CN108454057A - The method and its application of high molecular material/graphene nanocomposite material are prepared using continuous mixing in-situ reducing - Google Patents
The method and its application of high molecular material/graphene nanocomposite material are prepared using continuous mixing in-situ reducing Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/50—Details of extruders
- B29C48/76—Venting, drying means; Degassing means
- B29C48/762—Vapour stripping
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/50—Details of extruders
- B29C48/76—Venting, drying means; Degassing means
- B29C48/765—Venting, drying means; Degassing means in the extruder apparatus
- B29C48/766—Venting, drying means; Degassing means in the extruder apparatus in screw extruders
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- H05K9/0081—Electromagnetic shielding materials, e.g. EMI, RFI shielding
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- C08L2201/04—Antistatic
Abstract
The method and its application that high molecular material/graphene nanocomposite material is prepared using continuous mixing in-situ reducing are related to high molecular material/graphene nanocomposite material and its preparing technical field.Used equipment is a kind of water auxiliary molten mixing extrusion equipment.The preparation method of nanocomposite is to carry out mixing extrusion being added in a kind of water auxiliary molten mixing extrusion equipment after high molecular material and GO powder premix, a kind of green non-poisonous chemical reducing agent is dissolved in water and obtains chemical reducing agent aqueous solution, acquired solution is injected in extruder inner macromolecule material melt by metering pump and is kneaded, water plays a part of to promote the stripping dispersion of GO, in-situ chemical reduction and heat-treat in situ, is finally prepared into high molecular material/redox graphene (RGO) nanocomposite.In nanocomposite prepared by the present invention stripping of RGO and it is well dispersed, reducing degree is high, and the nanocomposite have preferable dielectric properties and mechanical property.
Description
Technical field
The present invention relates to high molecular material/graphene nanocomposite material and its preparing technical fields, more particularly to a kind of
The height reduction of graphene oxide is realized during continuous mixing and is preferably removed and is disperseed to prepare high performance polymer
The new method of material/graphene nanocomposite material and its application.
Background technology
Graphene has two-dimensional layer nanostructure and the performances such as excellent heat conductivity and conduction, in fields such as high molecular materials
It is with a wide range of applications.However the poor compatibility of graphene and high molecular material, easily reunite, this is unfavorable for it in height
Stripping in molecular material and dispersion.Graphene oxide (GO) is a kind of intermediate product in graphene preparation process, lamella
Surface carries a large amount of oxygen-containing group (carboxyl, carbonyl, epoxy group and hydroxyl).These oxygen-containing groups make GO not only can be in water
It realizes fine dispersion, obtains that there is two-dimensional layer nanostructure similar with graphene, and polar group is carried with most of
High molecular material have preferable compatibility.But these oxygen-containing groups can limit the electronics movement of GO lamellas and cause stronger
Phon scattering makes GO that the performances such as low conduction and heat conduction be presented.For this purpose, some researchers attempt to use GO powder as presoma,
So that it is obtained high molecular material/GO nanocomposites with polymer material mixing, then passes through in-situ chemical reduction or original
Position thermal reduction is to remove most of oxygen-containing group of GO sheet surfaces to restore the conjugation carbon backbone structure of graphene, to obtain
High molecular material/redox graphene (RGO) nanocomposite.
It prepares high molecular material/GO nanocomposites at present and realizes the process summary of the common method of GO in-situ reducings
It is as follows.Method is kneaded using solvent and prepares high molecular material/GO/ organic solvent solutions；Chemical reducing agent is added into the solution,
Make GO that in-situ chemical reduction occur under certain condition, or the solution is dried, high molecular material/GO nanocomposites are made, it is right
It, which carries out hot pressing, makes GO that thermal reduction in situ occur；In this way, high molecular material/RGO nanocomposites are made.This method exist with
Lower disadvantage.(1) a large amount of organic solvent need to be used, which increase costs, and harmful to environment；(2) in high molecular material/GO/
A few hours are reached the time required to the in-situ chemical reduction reaction carried out in organic solvent solution, this leads to high molecular material/RGO nanometers
The long preparation period of composite material；(3) it is limited by high molecular material thermal degradation temperature, temperature when thermal reduction reaction in situ is not
Preferably excessively high, this causes the reducing degree of GO in gained high molecular material/RGO nanocomposites relatively low, is embodied in gained RGO's
Carbon oxygen atom ratio (C/O ratios) is relatively low.It is compared to the above, prepare high molecular material/RGO nanometers again using melting mixing method
Condensation material does not use organic solvent, has many advantages, such as that at low cost, preparation is simple and the period is short.Have studies have shown that making containing change
High molecular material/GO mixtures of reducing agent carry out melting mixing in mixer can realize the in-situ chemical reduction of GO.But
It is that there are still following deficiencies for this method.(1) good strippings and dispersion of the RGO in high molecular material matrix are difficult to realize；(2) institute
Secure satisfactory grades RGO in sub- material/RGO nanocomposites reducing degree it is limited, C/O is relatively low；(3) it cannot achieve nano combined
It is prepared by the serialization of material；(4) most of reducing agent used by has certain toxicity.
Invention content
For the technical problems in the prior art, it is gone back in situ using continuous mixing the object of the present invention is to provide a kind of
Original prepares new method and its application of high molecular material/graphene nanocomposite material.This method can realize that graphene oxide exists
In high molecular material matrix it is preferable stripping and dispersion and height restore, while can serialization prepare high molecular material/graphite
Alkene nanocomposite.
To achieve the goals above, the present invention adopts the following technical scheme that.
The method that high molecular material/graphene nanocomposite material is prepared using continuous mixing in-situ reducing, including it is as follows
Step.
(1) chemical reducing agent is dissolved in deionized water, obtains certain density chemical reducing agent aqueous solution, is placed in storage
In fluid cylinder；
(2) extruder for starting water auxiliary molten mixing extrusion equipment, by the high molecular material and graphene oxide of premix
Powder mixture is added in extruder and carries out mixing extrusion；
(3) adjustment squeezes out machined parameters (including feeding capacity, screw speed and machine barrel temperature of each section), makes extruder water filling section
Interior high molecular material melt pressure is increased to and can keep the water of injection when being liquid at high temperature, by metering pump by step
(1) gained chemical reducing agent aqueous solution is injected with certain flow rate in the melt in extruder from water filling port；
(4) inject reducing agent aqueous solution extruder screw mixing effect under enter adjacent graphene oxide layer it
Between, promote stripping and dispersion and in-situ chemical reduction and in situ thermal reduction of the graphene oxide in high molecular material melt；
(5) water forms vapor in the generation vaporization of extruder exhaust section and is taken away from exhaust outlet by vacuum pump, goes out in head
It is compound that high molecular material/graphene nano that obtained graphene oxide is preferably removed and disperses and highly restore is squeezed out at mouthful
Material.
As a preferred embodiment, high molecular material is the thermoplastic macromolecule material of not facile hydrolysis.It is preferred that polymethylacrylic acid
Methyl esters, thermoplastic polyurethane elastomer, polyvinylidene fluoride, polypropylene or polystyrene.
As a preferred embodiment, chemical reducing agent is water-soluble, nontoxic chemical reducing agent.It is preferred that phenol, bisulfite
Sodium, xylitol, vitamin C or hydroiodic acid.
As a preferred embodiment, water auxiliary molten mixing extrusion equipment includes a single screw extrusion machine or twin-screw extrusion
The screw speed of machine, extruder is 20~500r/min, and barrel temperature is 100~300 DEG C；Also include a metering pump, metering
The injection rate of pump control chemical reducing agent aqueous solution.
As a preferred embodiment, melt pressure is higher than after stablizing in extruder water filling section when injection chemical reducing agent aqueous solution
2MPa。
As a preferred embodiment, a concentration of 0.01~1g/ml of chemical reducing agent aqueous solution；High molecular material and graphite oxide
The mass ratio of alkene powder is 100:0.04~100:20；Chemical reducing agent aqueous solution injection rate and height in step (2) in step (3)
The mass ratio of molecular material addition is 1:20~1:1.
The application of the method for high molecular material/graphene nanocomposite material is prepared using continuous mixing in-situ reducing, is used
In preparing dielectric material, electromagnetic shielding material, Heat Conduction Material and antistatic material etc..
The present invention prepares high molecular material/graphene that graphene oxide is preferably removed and disperses and highly restore and receives
The action principle of nano composite material is as described below.
(1) using a kind of water auxiliary molten mixing extrusion equipment (mainly comprising an extruder, a set of water filling device and one
Platform vacuum pump) a kind of high molecular material/graphene nanocomposite material is prepared, the raw material used when preparing includes a kind of high score
Sub- material, a kind of graphene oxide powder and a kind of chemical reducing agent.
(2) in the preparation process of the nanocomposite, chemical reducing agent aqueous solution is injected into the melt in extruder
In after, since the oxygen-containing group on graphene oxide layer surface has strong hydrophily, therefore hydrone is easy the mixing in screw rod
Effect is lower to be entered between adjacent graphene oxide layer, to increase interlayer spacing between the graphene oxide layers.Graphite oxide
The spacing of alkene lamella, which increases, promotes high molecular strand intercalation to enter between graphene oxide layer, to promote graphene oxide
Stripping and dispersion.
(3) in the preparation process of the nanocomposite, there are two types of the in-situ reducings that factor influences graphene oxide：Change
Learn reducing agent (electronation) and the heating of extruder and screw mixing (thermal reduction).The injection of chemical reducing agent aqueous solution is molten
After in body, water promotes the stripping and dispersion of graphene oxide, and more oxygen-containing groups is made to be exposed in high molecular material melt, from
And promote the thermal reduction in situ of graphene oxide；Water also increases the contact area of chemical reducing agent and graphene oxide, to promote
In-situ chemical into graphene oxide restores.
Generally speaking, the invention has the advantages that.
(1) technology (water auxiliary molten mixing extrusion) that uses of the present invention can be achieved continuous, batch production high molecular material/
Graphene nanocomposite material, operating process is simple and easy to do, easily controllable, and production cost is low, easy to spread, and application prospect is wide
It is wealthy.
(2) preparation process of high molecular material/graphene nanocomposite material of the invention does not use organic solvent, avoids
Solvent is kneaded method to the disagreeableness disadvantage of environment.
(3) the present invention overcomes normal melt mixing method to prepare high molecular material/graphene nanocomposite material process
In, redox graphene stripping and the shortcomings that poor dispersion.
(4) reducing agent and the insufficient disadvantage of graphite oxide alkene reaction, are improved in being kneaded the present invention overcomes normal melt
Chemical reaction effect between the two, redox graphene in high molecular material/graphene nanocomposite material of preparation
C/O than high.
(5) dielectric properties and mechanical property of high molecular material/graphene nanocomposite material prepared by the present invention are equal
It is higher than the relevant nanometer composite material prepared by normal melt mixing extrusion method.
Description of the drawings
Fig. 1 is the structural schematic diagram of water auxiliary molten mixing extrusion equipment used herein.In figure, A is extruder, B
It is the different section of extruder for water filling device, I-VII, 1 is feeding hopper, and 2 be liquid storage cylinder, and 3 be metering pump, and 4 be nozzle, and 5 be water ring
Formula vacuum pump, 6 be exhaust outlet.
Fig. 2 is the RGO powder extracted from thermoplastic polyurethane (TPU)/RGO nanocomposites prepared by the present invention
The thermogravimetric curve of GO powder last and of the present invention.In figure, curve 0 corresponds to GO powder, and curve 1 corresponds to comparative example 1, curve
2 corresponding embodiments 1.
Fig. 3 is adopted by the RGO powder and the present invention extracted from the TPU/RGO nanocomposites prepared by the present invention
X-ray photoelectron spectroscopy (XPS) spectrogram of GO powder.In figure, curve 0 corresponds to GO powder, and curve 1 corresponds to comparative example 1, bent
2 corresponding embodiment 1 of line.
Fig. 4 and Fig. 5 is respectively the transmission electron microscope of the TPU/RGO nanocomposites prepared by embodiment 1 and comparative example 1
(TEM) photo.
Fig. 6 is that the X-ray of the TPU/RGO nanocomposites and GO powder of the present invention prepared by the present invention is spread out
Penetrate (XRD) curve.In figure, curve 0 corresponds to GO powder, and curve 1 corresponds to comparative example 1,2 corresponding embodiment 1 of curve.
Fig. 7 is the dielectric constant of the TPU/RGO nanocomposites prepared by the present invention with the change curve of frequency.Figure
In, curve 0 corresponds to comparative example 1,1 corresponding embodiment 1 of curve.
Fig. 8 is adopted by the RGO powder and the present invention extracted from the TPU/RGO nanocomposites prepared by the present invention
Fourier transform infrared spectroscopy (FTIR) spectrogram of GO powder.In figure, curve 0 corresponds to GO powder, 1 corresponding embodiment of curve
2,2 corresponding embodiment 1 of curve.
Specific implementation mode
With reference to embodiment, the present invention will be further described in detail.
Embodiment 1
The water auxiliary molten mixing extrusion equipment that the present invention uses includes an extruder, a set of water filling device, Yi Taishui
Ring vacuum pumps.Along the flow direction of material, extruder barrel is equipped with spout, water filling port and exhaust outlet.Spout is for premix
The charging of high molecular material and graphene oxide powder mixture, water filling port are used for the injection of chemical reducing agent aqueous solution, exhaust
Mouth is used for the discharge of water vapour.Water filling port is equipped with nozzle, and nozzle connects water filling device, and water filling device includes liquid storage cylinder and metering
Pump.Exhaust outlet connects water-ring vacuum pump.
Vitamin C (VC) is added in deionized water, is stirred at room temperature to VC and is completely dissolved, obtain VC aqueous solutions
(0.39g/ml), is placed in liquid storage cylinder；Thermoplastic polyurethane (TPU) pellet and GO powder in mass ratio 100:After 1.9 premixs
It is added in extruder from spout (as shown in Figure 1, from I section) and carries out melting mixing；Machine water filling section (extruder Section IV to be extruded
Section) VC aqueous solutions when reaching 2MPa or more, inject melt by interior melt pressure by metering pump with certain flow rate (1.45L/h)
In.The mixing effect of screw rod makes the VC aqueous solutions of injection enter between adjacent graphene oxide layer, promotes GO in the melt
Stripping and dispersion and in-situ chemical reduction and thermal reduction in situ；Water forms vapor by true in exhaust section (Section VII section) vaporization
Sky pump is taken away from exhaust outlet；The TPU/RGO that GO is made and is preferably removed and disperses and highly restore is squeezed out in head exit
Nanocomposite.Extruder screw rotating speed is 80r/min, and barrel temperature is 160~210 DEG C.
Embodiment 2
The present embodiment uses the water auxiliary molten mixing extrusion equipment of embodiment 1, but feed way is different from embodiment 1.
Spout is used for the charging of high molecular material, and water filling port is used for the injection of the graphene oxide dispersion containing chemical reducing agent.
The stripping of GO powder ultrasonics is dispersed in water, GO dispersion liquids (10mg/ml) are obtained；Then by VC with 10 times of GO's
Quality is added in GO dispersion liquids and stirs to VC and is completely dissolved, and the GO dispersion liquids containing VC are made, are placed in liquid storage cylinder.In the dispersion
In liquid, water promotes the stripping and dispersion of GO as dispersant, increases the contact area of VC and GO.Extruder is added in TPU pellets
Middle carry out plastifying fusion；When pressure reaches 2MPa or more in melt in machine water filling section to be extruded, by metering pump by the GO containing VC
Dispersion liquid is injected with certain flow rate (1.45L/h) in TPU melts.In the mixing of the GO dispersion liquids and TPU melts containing VC of injection
In the process, GO is removed with dispersion liquid, is dispersed in TPU melts well, and in-situ chemical reduction and thermal reduction in situ occurs；Water
It vaporizes to form vapor and taken away from exhaust outlet by vacuum pump in exhaust section；Head exit squeeze out be made GO by preferable stripping and
The TPU/RGO nanocomposites of dispersion and height reduction.The mass ratio of wherein TPU and GO is 100:0.48.Extruder spiral shell
Bar rotating speed is 80r/min, and barrel temperature is 160~210 DEG C.
Embodiment 3
The present embodiment uses the water auxiliary molten mixing extrusion equipment of embodiment 1.
VC is added in deionized water, is stirred at room temperature to VC and is completely dissolved, obtain VC aqueous solutions (0.20g/ml), set
In liquid storage cylinder；TPU pellets and GO powder in mass ratio 100:It is added in extruder after 0.95 premix and carries out melting mixing；It waits for
When melt pressure reaches 2MPa or more in extruder water filling section, by metering pump by VC aqueous solutions with certain flow rate (1.45L/h)
It injects in melt.In the VC aqueous solutions of injection and the mixing process of the TPU melts containing GO, VC aqueous solutions are in extruder screw
Mixing effect it is lower enter between adjacent graphene oxide layer, promote graphene oxide stripping in the melt and dispersion and
In-situ chemical restores and thermal reduction in situ；Water vaporizes to form vapor and taken away from exhaust outlet by vacuum pump in exhaust section；In head
Exit, which squeezes out, is made the TPU/RGO nanocomposites that GO is preferably removed and disperseed and highly restore.Extruder screw
Rotating speed is 80r/min, and barrel temperature is 160~210 DEG C.
Embodiment 4
The present embodiment uses the water auxiliary molten mixing extrusion equipment of embodiment 1.
VC is added in deionized water, is stirred at room temperature to VC and is completely dissolved, obtain VC aqueous solutions (0.59g/ml), set
In liquid storage cylinder；TPU pellets and GO powder in mass ratio 100:It is added in extruder after 2.85 premixs and carries out melting mixing；It waits for
When melt pressure reaches 2MPa or more in extruder water filling section, by metering pump by VC aqueous solutions with certain flow rate (1.45L/h)
It injects in melt.In the VC aqueous solutions of injection and the mixing process of the TPU melts containing GO, VC aqueous solutions are in extruder screw
Mixing effect it is lower enter between adjacent graphene oxide layer, promote graphene oxide stripping in the melt and dispersion and
In-situ chemical restores and thermal reduction in situ；Water vaporizes to form vapor and taken away from exhaust outlet by vacuum pump in exhaust section；In head
Exit, which squeezes out, is made the TPU/RGO nanocomposites that GO is preferably removed and disperseed and highly restore.Extruder screw
Rotating speed is 80r/min, and barrel temperature is 160~210 DEG C.
Comparative example 1
This comparative example uses the extruder of embodiment 1.
In this comparative example, TPU pellets, GO powder and VC in mass ratio 100:1.9:19 premix after be added extruder in into
Row melting mixing squeezes out, to prepare TPU/RGO nanocomposites.Extruder screw rotating speed is 80r/min, and barrel temperature is
160~210 DEG C.
Effect analysis
Fig. 2 is adopted by the RGO powder and the present invention extracted from the TPU/RGO nanocomposites prepared by the present invention
The thermogravimetric curve of GO powder.This is to use thermogravimetric analyzer, in a nitrogen atmosphere, with the heating rate of 10 DEG C/min from room
Temperature is warming up to during 600 DEG C, tests change curve of the gained powder residual mass score with test temperature.GO powder is 150
Mass loss between~300 DEG C is mainly due to the decomposition of oxygen-containing group on GO lamellas.Compared with comparative example 1, embodiment 1 pair
Mass loss of the RGO powder answered between 150~300 DEG C is relatively low, this show the oxygen-containing group of the RGO sheet surfaces remnants compared with
Few, i.e., the reducing degree of GO is higher in the TPU/RGO nanocomposites prepared by embodiment 1.Fig. 3 is prepared by the present invention
TPU/RGO nanocomposites in the XPS spectrum figure of RGO powder and GO powder of the present invention that extracts.As it can be seen that GO
The C/O of powder is relatively low, this shows GO sheet surfaces, and there are a large amount of oxygen-containing groups；Compared with comparative example 1, embodiment 1 pair
For the C/O for the RGO powder answered than high, this shows that the oxygen-containing group of its sheet surfaces remnants is less, demonstrates above-mentioned thermogravimetric test
The phenomenon that reflected.
Fig. 4 and Fig. 5 is respectively the TPU/RGO nanocomposite TEM photos prepared by embodiment 1 and comparative example 1.It can
See, the stripping of RGO and dispersion ratio comparative example 1 is good in 1 gained TPU/RGO nanocomposites of embodiment.Fig. 6 is by the present invention
The XRD curves of prepared TPU/RGO nanocomposites and GO powder of the present invention.At 2 θ=10.5 ° and 25.4 °
Diffraction maximum be respectively GO and RGO diffraction maximum.Compared with comparative example 1, the XRD curves corresponding to embodiment 1 are in 2 θ=10.5 °
The intensity of the diffraction maximum at place is smaller, this show the reducing degree of GO in the TPU/RGO nanocomposites prepared by embodiment 1 compared with
Height, this is consistent with thermogravimetric test (Fig. 2) and XPS test (Fig. 3) acquired results.Although the nano combined material prepared by embodiment 1
The reducing degree of GO is higher in material, but diffraction peak intensity of the XRD curves of the nanocomposite at 25.4 ° and comparative example 1
It is almost the same, which imply RGO more in the nanocomposite prepared by embodiment 1 to be freely distributed with form of single sheet
In TPU matrixes.It can be seen that the stripping of RGO in 1 gained nanocomposite of embodiment and well dispersed, this and TEM are surveyed
Test result (Figure 4 and 5) is consistent.
1 comparative example 1 of table is compared with the performance of the TPU/RGO nanocomposites prepared by embodiment 1
Table 1 is comparative example 1 compared with the performance of the PVDF/RGO nanocomposites prepared by embodiment 1.Fig. 7 is this hair
The dielectric constant of bright prepared TPU/RGO nanocomposites with frequency change curve.As it can be seen that 1 gained nanometer of embodiment
The dielectric constant of composite material is higher, this is attributable to the preferable stripping and dispersion of GO and height in the nanocomposite and goes back
It is former.The tensile strength of 1 gained nanocomposite of embodiment is obviously higher than comparative example 1, this is attributed to the nanocomposite
The stripping of middle RGO and well dispersed.
In summary by prepared by embodiment 1 and comparative example 1 TPU/RGO nanocomposites and from the nano combined material
The RGO powder extracted in material is compared visible：With normal melt mixing extrusion (i.e. mixing side used by comparative example 1
Method) it compares, water auxiliary mixing extrusion has been obviously promoted the stripping, dispersion and in-situ reducing of GO, and then improves nanocomposite
Mechanics and dielectric properties.
Fig. 8 is adopted by the RGO powder and the present invention extracted from the TPU/RGO nanocomposites prepared by the present invention
The FTIR spectrograms of GO powder.The FTIR spectrograms of GO powder are in 3350cm-1The peak at place is the peak of O-H groups.With 2 phase of embodiment
Than O-H groups peak is obviously weaker in the FTIR spectrograms corresponding to embodiment 1, this shows in 1 gained nanocomposite of embodiment
The reducing degree of GO is higher.As it can be seen that feed way used by embodiment 1 is more conducive to the in-situ reducing of GO.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, it is other it is any without departing from the spirit and principles of the present invention made by changes, modifications, substitutions, combinations, simplifications,
Equivalent substitute mode is should be, is included within the scope of the present invention.
Claims (10)
1. the method for preparing high molecular material/graphene nanocomposite material using continuous mixing in-situ reducing, which is characterized in that
Include the following steps：
(1) chemical reducing agent is dissolved in deionized water, obtains certain density chemical reducing agent aqueous solution, is placed in liquid storage cylinder
In；
(2) extruder for starting water auxiliary molten mixing extrusion equipment, by the high molecular material and graphene oxide powder of premix
Mixture is added in extruder and carries out mixing extrusion；
(3) adjustment squeezes out machined parameters, including feeding capacity, screw speed and machine barrel temperature of each section, make in extruder water filling section
High molecular material melt pressure is increased to and can keep the water of injection when being liquid at high temperature, by metering pump by step (1)
Gained chemical reducing agent aqueous solution is from water filling port in the melt in certain flow rate injection extruder；
(4) between the reducing agent aqueous solution injected enters adjacent graphene oxide layer under the mixing effect of extruder screw,
Promote stripping and dispersion and in-situ chemical reduction and in situ thermal reduction of the graphene oxide in high molecular material melt；
(5) water forms vapor in the generation vaporization of extruder exhaust section and is taken away from exhaust outlet by vacuum pump, in head exit
It squeezes out and high molecular material/graphene nano composite wood that graphene oxide is preferably removed and disperses and highly restore is made
Material.
2. described in accordance with the claim 1 prepare high molecular material/graphene nano composite wood using continuous mixing in-situ reducing
The method of material, it is characterised in that：High molecular material is the thermoplastic macromolecule material of not facile hydrolysis, preferably poly-methyl methacrylate
Ester, thermoplastic polyurethane elastomer, polyvinylidene fluoride, polypropylene or polystyrene.
3. described in accordance with the claim 1 prepare high molecular material/graphene nano composite wood using continuous mixing in-situ reducing
The method of material, it is characterised in that：Chemical reducing agent is water-soluble, nontoxic chemical reducing agent, preferably phenol, bisulfite
Sodium, xylitol, vitamin C or hydroiodic acid.
4. described in accordance with the claim 1 prepare high molecular material/graphene nano composite wood using continuous mixing in-situ reducing
The method of material, it is characterised in that：Water auxiliary molten mixing extrusion equipment includes a single screw extrusion machine or double screw extruder,
Extruder screw rotating speed is 20~500r/min, and barrel temperature is 100~300 DEG C；Also include a metering pump, metering pump control
The injection rate of reducing agent aqueous solution.
5. described in accordance with the claim 1 prepare high molecular material/graphene nano composite wood using continuous mixing in-situ reducing
The method of material, it is characterised in that：A concentration of 0.01~1g/ml of chemical reducing agent aqueous solution；High molecular material and graphite oxide
The mass ratio of alkene powder is 100:0.04~100:20；Chemical reducing agent aqueous solution injection rate and height in step (2) in step (3)
The mass ratio of molecular material addition is 1:20~1:1.
6. described in accordance with the claim 1 prepare high molecular material/graphene nano composite wood using continuous mixing in-situ reducing
The method of material, it is characterised in that：Melt pressure when injecting chemical reducing agent aqueous solution in extruder water filling section is higher than after stablizing
2MPa。
7. described in accordance with the claim 1 prepare high molecular material/graphene nano composite wood using continuous mixing in-situ reducing
The method of material, it is characterised in that：In the preparation process of the nanocomposite, chemical reducing agent aqueous solution is injected into extruder
After in interior melt, since the oxygen-containing group on graphene oxide layer surface has strong hydrophily, therefore hydrone is easy in spiral shell
The mixing effect of bar is lower to be entered between adjacent graphene oxide layer, to increase interlayer spacing between the graphene oxide layers；
The spacing of graphene oxide layer, which increases, promotes high molecular strand intercalation to enter between graphene oxide layer, to promote oxygen
The stripping and dispersion of graphite alkene.
8. described in accordance with the claim 1 prepare high molecular material/graphene nano composite wood using continuous mixing in-situ reducing
The method of material, it is characterised in that：Water promotes the stripping and dispersion of graphene oxide, and more oxygen-containing groups is made to be exposed to macromolecule
In material melt, to promote the thermal reduction in situ of graphene oxide.
9. described in accordance with the claim 1 prepare high molecular material/graphene nano composite wood using continuous mixing in-situ reducing
The method of material, it is characterised in that：Water increases the contact area of chemical reducing agent and graphene oxide, to promote graphene oxide
In-situ chemical reduction.
10. preparing high molecular material/graphite using continuous mixing in-situ reducing according to described in any one of claim 1 to 9
The application of the method for alkene nanocomposite, it is characterised in that：It is used to prepare dielectric material, electromagnetic shielding material, Heat Conduction Material
And antistatic material.
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Citations (5)
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|---|---|---|---|---|
| CN101864098A (en) * | 2010-06-03 | 2010-10-20 | 四川大学 | Preparation method of polymer/graphene composite material through in situ reduction |
| CN102161785A (en) * | 2011-03-10 | 2011-08-24 | 四川大学 | Preparation method of graphene/polymer nano composite material |
| CN103183847A (en) * | 2013-04-12 | 2013-07-03 | 北京化工大学 | Graphene elastomer nano composite material with high dielectric constant and low dielectric loss and preparation method thereof |
| WO2014060684A1 (en) * | 2012-10-19 | 2014-04-24 | Arkema France | Method for producing a graphene-based thermoplastic composite material |
| CN104441544A (en) * | 2014-12-09 | 2015-03-25 | 宁波大学 | Extrusion molding method of graphene modified nylon 66 high-strength composite thin products |
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2018
- 2018-02-11 CN CN201810141960.8A patent/CN108454057B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101864098A (en) * | 2010-06-03 | 2010-10-20 | 四川大学 | Preparation method of polymer/graphene composite material through in situ reduction |
| CN102161785A (en) * | 2011-03-10 | 2011-08-24 | 四川大学 | Preparation method of graphene/polymer nano composite material |
| WO2014060684A1 (en) * | 2012-10-19 | 2014-04-24 | Arkema France | Method for producing a graphene-based thermoplastic composite material |
| CN103183847A (en) * | 2013-04-12 | 2013-07-03 | 北京化工大学 | Graphene elastomer nano composite material with high dielectric constant and low dielectric loss and preparation method thereof |
| CN104441544A (en) * | 2014-12-09 | 2015-03-25 | 宁波大学 | Extrusion molding method of graphene modified nylon 66 high-strength composite thin products |
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