CN108586737A - A kind of conducting polymer/graphene complex and preparation method thereof - Google Patents
A kind of conducting polymer/graphene complex and preparation method thereof Download PDFInfo
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- CN108586737A CN108586737A CN201810224361.2A CN201810224361A CN108586737A CN 108586737 A CN108586737 A CN 108586737A CN 201810224361 A CN201810224361 A CN 201810224361A CN 108586737 A CN108586737 A CN 108586737A
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/02—Polyamines
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- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
- C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
- C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
- C08G61/126—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one sulfur atom in the ring
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/042—Graphene or derivatives, e.g. graphene oxides
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- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
- C08G2261/11—Homopolymers
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- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
- C08G2261/324—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed
- C08G2261/3247—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed containing combinations of different heteroatoms other than nitrogen and oxygen or nitrogen and sulfur
Abstract
A kind of conducting polymer/graphene complex of present invention offer and preparation method thereof, is related to technical field of composite materials.Preparation method is：Ionic liquid and graphene are mixed, ball milling obtains the colloid of black.Wherein, the anion structure in ionic liquid is hydrophobic anion.The monomer of conducting polymer is added in obtained colloid, oxide is added after first grinding, then regrinds 4~12h, obtain mixture.Mixture obtains conducting polymer/graphene complex through being filtered, washed, drying.Using hydrophobic ionic liquid as the lytic agent of the dispersant of graphene and conducting polymer, obtained compound productivity is high, high-quality.It is pollution-free using mechanical grinding method, solvent is not used, it is simple for process, it can continuously produce the composite material of conducting polymer and graphene in enormous quantities, ionic liquid is recyclable, and production cost is low, has a extensive future.
Description
Technical field
The present invention relates to technical field of composite materials, and more particularly to a kind of conducting polymer/graphene complex and its
Preparation method.
Background technology
With polyaniline, polypyrrole, polythiophene and its derivative, which are the conducting polymer of representative, has that density is light, molecular structure
The advantages that good with electric conductivity can be designed, in lithium ion battery, ultracapacitor, electromagnetic interference shield, microwave and radar-wave absorbing
Material, nonlinear optics, luminescent device, sensor and indicator, catalyst, electronic field emission, field-effect transistor, Schottky
Diode, the storage of erasable optical information, digital storage equipment, anisotropic membrane, diaphragm, electrochromic device, electromechanical actuator resist
Electrostatic, anticorrosive coating, fuel cell and solar cell etc. have a wide range of applications.But there is also solid for conducting polymer
There is disadvantage, such as the low conductivity under dedoping state；Condition of palsticity difference influences its machinability；Its rigid molecule chain leads to mechanics
Poor performance, molecule are easily broken so that its performance degradation；Chemical stability is not satisfactory, application it is upper also and inorganic material
There are certain gaps etc., to seriously affect the large-scale application of conducting polymer.
Graphene has bigger serface, and unique mechanics, electricity, magnetics, optically and thermally performance can be used as reinforcing agent
Effectively improve conductive characteristic, mechanical characteristic, chemical stability and the thermal characteristics etc. of conducting polymer matrix with additive.Especially
With the maturation of graphene technique, graphene cost drastically reduces, be graphene modified conductive polymer with large-scale application
It provides the foundation.However, the intrinsic hydrophobicity of graphene is to prepare the major obstacle of conducting polymer uniform fold graphene.For
Overcome the problems, such as this, adds surfactant, stabilizer and the graphene of chemical modification in the synthesis process and have proved to be
Successfully prepare the effective ways of conducting polymer coated graphite alkene.
Inventor the study found that above-mentioned method of modifying not only technique is more complex, but also be easy in modifying process to make graphite
The structure of alkene is destroyed, and the attenuating of the performances such as graphene electricity, heat, mechanics is caused.Or understanding in graphite in modifying process
Alkene surface-adsorbed macromolecule hinders the direct combination of graphene and conducting polymer, reduces the performance to conducting polymer
Improve.In addition, graphene and conducting polymer is compound generally by chemical polymerization or electropolymerization method in aqueous solution or organic
It is prepared in solvent, easily causes environmental pollution, low yield is extensive to prepare difficulty.
Invention content
The purpose of the present invention is to provide a kind of preparation method of conducting polymer/graphene complex, this preparation methods
Simply, easily operated, yield is high, can realize extensive preparation.
Another object of the present invention is to provide a kind of conducting polymer/graphene complexes, with green solvent ionic liquid
For body as dispersant, conducting polymer is uniformly coated on graphene surface, and product quality is more excellent.
The present invention solves its technical problem using following technical scheme to realize.
The present invention proposes a kind of preparation method of conducting polymer/graphene complex, includes the following steps：
S1, ionic liquid and graphene are mixed, and ball milling obtains the colloid of black；
The monomer of conducting polymer is added in the colloid by S2, and after first grinding, oxide is added to the glue
Then body regrinds 4~12h, obtains mixture；
The mixture is filtered, washed, dries by S3, obtains conducting polymer/graphene complex.
The present invention proposes a kind of conducting polymer/graphene complex, is made according to above-mentioned preparation method.
The advantageous effect of conducting polymer/graphene complex of the embodiment of the present invention and preparation method thereof is：
Hydrophobic ionic liquid is in the preparation process of compound, first, making point of graphene with green solvent ionic liquid
Powder ensure that the fine dispersion of graphene, while ionic liquid will not destroy the molecular structure of graphene, also not in graphene
Surface introduces the macromolecular or polymer of insulation so that electric conductivity of compound etc. is more excellent.Second is that ionic liquid can be with
It can such as aniline salt and its derivative, the lytic agent of pyrroles and its derivative, thiophene and derivatives as polymer monomer
Dispersed polymeres monomer well obtains the compound of polymer uniform coated graphite alkene.Third, hydrophobic ionic liquid can be with
Recycling reduces production cost, and being dissolved in unemployed polymer monomer, oligomer in ionic liquid can be sharp again
With improving the utilization rate of polymer monomer.
The method being combined using the multi-function action and mechanical ball mill of ionic liquid is not used any solvent, avoided
Environmental pollution.The method and process of mechanical ball mill is simple, and parameters are easily controllable, can continuously produce conducting polymer in enormous quantities
Object/graphene complex.The yield for the compound that this method obtains is significantly higher than common chemistry of aqueous solution polymerization, better than
Electrochemical polymer method.
Description of the drawings
In order to illustrate the technical solution of the embodiments of the present invention more clearly, below will be to needed in the embodiment attached
Figure is briefly described, it should be understood that the following drawings illustrates only certain embodiments of the present invention, therefore is not construed as pair
The restriction of range for those of ordinary skill in the art without creative efforts, can also be according to this
A little attached drawings obtain other relevant attached drawings.
Fig. 1 is to be formed by colloid after graphene and ionic liquid ball milling in step of embodiment of the present invention S1；
Fig. 2 is the schematic diagram of step S1 intermediate ion liquid dispersed graphite alkene of the embodiment of the present invention；
Fig. 3 is the scanning electron microscope (SEM) photograph of polyaniline/graphene complex made from the embodiment of the present invention 1；
Fig. 4 is the transmission electron microscope picture of polyaniline/graphene complex made from the embodiment of the present invention 1；
Fig. 5 is the scanning electron microscope (SEM) photograph of poly- 3,4- ethylenedioxy thiophenes/graphene complex made from the embodiment of the present invention 2；
Fig. 6 is the transmission electron microscope picture of poly- 3,4- ethylenedioxy thiophenes/graphene complex made from the embodiment of the present invention 2.
Specific implementation mode
It in order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below will be in the embodiment of the present invention
Technical solution be clearly and completely described.The person that is not specified actual conditions in embodiment, builds according to normal condition or manufacturer
The condition of view carries out.Reagents or instruments used without specified manufacturer is the conventional production that can be obtained by commercially available purchase
Product.
Conducting polymer/graphene complex of the embodiment of the present invention and preparation method thereof is specifically described below.
The embodiment of the present invention provides a kind of preparation method of conducting polymer/graphene complex, includes the following steps：
S1, ionic liquid and graphene are mixed, and ball milling obtains the colloid of black, wherein the anion in ionic liquid
Structure is hydrophobic anion.
Ionic liquid be primarily referred to as cation or anion constitute in room temperature or be bordering on the salt being in a liquid state at room temperature.From
Sub- liquid has that low volatility, wider electrochemical window, chemical stability be good, higher conductivity, be acknowledged as after
The third green reaction medium after supercritical fluid and aqueous two-phase.Ionic liquid containing hydrophobic anion being capable of conduct
The dispersant of graphene and the lytic agent of polymer monomer, will not destroy the structure of graphene, will not draw on the surface of graphene
The macromolecular or polymer for entering insulation ensure that the good compound of graphene and conducting polymer, ensure the quality of product.
Further, in a preferred embodiment of the present invention, the structural formula of the cation in ionic liquid is as follows
Any one：
Wherein, B1It arrives
B10It is independent to be selected from following group：Halogen, protium, by C1-C25In alkynyl, benzyl, alkyl and phenyl that alkyl is constituted
One kind.Further, B1To B10May include the hetero atoms such as oxygen, nitrogen, silicon and sulphur, and alternative includes chlorine, bromine, fluorine, iodine
Equal elements.
Further, in a preferred embodiment of the present invention, the anion structure formula of ionic liquid can be hydrophobicity the moon from
Sub- BF4 —、PF6 —、ClO4 —、(CF3SO2)2N—、CH3CO2 —、CH3OSO3 —、CF3SO3 —、HCF2CF2SO3 —、CF3CHFCF2SO3 —、
HCClFCF2SO3 —、(CF3SO2)2N—、(CF3CF2SO2)2N—、(CF3SO2)3C—、CF3CO2 —、CF3OCFHCF2SO3 —、
CF3CF2OCFHCF2SO3 —、CF3CFHOCF2CF2SO3 —Deng.
Further, in a preferred embodiment of the present invention, the quality of graphene is the 0.1%-4% of ionic liquid, into one
The quality on step ground, graphene is 2%.
Further, in a preferred embodiment of the present invention, in the step, the agate of at least two diameters is used in mechanical milling process
Nao mill balls.Preferably, mechanical milling process is：The agate grinding of 20 diameter 1cm and 15 diameter 0.5cm is added in grinding pot
Ball.Agate grinding pot is obtained into the colloid of black after 1 hour in planetary ball mill with 400 revs/min of ball millings, as shown in Figure 1.
In above-mentioned process of lapping, the positive charge layer of ionic liquid can be adsorbed on graphene surface, pass through weak Van der Waals force
Effect can effectively shield strong π-pi accumulation effect between graphene layer.Therefore, graphene can be effectively dispersed in above-mentioned ionic liquid
In body.The schematic diagram of ionic liquid dispersed graphite alkene is as shown in Figure 2.
The monomer of conducting polymer is added in the colloid that step S1 is obtained by S2, and after first grinding, oxide is added extremely
Then the colloid regrinds 4~12h, obtains mixture.
It is understood that different polymer monomers is added in this step, then can be obtained different conducting polymers/
Graphene complex.Polymer monomer can be aniline salt, anil salt, pyrroles, azole derivatives, thiophene, thiophene-based
Derivative etc..
For example, anilinechloride, aniline sulfate, aniline camsilate, phenylglycine salt, oxalic anilide salt etc. is added
Aniline salt obtains polyaniline/graphene complex.Or o-chloraniline, 4- chloroanilines, o-aminoanisole, adjacent ethoxy is added
Anils and hydrochloric acid, sulfuric acid, camphorsulfonic acid, acetic acid, the grass such as base aniline, adjacent butylaniline, ortho-aminotoluene, ortho-nitraniline
The anil salt that the acid such as acid is formed, obtains polyaniline derivative/graphene conductive polymer.Pyrroles or 3- alkylated pyrazoles is added
It coughs up, the azole derivatives such as 3- carboxy pyrroles obtain the compound of polypyrrole or Polypyrrole derivatives and graphene.3- methyl is added
Thiophene, 3,4- ethylenedioxy thiophenes, 3- (4- fluorobenzene) thiophene, 2,5- dicarboxylic acids -3,4- ethylenedioxy thiophenes, 2,3,5- trimethyls
Thiophene, tri- bromothiophenes of 2,3,5-, 2,3- dibromo thiophenes, the bromo- 3 methyl thiophenes of 2-, the bromo- 3 methyl thiophenes of 2-, 2- methoxyl group thiophenes
The thiophene derivants such as pheno, 3,4- dimethoxy-thiophenes, obtain the compound of polythiophene-based derivatives and graphene.
Further, in a preferred embodiment of the present invention, the quality of the monomer of conducting polymer is the 2%- of ionic liquid
10%.It is further preferable that the mass fraction of monomer is 4%-6%.Under the ratio, ionic liquid can preferably dissolve list
Body provides suitable condition, yield higher for monomer polymerization.
After the monomer of conducting polymer is added, 0.5-1h is ground, oxide is then added.Preferably, oxide is selected from
(NH4)2S2O8、K2Cr2O7、FeCl3、FeCl4、CuCl2、KIO3In it is one or more.It is further preferable that oxide is selected from
(NH4)2S2O8, (NH4)2S2O8Not metal ion, oxidability is strong, has more preferably with its polymer obtained as oxidant
Electric conductivity.
Further, in a preferred embodiment of the present invention, in the step, the molal weight ratio of oxide and polymer monomer
It is 0.5~5:1.It is highly preferred that (NH4)2S2O8For oxide, molal weight ratio is 0.8~1:When 1, conducting polymer and graphite
The combination of alkene is more preferably.
Further, in a preferred embodiment of the present invention, in the step, in process of lapping, point 2~4 addition oxidations
Object, per 8~10min of minor tick.It is highly preferred that oxide is added three times, per minor tick 10min, obtained conducting polymer
Electric conductivity is more preferable.
In polymer process, the oligomer absorption of conducting polymer is on the surface of graphene.With the progress of polymerization, conduction is poly-
It closes object to adsorb on the surface of graphene by π-π interactions, to the compound that forming properties are stable, yield is high.In compound
Conducting polymer relative to addition monomer yield up to 88% or more, far above conducting polymer 40% in common aqueous solution
Yield.
The obtained mixtures of step S2 are filtered, washed, dry, obtain polyaniline/graphene complex or polyaniline by S3
Derivative/graphene complex.
Preferably, after mixture filtering, organic solvent (carbon tetrachloride, ether, dichloromethane, petroleum ether, trichlorine are used respectively
Methane, toluene, n-hexane, normal heptane, butyl acetate, methyl tertiary butyl ether(MTBE), isopropyl ether, isobutanol etc.) and water washing, with removal
Oligomer and unreacted reactant, the product after being washed out, dry 40~52h under the conditions of 50~65 DEG C.
After the compound of conducting polymer and graphene is made, the organic layer and water layer of above-mentioned washing are extracted
Separation, and after distilling out organic solvent, be dried in vacuo for 24 hours under the conditions of 60 DEG C, gained ionic liquid is reusable, uses again
In dispersed graphite alkene.After ionic liquid is repeated 4 times application, the conducting polymer yield of gained only declines 4-16%.
The embodiment of the present invention also provides a kind of conducting polymer/graphene complex, according to above-mentioned preparation method system
.Obtained compound quality is uniform, performance is stablized.
The feature and performance of the present invention are described in further detail with reference to embodiments.
Embodiment 1
A kind of polyaniline/graphene complex provided in this embodiment is made according to following steps：
(1) graphene that 10g ionic liquids and its mass fraction are 2% is put into agate grinding pot.In grinding pot
The agate mill ball of 20 1cm diameters and 15 0.5cm diameters is added.By agate grinding pot in planetary ball mill with 400 turns/
The colloid of black is obtained after minute ball milling 1h.Wherein, ionic liquid is 1- butyl -3- methylimidazole hexafluorophosphates, structural formula
For
(2) 0.5g anilinechlorides are added in above-mentioned colloid and continue to grind 0.5h.Then ammonium persulfate is added in three times
0.24g is added every time per minor tick 10min as oxide.Grinding 6h is then proceeded to, black mixture gradually becomes blackish green
Mixture of colours object.
(3) mixture obtained by step (2) is filtered, is used in combination ether and deionized water to wash, to remove oligomer
And unreacted reactant, it is then 48 hours dry under the conditions of 60 DEG C.Obtain polyaniline/graphene complex.
The yield of polyaniline is 88.9% in polyaniline/graphene complex.The scanning electron microscope (SEM) photograph of compound such as Fig. 3 institutes
Show, perspective electron microscope is as shown in Figure 4.By Fig. 3 and 4 it is found that polyaniline is uniformly coated on graphene surface.
(4) cleaning solution in collection step (3), that is, the organic layer and water layer obtained after washing, after carrying out extraction and separation, then
The ionic liquid recycled by vacuum distillation.Using the ionic liquid of recycling as raw material, using the side in step (1)-(3)
Method obtains polyaniline/graphene complex, and after testing, the yield of polyaniline is 87.2% in the compound.
Embodiment 2
(1) graphene that 10g ionic liquids and its mass fraction are 2% is put into agate grinding pot.In grinding pot
The agate mill ball of 20 1cm diameters and 15 0.5cm diameters is added.By agate grinding pot in planetary ball mill with 400 turns/
The colloid of black is obtained after minute ball milling 1h.Wherein, ionic liquid is 1- butyl -3- methyl imidazolium tetrafluoroborates, structural formula
For
(2) the distilled 3,4- ethylenedioxy thiophenes of 1g are added in above-mentioned colloid and continue to grind 0.5h.Then in three times
Ferric trichloride is added, 0.56g is added every time per minor tick 10min as oxide.Grinding 8h is then proceeded to, mixture is obtained.
(3) mixture obtained by step (2) is filtered, is used in combination ether and deionized water to wash, to remove oligomer
And unreacted reactant, it is then 48 hours dry under the conditions of 60 DEG C.Obtain poly- 3,4- ethylenedioxy thiophenes/graphene complex.
The yield of polyaniline is 89.6% in poly- 3,4- ethylenedioxy thiophenes/graphene complex.The scanning electricity of compound
Mirror figure is as shown in figure 5, perspective electron microscope is as shown in Figure 6.By Figures 5 and 6 it is found that poly- 3,4-ethylene dioxythiophene is uniformly coated on
Graphene surface.
Comparative example 1
A kind of polyaniline/graphene complex that this comparative example provides is made according to following steps：
(1) 0.2g graphenes are added in the polyvinylpyrrolidone aqueous solution of certain solubility, ultrasonic 30min, it will
Obtained mixed liquor ice is put into mechanical agitation 10min in ice-water bath to 0 DEG C.
The hydrochloric acid solution of 0.5M and 0.5g aniline monomers are added in above-mentioned mixed liquor, one is stirred in ice bath immediately
Between.0.72g ammonium persulfates are taken to be dissolved in distilled water, and ice is to 0 DEG C.It is then added to initiation reaction in above-mentioned mixed liquor.It will
Obtained product is washed with ethyl alcohol and deionized water, then 48 hours dry under the conditions of 60 DEG C.It is multiple to obtain polyaniline/graphene
Close object.The yield of polyaniline is 40.7% in polyaniline/graphene complex.
Embodiments described above is a part of the embodiment of the present invention, instead of all the embodiments.The reality of the present invention
The detailed description for applying example is not intended to limit the range of claimed invention, but is merely representative of the selected implementation of the present invention
Example.Based on the embodiments of the present invention, those of ordinary skill in the art are obtained without creative efforts
Every other embodiment, shall fall within the protection scope of the present invention.
Claims (10)
1. a kind of preparation method of conducting polymer/graphene complex, which is characterized in that include the following steps：
S1, ionic liquid and graphene are mixed, and ball milling obtains the colloid of black, wherein the anion in the ionic liquid
Structure is hydrophobic anion；
The monomer of conducting polymer is added in the colloid by S2, and after first grinding, oxide is added to the colloid, so
4~12h is regrind afterwards, obtains mixture；
The mixture is filtered, washed, dries by S3, obtains conducting polymer/graphene complex.
2. the preparation method of conducting polymer/graphene complex according to claim 1, feature exist
In, in step S1, in the ionic liquid cation structural formula be as follows any one：Wherein, B1To B10It is independent
It is selected from following group：Halogen, protium, by C1-C25One kind in alkynyl, benzyl, alkyl and phenyl that alkyl is constituted.
3. the preparation method of conducting polymer/graphene complex according to claim 2, which is characterized in that described to dredge
Aqueous anion is selected from BF4 —、PF6 —、ClO4 —、(CF3SO2)2N—、CH3CO2 —、CH3OSO3 —、CF3SO3 —、HCF2CF2SO3 —、
CF3CHFCF2SO3 —、HCClFCF2SO3 —、(CF3SO2)2N—、(CF3CF2SO2)2N—、(CF3SO2)3C—、CF3CO2 —、
CF3OCFHCF2SO3 —、CF3CF2OCFHCF2SO3 —、CF3CFHOCF2CF2SO3 —In it is one or more.
4. the preparation method of conducting polymer/graphene complex according to claim 3, which is characterized in that for institute
State the cationic structural formula of ionic liquid, B1To B10One or more groups in, containing a kind of in oxygen, nitrogen, silicon and sulphur
Or a variety of hetero atoms, and contain one or more elements in chlorine, bromine, fluorine, iodine.
5. the preparation method of conducting polymer/graphene complex according to claim 1, which is characterized in that the stone
The quality of black alkene is the 0.1%-4% of the ionic liquid.
6. the preparation method of conducting polymer/graphene complex according to claim 1, which is characterized in that step S2
In, the one kind of the monomer in aniline salt, anil salt, pyrroles, azole derivatives, thiophene, thiophene derivants.
7. the preparation method of conducting polymer/graphene complex according to claim 1, which is characterized in that the oxygen
Compound is selected from (NH4)2S2O8、K2Cr2O7、FeCl3、FeCl4、CuCl2、KIO3In it is one or more.
8. the preparation method of conducting polymer/graphene complex according to claim 1, which is characterized in that the oxygen
The molal weight ratio of compound and the monomer is 0.5-5:1.
9. the preparation method of conducting polymer/graphene complex according to claim 1, which is characterized in that the list
The quality of body is the 2%-10% of the ionic liquid.
10. a kind of conducting polymer/graphene complex, which is characterized in that according to system described in any one of claim 1-9
Preparation Method is made.
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