CN104650498B - A kind of Graphene/polymer composite conductive thin film material and preparation method thereof - Google Patents
A kind of Graphene/polymer composite conductive thin film material and preparation method thereof Download PDFInfo
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- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
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- C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
- C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2327/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08J2327/06—Homopolymers or copolymers of vinyl chloride
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- C08L2203/16—Applications used for films
Abstract
The invention discloses a kind of Graphene/polymer composite conductive thin film material, belong to antistatic macromolecule technical field of composite materials.The composite conductive thin film material includes Graphene and polymeric matrix, and the Graphene constitutes conductive network in composite conductive thin film material.It is first in the aqueous solution containing dispersant that graphene dispersion is uniform, obtain graphene suspension.Then after being added to polymer beads in above-mentioned suspension and be allowed to well mixed, then through fast filtering and the powdered presoma for being dried to obtain above-mentioned composite.Most obtain Graphene/polymer composite conductive thin film material through vulcanizing press hot pressing afterwards.Because the two-dimensional graphene with big radius-thickness ratio can constitute electric transmission network in composite conductive film, therefore the electric conductivity of composite can be significantly increased（Volume resistance drops to 103The Ω orders of magnitude）, the polyvinyl chloride laminated film is applied to antistatic or electromagnetic shielding occasion.
Description
Technical field
The present invention relates to antistatic macromolecule technical field of composite materials, and in particular to a kind of Graphene/polymer is combined
Conductive film material and preparation method thereof.
Background field
With the development of modern electronics industry, information industry and new and high technology, conducting polymer is used as functional high-polymer
New material has caused the great attention of scientists from all over the world and enterpriser, theoretical in recent years rapid with Practical Research progress.Polymer
Referring to polymer and conductive material heterogeneous composite material obtained from by being either physically or chemically combined based conductive composite material more.
With traditional conductive material metal phase ratio, polymer base conductive composite material has lightweight, easy processing, corrosion-resistant and resistance
Rate can be the features such as interior regulation in a big way and widely used.Polyvinyl chloride (PVC), as one of four large-engineering materials, is a kind of
The general-purpose plastics being widely used.By conductive material（Particularly various charcoal system conductive fillers for example carbon black, graphite, CNT and
Graphene etc.）It is a kind of method of low cost manufacture permanence antistatic material to be filled into Corvic, using the method
The conductive polyvinyl chloride of preparation can meet the good electrostatic required by packaging material and anti-static material as electronic component
Dissipation performance.
Develop meet it is antistatic require again keep the excellent mechanical property of matrix polymer polyvinyl chloride be urgently to solve
Problem certainly.
Its excellent mechanical property is kept while the electric conductivity for improving poly chlorine polyvinyl（As shock resistance,
Toughness and elongation etc.）It is the emphasis of conducing composite material research in recent years.Prepare the charcoal system that conducting polymer is used at present
Conductive filler is typically carbon black or graphite, according to the pattern and electrical conduction mechanism of these conducting particles, to reach preferably conductive effect
Really, the addition of conductive agent is typically greater than 10%, adds so many conductive agent to reduce the mechanical property of matrix polymer
Can, the application of final influence conducting polymer.
Therefore, a kind of suitable method for preparing polymer composites is studied, makes the polymer composites prepared
It is particularly important that electric conductivity in the packaging material and anti-static material as electronic component reaches requirement.
The content of the invention
It is difficult to poly- to solve Graphene present in Graphene present in prior art/polymer composites preparation
Problem that is dispersed and constituting effective conductive network in compound, the present invention proposes one kind and can give full play to graphene conductive
Polymer composites of performance advantage and preparation method thereof.
To achieve the above object, the technical scheme is that：
A kind of Graphene/polymer composite conductive thin film material, including Graphene and polymeric matrix, Graphene is compound
Weight percentage in conductive film is 0.5-5%（Preferably 1.5-4%）, the Graphene is in composite conductive thin film material
Constitute conductive network.
The Graphene is prepared by intercalation stripping method or graphite oxidation reducing process, and the size range of Graphene is 10-50 μ
m；The polymeric matrix is one or more in polyvinyl chloride, polystyrene, polyester, polyethylene and polypropylene.
The thickness of the composite conductive thin film is 0.1-2mm.
The volume resistance and sheet resistance minimum 10 of the composite conductive thin film3The Ω orders of magnitude, specific insulation reaches
106The Ω cm orders of magnitude, surface resistivity reaches 106Ω/ orders of magnitude.
The preparation method of above-mentioned Graphene/polymer composite conductive thin film material is：Graphene uniform is dispersed in first
In the aqueous solution containing surfactant, the suspension of Graphene is formed, granulated polymer is then distributed to Graphene
In suspension, sequentially pass through filter and be dried to obtain the composite powder of graphene coated polymer, then by the composite powder through hot pressing
Obtain Graphene/polymer composite conductive thin film material.The method specifically includes following steps：
（1）The preparation of the suspension of Graphene：First by surfactant according to surfactant：The weight of water=0.1-3%
Amount ratio is added in deionized water, obtains the aqueous solution containing surfactant, and Graphene is then added under agitation,
The addition of Graphene is 1-10mg in every milliliter of aqueous solution containing surfactant, and stirring is then sonicated 30-60 after 1 hour
Minute, obtain the suspension of Graphene；
（2）Granulated polymer is added to step under agitation in the desired amount（1）The suspension of gained Graphene
In, ultrasound is quick again after 1 hour to be stirred more than 6 hours, obtains Graphene/polymer suspension；
（3）By step（2）Gained Graphene/polymer suspension carries out vacuum filtration, is then dried under the conditions of 100 DEG C
Afterwards, the composite powder of graphene coated polymer is obtained；Through step（2）Mode carries out suction filtration and drying again after processing, and can keep away
Exempt from Graphene reunion, and realize graphene coated to polymer beads.
（4）By the composite powder of graphene coated polymer using vulcanizing press in 160-200 DEG C of temperature and 2-4MPa
Pressure is pushed 6-10 minutes, is made Graphene/polymer composite conductive thin film.
The surfactant is polyvinylpyrrolidone, polyvinyl alcohol, silane coupler or titanate coupling agent etc..
The granulated polymer is preceding by plastics processing in use, and processing procedure is：A certain amount of graininess is weighed to gather
Compound, is 100 by polymer and plasticizer weight ratio：60 add dioctyl phthalate plasticizer, 80 after stirring
Processed 1 hour under the conditions of DEG C, the polymer for being plastified.
Design principle of the present invention is as follows：
Up-and-coming youngster's Graphene in carbon series fillings is moved due to its excellent electric conductivity, at room temperature high electronics
Shifting rate 2 × 105cm2v-1s-1, radius-thickness ratio very high（Approximately more than 5000）, it is added percentage by weight not in matrix polymer
During foot 3%, can just reach specific insulation and drop to 106Below the Ω cm orders of magnitude, antistatic requirement is met.Graphene is due to adding
Dosage is less, and due to the pattern of Graphene, the mechanical property to matrix polymer is not almost damaged, or even has certain journey
The humidification of degree.Graphene has following remarkable advantage compared with other conductive agents：
（1）Graphene has excellent electric conductivity, and electron mobility is up to 2 × 105cm2v-1s-1, than the load being currently known
Maximum material indium antimonide twice high of stream transport factor or so.Simultaneously Graphene resistance value at room temperature only have copper three/
Two.These performance specification Graphenes are conductive materials most excellent at present.
（2）Graphene has radius-thickness ratio very high（Up to more than 5000）.The two-dimension plane structure of Graphene makes it than zero
Dimension or one-dimensional electric material are more easy to constitute conductive network in the base, therefore can significantly reduce the consumption of conductive agent.
（3）Graphene has very big specific surface area, and theoretical value is up to 2600m2/g.Graphene specific surface so high
Product, can be conducive to improving its interaction with matrix polymer, strengthen interface bonding energy.
（4）Graphene has an excellent mechanical property, preferable Graphene tensile strength is 42N/m, about ordinary steel
100 times, Young's modulus is 1100GPa, fracture strength 125GPa.Appropriate Graphene is added in polymer, Graphene exists
While improving polymer conductivity, can also the effect of haveing a certain upgrade to its mechanical property.
The present invention proposes the complex method of a kind of new Graphene and polymer, i.e., first by graphene dispersion in the aqueous solution
In, the particle of polymer is scattered in above-mentioned solution again then, obtained a homogeneous mixture after fully ultrasound and stirring, by this
Aaerosol solution rapid vacuum filtration, the compound for being dried to obtain graphene coated polymer.The scanned electron microscopic observation of the compound
It was found that graphene uniform be coated on the outer surface of polymer beads, it was demonstrated that Graphene realizes uniform point in fluoropolymer resin
Dissipate, this lays the foundation for Graphene constitutes conductive network in matrix resin.The compound warp of above-mentioned graphene coated polymer
The specific insulation that hot pressing obtains composite conductive film reaches 106The Ω cm orders of magnitude, surface resistivity reaches 106Ω/ quantity
Level, can meet antistatic requirement.The solvent of the method dispersed graphite alkene selects water, it is possible to prevente effectively from being made using organic solvent
Into environmental pollution, it can be considered that being environment-friendly method.The method suitable industrial-scale production simple for process.
Find that performance of the yardstick of Graphene to the electric conductivity of the composite for obtaining has large effect in the present invention,
Therefore the Graphene size range that the present invention is used is 10-50 μm.This Graphene easily disperses, it is easy in spherical PVC
Surface forms clad, advantageously forms effective conductive network, only constitutes effective conductive network, could make what is obtained
Composite has good electric conductivity, meets Graphene/PVC laminated films wanting in terms of for antistatic or electromagnetic shielding
Ask.
Advantages of the present invention is as follows：
1st, the present invention appropriate Graphene is added in polymeric material using ad hoc approach and realize it is dispersed, by
Electric transmission network can be constituted in composite conductive film in the two-dimensional graphene with big radius-thickness ratio, therefore can be significantly increased
The electric conductivity of composite（Volume resistance drops to 103The Ω orders of magnitude）, polymer composites are met as electronics unit
The conduction needs during occasion of the packaging material, anti-static material and electromagnetic shielding of part.
2nd, the Graphene/polymer composite film material prepared with the present invention, with good electric conductivity, volume（Table
Face）Resistance is minimum to can reach 103The Ω orders of magnitude, specific insulation is up to 106The Ω cm orders of magnitude；Surface resistivity is up to 106
Ω/ orders of magnitude.
Selected solvent is water when the 3rd, with present invention preparation graphene dispersion suspension, and water is environmentally friendly, is again
Cheap raw material, and water can recycle, therefore in the absence of problem of environmental pollution.
4th, the process is simple of Graphene/polyvinyl chloride laminated film is prepared with the present invention, production efficiency is high, it is easy to accomplish work
Industry large-scale production.
Brief description of the drawings
Fig. 1 is the stereoscan photograph of 1 Graphene of embodiment/polyvinyl chloride composite powder.
Fig. 2 is the stereoscan photograph of 2 Graphenes of embodiment/polyvinyl chloride composite powder.
Fig. 3 is the stereoscan photograph in the cross section of 1 Graphene of embodiment/polyvinyl chloride laminated film.
Specific embodiment
The present invention is described in detail in detail with reference to the accompanying drawings and examples.
Embodiment 1
Graphene/PVC composite conductive thin film materials are prepared, Graphene content in composite conductive thin film material is
1.0wt%。
First to particulate polyvinyl chloride（PVC）Carry out plastics processing：30 grams of O-phthalics are added in 50 grams of polyvinyl chloride resin
Dioctyl phthalate, the graininess PVC after being plastified for 1 hour through 80 DEG C of curings after stirring.By 0.75 gram of Graphene（GNS）,
It is added to 100 milliliters of 2wt% polypyrrole alkanones（PVP）In the aqueous solution, agitated 1h and ultrasonically treated 30min obtain GNS successively
Dispersed suspension.78.8 grams of PVC through plastifying are added in the suspension of above-mentioned GNS, ultrasonic disperse 1 hour, stirring
10 hours, then through being dried to obtain PVC/GNS Compound Black grey powder under the conditions of vacuum filtration, 100 DEG C.
Fig. 1 is the stereoscan photograph of the Graphene/polyvinyl chloride composite powder obtained after drying, therefrom can from figure
Go out graphene uniform to be coated on polyvinyl chloride particles, the two realizes perfect combination, is next step structure in laminated film
Laid the foundation into conductive network.
Take the appropriate powder to be placed on hydraulic press at 160 DEG C, 2MPa pressure pushes and obtains within 10 minutes Graphene/PVC and be combined
Conductive film material, Fig. 3 is the cross section stereoscan photograph of the laminated film, it can be seen that Graphene is thin from photo
Conductive network is constituted in film, it is ensured that the laminated film has certain electric conductivity.After tested, the volume resistance of the conducting film is
6700 Ω, specific insulation 3.7 × 106Ω·cm；Sheet resistance 2.9 × 104Ω, surface resistivity 1.3 × 107Ω/□。
Embodiment 2
Graphene/PVC composite conductive thin film materials are prepared, Graphene content in composite conductive thin film material is
1.25wt%。
First to particulate polyvinyl chloride（PVC）Carry out plastics processing：Process is with embodiment 1.By 1 gram of Graphene（GNS）
It is added to 100 milliliters of 2wt% polypyrrole alkanones（PVP）In the aqueous solution, to obtain GNS equal for agitated 1h and ultrasonically treated 50min successively
Even dispersion suspension.78.4 grams of PVC through plastifying are added in the suspension of above-mentioned GNS, ultrasonic disperse 1 hour, stirring 10
Hour, then through being dried to obtain PVC/GNS Compound Black grey powder under the conditions of vacuum filtration, 100 DEG C.
Fig. 2 is the stereoscan photograph of the Graphene/polyvinyl chloride composite powder obtained after drying, it can be seen that Graphene
It is evenly coated on polyvinyl chloride particles, the two realizes perfect combination, is that next step constitutes conductive mesh in laminated film
Network lays the foundation.
Take the appropriate powder to be placed on hydraulic press at 160 DEG C, 2MPa pressure is pushed 10 minutes and obtains composite conductive film, and this is led
The volume resistance of electrolemma is 4000 Ω, specific insulation 1.7 × 106Ω·cm；The Ω of sheet resistance 3200, surface resistivity 1.4
×106Ω/□。
Embodiment 3
Graphene/PVC composite conductive thin film materials are prepared, Graphene content in composite conductive thin film material is
2.5wt%。
The polyvinyl chloride resin method of DOP plasticizings is prepared with embodiment 1.By 2 grams of Graphenes（GNS）200 milliliters of 2wt% are added to gather
Pyrrolidones（PVP）In the aqueous solution, agitated 1h and ultrasonically treated 1h obtain the dispersed suspension of GNS successively.By 76.8 grams
PVC through plastifying is added in the suspension of above-mentioned GNS, ultrasonic disperse 1 hour, is stirred 10 hours, then through vacuum filtration, 100
PVC/GNS Compound Black grey powder is dried to obtain under the conditions of DEG C.The appropriate powder is taken to be placed on hydraulic press in 160 DEG C, 2MPa pressures
Power is pushed 10 minutes and obtains composite conductive film, and the volume resistance of the conducting film is 3830 Ω, specific insulation 1.65 × 106Ω·
cm；The Ω of sheet resistance 2200, surface resistivity 1.15 × 106Ω/□。
Embodiment 4
Graphene/PE composite conductive thin film materials are prepared, Graphene content in composite conductive thin film material is 2.5wt%.
By 2 grams of Graphenes（GNS）It is added to 200 milliliters of 2wt% polypyrrole alkanones（PVP）In the aqueous solution, agitated 1h successively
The dispersed suspension of GNS is obtained with ultrasonically treated 50min.78 grams of PE are added in the suspension of above-mentioned GNS, ultrasonic disperse
1 hour, stir 10 hours, then through being dried to obtain PE/GNS Compound Black grey powder under the conditions of vacuum filtration, 100 DEG C.
Take the appropriate powder to be placed on hydraulic press at 160 DEG C, 2MPa pressure is pushed 10 minutes and obtains composite conductive film, and this is led
The volume resistance of electrolemma is 3500 Ω, specific insulation 1.5 × 106Ω·cm；The Ω of sheet resistance 4000, surface resistivity 1.75
×106Ω/□。
Embodiment 5
Graphene/polypropylene composite materials conductive film material is prepared, Graphene content in composite conductive thin film material is
2wt%。
By 1 gram of Graphene（GNS）It is added to 100 milliliters of 2wt% polypyrrole alkanones（PVP）In the aqueous solution, agitated 1h successively
The dispersed suspension of GNS is obtained with ultrasonically treated 50min.49 grams of polypropylene is added in the suspension of above-mentioned GNS, is surpassed
Sound disperses 1 hour, stirs 10 hours, then through being dried to obtain PVC/GNS Compound Black grey powder under the conditions of vacuum filtration, 100 DEG C.
Take the appropriate powder to be placed on hydraulic press at 150 DEG C, 2MPa pressure is pushed 10 minutes and obtains composite conductive film, and this is led
The volume resistance of electrolemma is 8000 Ω, specific insulation 3.4 × 106Ω·cm；The Ω of sheet resistance 9000, surface resistivity 3.5
×106Ω/□。
Comparative example 1
Prepare the PVC film without Graphene.The polyvinyl chloride resin method of DOP plasticizings is prepared with embodiment 1.Take appropriate DOP plasticizings
PVC powder be placed on hydraulic press at 160 DEG C, 2MPa pressure is pushed 10 minutes and obtains composite conductive film, the volume of the conducting film
Resistance is 5.8 × 109Ω, specific insulation 2.3 × 1012Ω·cm；Sheet resistance 4.2 × 1012Ω, surface resistivity 1.8 ×
1012Ω/□。
Comparative example 2
Change pressure to prepare Graphene weight in PVC is the conductive composite film of 2wt%.Prepare the PVC trees of DOP plasticizings
Fat method is with embodiment 1.The method of GNS/PVC composite powders is prepared with embodiment 2.Appropriate GNS/PVC composite powders are taken to be placed on
At 160 DEG C on hydraulic press, 20MPa pressure is pushed 10 minutes and obtains composite conductive film, and the volume resistance of the conducting film is 4.79 ×
108Ω, specific insulation 2.8 × 1010Ω·cm；Sheet resistance 5.35 × 108Ω, surface resistivity 6.78 × 1011Ω/□。
Claims (6)
1. the preparation method of a kind of Graphene/polymer composite conductive thin film material, it is characterised in that：The composite conductive thin film
Material includes Graphene and polymeric matrix, and weight percentage of the Graphene in composite conductive thin film is 0.5-5%, described
Graphene constitutes conductive network in composite conductive thin film material；The Graphene is reduced by intercalation stripping method or graphite oxidation
Prepared by method, the size range of Graphene is 10-50 μm；The volume resistance and sheet resistance of the composite conductive thin film are minimum
103The Ω orders of magnitude, specific insulation reaches 106The Ω cm orders of magnitude, surface resistivity reaches 106Ω/ orders of magnitude；
The preparation method of the Graphene/polymer composite conductive thin film material is：First by graphene uniform be dispersed in containing
In the aqueous solution of surfactant, the suspension of Graphene is formed, then granulated polymer is distributed to the suspension of Graphene
In liquid, sequentially pass through filter and be dried to obtain the composite powder of graphene coated polymer, then the composite powder is obtained through hot pressing
Graphene/polymer composite conductive thin film material；The method specifically includes following steps：
(1) preparation of the suspension of Graphene：First by surfactant according to surfactant：The weight of water=0.1-3%
Ratio is added in deionized water, obtains the aqueous solution containing surfactant, Graphene is then added under agitation, often
The addition of Graphene is 1-10mg in the aqueous solution of the milliliter containing surfactant, and stirring is then sonicated 30-60 points after 1 hour
Clock, obtains the suspension of Graphene；
(2) granulated polymer is added in the suspension of step (1) gained Graphene under agitation in the desired amount, is surpassed
Sound is quick again after 1 hour to be stirred more than 6 hours, obtains Graphene/polymer suspension；
(3) step (2) gained Graphene/polymer suspension is carried out into vacuum filtration, after then being dried under the conditions of 100 DEG C,
Obtain the composite powder of graphene coated polymer；
(4) composite powder of graphene coated polymer is used into vulcanizing press in 160-200 DEG C of temperature and 2-4MPa pressure
Push 6-10 minutes, be made Graphene/polymer composite conductive thin film.
2. the preparation method of Graphene according to claim 1/polymer composite conductive thin film material, it is characterised in that：
Weight percentage of the Graphene in composite conductive thin film is 1.5-4%.
3. the preparation method of Graphene according to claim 1/polymer composite conductive thin film material, it is characterised in that：
The polymeric matrix is one or more in polyvinyl chloride, polystyrene, polyester, polyethylene and polypropylene.
4. the preparation method of Graphene according to claim 1/polymer composite conductive thin film material, it is characterised in that：
The thickness of the composite conductive thin film is 0.1-2mm.
5. the preparation method of Graphene according to claim 1/polymer composite conductive thin film material, it is characterised in that：
The surfactant is polyvinylpyrrolidone, polyvinyl alcohol, silane coupler or titanate coupling agent.
6. the preparation method of Graphene according to claim 1/polymer composite conductive thin film material, it is characterised in that：
The granulated polymer is preceding by plastics processing in use, and processing procedure is：A certain amount of granulated polymer is weighed, by poly-
Compound is 100 with plasticizer weight ratio：60 add dioctyl phthalate plasticizer, locate under the conditions of 80 DEG C after stirring
Reason 1 hour, the polymer for being plastified.
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