparation method of graphene/carbon nano-tube aerogel polymer conducing composite material according to claim 1, its It is characterised by：The preparation method of graphene/carbon nano-tube aeroge in step (1) is as follows：First step：Finely dispersed graphene oxide (GO) solution is first prepared, aminated carbon nano tube is then added oxygen In graphite alkene solution, ultrasonic disperse is uniform, obtains mixed liquor；Second step：After mixed liquor obtained by first step is carried out microwave or ultraviolet irradiation, then in 70 DEG C~96 DEG C of temperature The lower reaction 2h~20h of degree, obtains hydrogel；Third step：Carry out that supercritical carbon dioxide is dry or freeze-drying to the hydrogel obtained by second step, obtain graphene/ Carbon nanotube aerogel.
- 7. the preparation method of graphene/carbon nano-tube aerogel polymer conducing composite material according to claim 6, its It is characterised by：In the mixed liquor obtained by first step, graphene oxide and aminated carbon nano tube mass ratio are 1：0.1~5.
- 8. the preparation method of graphene/carbon nano-tube aerogel polymer conducing composite material according to claim 6, its It is characterised by：In the second step, during microwave treatment, microwave frequency is 20~20000MHZ, microwave treatment time is 0.1~ 400min, microwave output power are 50W~50000W, and during ultraviolet processing, the wavelength of ultraviolet light is 100~400nm, ultraviolet light work( Rate is 50W~5000W, and ultraviolet processing time is 0.1~400min.
- 9. the preparation method of graphene/carbon nano-tube aerogel polymer conducing composite material according to claim 6, its It is characterised by：In the first step, in ultrasound, temperature is 40~90 DEG C, and ultrasonic time is 0.5~4h, in third step, In freeze-drying, cryogenic temperature is -196~-2 DEG C, and drying temperature is 0~50 DEG C, and it is 3~30000Pa to dry vacuum, is done The dry time is 4~72h.
- A kind of 10. graphene/carbon nano-tube aerogel polymer conducing composite material as described in any one of claim 1~9 Application, it is characterised in that：The graphene/carbon nano-tube aerogel polymer conducing composite material in conducing composite material or Application in elastic conductor field.
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