CN105111701B - Conductive carbon/polymer based composite material and preparation method thereof - Google Patents
Conductive carbon/polymer based composite material and preparation method thereof Download PDFInfo
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Abstract
The invention provides a conductive carbon/polymer based composite material comprising conductive carbon and a polymer, wherein the weight of the conductive carbon accounts for 1-45% of that of the polymer. The invention also provides a preparation method of the composite material. The preparation method comprises the following steps: (1) dispersing the conductive carbon in a solvent to obtain conductive carbon dispersion; (2) heating a solid polymer to obtain molten dispersion; (3) adding the conductive carbon dispersion into the molten dispersion, heating and stirring uniformly to remove the solvent so as to obtain a molten mixed material, wherein the weight of the conductive carbon accounts for 1-45% of that of the solid polymer, and the heating temperature is 0-10 DEG C higher than the melting temperature of the solid polymer; and (4) pouring the molten mixed material into a mold, cooling quickly for molding, and demolding to prepare the conductive carbon/polymer based composite material. By adopting the preparation method provided by the invention, the problems of the prior art are solved; and the preparation method is simple in process, relatively low in cost and suitable for industrial production.
Description
Technical field
The present invention relates to field of polymer-base composite material, more particularly to a kind of conductive carbon/polymer matrix composite
And preparation method thereof.
Background technology
At present, because low melting point polymer material such as PLA etc. is with good performance, it is applied rapidly in each neck
Domain.In order to improve the electric conductivity of polymeric material, conductive carbon such as CNT, SP are often added in low melting point polymer material
Or expanded graphite etc., to obtain the conductive carbon/polymer matrix composite with excellent conductive performance.
At present the conventional preparation method of conductive carbon/polymer matrix composite include melt-blending process, solution blended process and
Situ aggregation method etc..Melt-blending process is in the polymer being added directly into conductive carbon under molten state, by churned mechanically
Method makes it be mixed to form composite.This method can only make conductive carbon and polymer reach being well mixed for statement, and
Due to the polymer viscosity of molten state it is higher, it is difficult to dispersed conductive carbon, therefore be only suitable for preparing conductive carbon content relatively low
Composite.Solution blended process is usually that first conductive powder is distributed in the good solvent of soluble polymeric thing, is subsequently added
Polymer, after mixing, heating evaporation removes solvent, obtains composite.Using evaporation process during solution blended process in solvent
In, conductive carbon agglomeration is serious, causes conductive carbon skewness in the composite.Situ aggregation method be first by conductive carbon with
Monomer mixes, then carries out the method that polymerisation generates composite under certain condition.Situ aggregation method passes through polycondensation reaction
Make to form covalent bond between conductive carbon and polymer, strengthen the interface interaction between conductive carbon and polymer, but situ aggregation method is only
It is suitable for monomer, aggregated macromolecular material is not applied to, and it is relatively costly.
Therefore, it is to solve the problems, such as current conductive carbon/polymer matrix composite preparation method, it is necessary to provide one
Plant new conductive carbon/polymer matrix composite and preparation method thereof.
The content of the invention
To solve the above problems, the embodiment of the present invention aims to provide a kind of conductive carbon/polymer matrix composite and its system
Preparation Method, conductive carbon is evenly distributed in conductive carbon/polymer matrix composite, and the preparation method process is simple, cost are relatively low.
In a first aspect, the invention provides a kind of conductive carbon/polymer matrix composite, including conductive carbon and polymer,
The weight of the conductive carbon is the 1%-45% of the polymer weight.
Preferably, the weight of the conductive carbon is the 35%-45% of the polymer weight.
Preferably, the polymer is low melting point polymer of the fusing point less than or equal to 500 DEG C.
It is highly preferred that the polymer is PLA, polycaprolactone, polyarylate, polystyrene, Merlon and poly- methyl
At least one in methyl acrylate.
In conductive carbon/polymer matrix composite that first aspect present invention is provided, the content of the conductive carbon is higher, institute
State conductive carbon to be distributed in the conductive carbon/polymer matrix composite more uniformly, improve the conductive carbon/polymer matrix
The electric conductivity of composite.
Second aspect, the invention provides a kind of preparation method of conductive carbon/polymer matrix composite, including following step
Suddenly：
(1) conductive carbon is scattered in solvent and obtains conductive carbon dispersion liquid；
(2) solid polymer is carried out heating the polymer for obtaining molten state；
(3) the conductive carbon dispersion liquid is added in the polymer of the molten state, the weight of the conductive carbon is institute
The 1%-45% of solid polymer weight is stated, is heated and is stirred to remove solvent, the temperature of the heating is than step (2) institute
The heating melt temperature for stating solid polymer is high 0-10 DEG C, obtains the mixing material of molten state；
(4) mixing material of the molten state is poured in mould, fast cooling shaping, the demoulding, conductive carbon/polymerization is obtained
Thing based composites, in the conductive carbon/polymer matrix composite, the weight of the conductive carbon is the polymer weight
1%-45%.
Preferably, in step (1) before the conductive carbon is placed in solvent, first using acid or surfactant to institute
Stating conductive carbon carries out surface modification.
It is highly preferred that adopt acid that the method for surface modification is carried out to the conductive carbon for：By the conductive carbon be placed in sulfuric acid,
In at least one acid in nitric acid and phosphoric acid, 1-5h is reacted at 25-90 DEG C, filtered, carried out after filter residue is repeatedly washed
Vacuum drying, grinding, are obtained the conductive carbon of surface modification.
It is highly preferred that adopt surfactant that the method for surface modification is carried out to the conductive carbon for：By the conductive carbon
In being placed in the solution containing surfactant, ultrasonic disperse 1h-5h obtains the conductive carbon solution of surface modification.
Preferably, in step (2) in the polymer heating process, organic solvent is added, is stirred, melted
The polymer of state, the organic solvent is at least one in dimethylformamide (DMF) and 1-METHYLPYRROLIDONE (NMP).
Preferably, the method for fast cooling shaping is described in step (4)：The mixing material of the molten state is carried out cold
At least one lyophilized dry or in the mixing material of the molten state in addition deionized water and alcohol, makes the molten state
Mixing material fast cooling shaping.
Present invention incorporates melt-blending process and solution blended process, there is provided a kind of new conductive carbon/polymer matrix is combined
The preparation method of material, the preparation method in a heated condition removes conductive carbon dispersion liquid and the mixed with polymers of molten state
Solvent, finally quenching shaping is prepared and is well mixed and the conductive carbon with excellent conductive capability/low melting point polymer base is compound
Material.What the preparation method that the present invention is provided overcame that melt-blending process can only achieve that conductive carbon and polymer take a stand is well mixed
And the viscosity of polymer melt is high, is only suitable for preparing the problem of the relatively low composite of conductive carbon content, and overcome solution
Blending method in the evaporation process of solvent, reunite seriously, the problem of skewness by conductive carbon particle.Meanwhile, what the present invention was provided
The preparation method process is simple of conductive carbon/polymer matrix composite, cost are relatively low, and obtained conductive carbon/polymer matrix is combined
Conductive carbon content is higher in material, and is distributed more uniform.
To sum up, beneficial effect of the present invention includes the following aspects：
(1) in conductive carbon/polymer matrix composite that the present invention is provided, the content of the conductive carbon is higher, described to lead
Electrical carbon is distributed more uniformly in conductive carbon/polymer matrix composite, improves the conductive carbon/polymer matrix composite
Electric conductivity；
(2) conductive carbon dispersion liquid and the mixed with polymers of molten state are removed in a heated condition solvent, finally by the present invention
Quenching shaping, has been obtained and has been well mixed and with excellent electric conductivity conductive carbon/polymer matrix composite.It is prepared by the present invention
Method process is simple, cost is relatively low, is conducive to industrialization production.
Description of the drawings
Fig. 1 is the preparation method process chart of the conductive carbon/polymer matrix composite of an embodiment of the present invention；
Fig. 2 is the preparation method process chart of the conductive carbon/polymer matrix composite of the embodiment of the present invention one.
Specific embodiment
Described below is the preferred embodiment of the embodiment of the present invention, it is noted that for the common skill of the art
For art personnel, on the premise of without departing from embodiment of the present invention principle, some improvements and modifications can also be made, these improvement
With the protection domain that retouching is also considered as the embodiment of the present invention.
In a first aspect, the invention provides a kind of conductive carbon/polymer matrix composite, including conductive carbon and polymer,
The weight of conductive carbon is the 1%-45% of polymer weight.
In embodiment of the present invention, the weight of conductive carbon is the 35%-45% of polymer weight.
In embodiment of the present invention, the deviation of the resistivity value at each position in conductive carbon/polymer matrix composite
Less than 20 Ω cm.
Deviation refers to the difference of single resistivity value and resistivity mean value.
The resistivity value size at each position is close in conductive carbon/polymer matrix composite, each position resistivity number
The gap of value is less, illustrates that electrical carbon is distributed in conductive carbon/polymer matrix composite more uniform.
In embodiment of the present invention, in step (1) conductive carbon be carbon black, carbon fiber, CNT, activated carbon, carbosphere,
At least one in expanded graphite, Graphene and conductive carbon SP.
In embodiment of the present invention, the particle diameter of conductive carbon material is 10nm-50 μm in step (1).
In embodiment of the present invention, polymer is low melting point polymer of the fusing point less than or equal to 500 DEG C.
In embodiment of the present invention, polymer is PLA (PLA), polycaprolactone (PCL), polyarylate (PAR), polyphenyl second
At least one in alkene (PS), Merlon (PC) and polymethyl methacrylate (PMMA).
In conductive carbon/polymer matrix composite that first aspect present invention is provided, the content of conductive carbon is higher, improves
The electric conductivity of conductive carbon/polymer matrix composite.
Second aspect, as shown in figure 1, systems of the Fig. 1 for the conductive carbon/polymer matrix composite of an embodiment of the present invention
Preparation Method process chart；Comprise the following steps：
(1) conductive carbon is scattered in solvent and obtains conductive carbon dispersion liquid；
(2) solid polymer is carried out heating the polymer for obtaining molten state；
(3) conductive carbon dispersion liquid is added in the polymer of molten state, the weight of conductive carbon is solid polymer weight
1%-45%, heat and stir to remove solvent, the temperature of heating than step (2) solid polymer plus heat fusing temperature
Spend high 0-10 DEG C, obtain the mixing material of molten state；
(4) mixing material of molten state is poured in mould, fast cooling shaping, the demoulding, conductive carbon/polymer matrix is obtained
Composite, in conductive carbon/polymer matrix composite, the weight of conductive carbon is the 1%-45% of polymer weight.
In embodiment of the present invention, solvent is absolute ethyl alcohol, deionized water, dimethylformamide and N- first in step (1)
At least one in base pyrrolidones；
In embodiment of the present invention, in step (1) conductive carbon be carbon black, carbon fiber, CNT, activated carbon, carbosphere,
At least one in expanded graphite, Graphene and conductive carbon SP.
In embodiment of the present invention, the particle diameter of conductive carbon material is 10nm-50 μm in step (1).
In embodiment of the present invention, the mass fraction of conductive carbon is 1%-45% in conductive carbon dispersion liquid.
In embodiment of the present invention, polymer is low melting point polymer of the fusing point less than or equal to 500 DEG C.
In embodiment of the present invention, polymer is PLA (PLA), polycaprolactone (PCL), polyarylate (PAR), polyphenyl second
At least one in alkene (PS), Merlon (PC) and polymethyl methacrylate (PMMA).
In embodiment of the present invention, in step (1) before conductive carbon is placed in solvent, first using acid or surface-active
Agent carries out surface modification to conductive carbon.
By carrying out surface modification to conductive carbon, the functional groups such as carboxyl, hydroxyl can be introduced in conductive carbon surface, be improve
The dispersiveness of conductive carbon and the Interface adhesive strength with polymer, contribute to being well mixed for conductive carbon and polymer, prevent from leading
The reunion of electrical carbon.
In embodiment of the present invention, adopt acid that the method for surface modification is carried out to conductive carbon for：By conductive carbon be placed in sulfuric acid,
In at least one acid in nitric acid and phosphoric acid, 1-5h is reacted at 25-90 DEG C, filtered, carried out after filter residue is repeatedly washed
Vacuum drying, grinding, are obtained the conductive carbon of surface modification.
The addition of acid floods conductive carbon, does not do specifically limited.
The follow-up conductive carbon of surface modification is scattered in solvent obtains conductive carbon dispersion liquid.
In embodiment of the present invention, adopt surfactant that the method for surface modification is carried out to conductive carbon for：By conductive carbon
In being placed in the solution containing surfactant, ultrasonic disperse 1h-5h obtains the conductive carbon solution of surface modification.
In embodiment of the present invention, the weight of surfactant is 0.05-0.8 times of conductive carbon weight, surfactant
Lead in -100 and polyvinylpyrrolidone extremely for lauryl sodium sulfate (SDS), neopelex (SDBS), Qula
Few one kind.
The follow-up conductive carbon solution of surface modification is scattered in solvent obtains conductive carbon dispersion liquid.
In embodiment of the present invention, scattered method is in step (1)：Disperseed using ball milling, grinding, sand milling or dispersion machine
Method make conductive carbon form conductive carbon dispersion liquid in a solvent.
Conductive carbon favorable dispersibility in obtained conductive carbon dispersion liquid, exists on apparent without big conductive carbon particle, and not
Can settle.
In embodiment of the present invention, heating-up temperature≤500 DEG C in step (2).
In embodiment of the present invention, in step (2) in polymer heating process, organic solvent is added, stirred, obtained
To the polymer of molten state, organic solvent is at least in dimethylformamide (DMF) and 1-METHYLPYRROLIDONE (NMP)
Kind.
When molten polymer viscosity is larger, when such as stirring motionless or difficult stirring using mixing plant, addition has on a small quantity
Machine solvent, to reduce the viscosity of molten polymer, is conducive to the uniform mixing of the polymer of subsequent conductive carbon and molten state, has
The composite higher beneficial to conductive carbon content is obtained.
In embodiment of the present invention, the addition of organic solvent is that the viscosity that can reduce polymer makes it in step (2)
Contribute to stirring, concrete addition is not limited.
In embodiment of the present invention, in step (3), mixing time is 4-12h.
In embodiment of the present invention, mixing speed is 100rpm-1000rpm in step (3).
In embodiment of the present invention, the weight of conductive carbon is the 35%-45% of solid polymer weight in step (3).
Vapored away by making solvent major part in lasting heating process in step (3).In this process, polymer begins
It is kept molten by eventually, conductive carbon is evenly distributed in molten polymer, it is to avoid because temperature is slow during solvent volatilization process
Reduction causes conductive carbon reunion segregation.
In embodiment of the present invention, step is added to conductive carbon dispersion liquid in the polymer of molten state in (3), is continuing
It is stirred uniformly to remove solvent under the conditions of heating evaporation or vacuum distillation.
By by the mixed with polymers of conductive carbon dispersion liquid and molten state, having the advantages that：First, compared to general
The conductive carbon of powder is added directly in the polymer of molten state, and the present invention is added to conductive carbon in the form of dispersion liquid
In molten polymer, conductive carbon is disperseed in the polymer more uniform；Secondly, during conductive carbon and mixed with polymers, polymerization
Thing remains molten condition, while under constant agitation, conductive carbon is evenly distributed on all the time in molten polymer, is kept away
Because temperature slowly reduces causing conductive carbon reunion segregation when exempting from solvent volatilization process；Finally, conductive carbon dispersion liquid of the present invention and
During the mixed with polymers of molten state, heating stirring is only needed, it is not necessary to which high equipment such as double screw extruder is true
Empty heating stirring equipment etc..
By carrying out surface modification to conductive carbon, the functional groups such as carboxyl, hydroxyl are introduced in conductive carbon surface, improve it
Dispersiveness and the Interface adhesive strength with polymer, can enter during the mixed with polymers of conductive carbon dispersion liquid and molten state
One step improves the dispersiveness of conductive carbon.
By adding organic solvent in molten polymer, the viscosity of molten polymer can be reduced, after being conducive to
The uniform mixing of the polymer of continuous conductive carbon and molten state, is conducive to obtaining the higher composite of conductive carbon content.
In embodiment of the present invention, the method for fast cooling shaping is in step (4)：The mixing material of molten state is carried out
Freeze-drying adds deionized water and at least one in alcohol in the mixing material of molten state, makes the mixing material of molten state
Material fast cooling shaping.
By fast cooling shaping, on the one hand, the solvent that can completely do not volatilize with removal step (3), conductive carbon/polymerization is made
Solvent is not contained in thing based composites；On the other hand, it is possible to achieve conductive carbon/polymer matrix composite is quickly cooled down, prevent
The only reunion segregation of the conductive carbon particle during its Slow cooling.
In embodiment of the present invention, cryodesiccated temperature is less than room temperature.
In embodiment of the present invention, cryodesiccated temperature is -10 DEG C -10 DEG C.
In embodiment of the present invention, the mixing material of at least one addition submergence molten state in deionized water and alcohol
Material.
The shape of conductive carbon/polymer matrix composite depends on the shape of mould, can be prepared into tabular, round shape, squeeze
Go out shaping or flake etc..
In conductive carbon/polymer matrix composite, the weight of conductive carbon is the 35%-45% of polymer weight.
Present invention incorporates melt-blending process and solution blended process, there is provided a kind of new conductive carbon/polymer matrix is combined
The preparation method of material, the preparation method in a heated condition or subtracts conductive carbon dispersion liquid and the mixed with polymers of molten state
Remove solvent under pressure distillation condition, finally quenching shaping, prepare be well mixed and the conductive carbon with excellent conductive capability/it is low
Melting polymers based composites.The preparation method that the present invention is provided overcomes melt-blending process and can only achieve conductive carbon and polymerization
What thing was taken a stand be well mixed and the viscosity of polymer melt is high, is only suitable for preparing asking for the relatively low composite of conductive carbon content
Topic, and solution blended process is overcome in the evaporation process of solvent, conductive carbon particle is reunited seriously, the problem of skewness.
The preparation method process is simple of conductive carbon/polymer matrix composite that the present invention is provided, cost are relatively low, obtained composite
Middle conductive carbon can mix with polymer uniform.
Embodiment one
A kind of preparation method of conductive carbon/polymer matrix composite, as shown in Fig. 2 Fig. 2 is leading for present invention enforcement one
The preparation method process chart of electrical carbon/polymer matrix composite, comprises the following steps：
(1) it is 3 to take 100g CNTs and be placed in the concentrated sulfuric acid of 1200mL and red fuming nitric acid (RFNA) volume ratio:In 1 nitration mixture, at 40 DEG C
Lower reaction 2h, then filters, and is in repeatedly after neutrality, to be vacuum dried and ground up to water lotion by filter residue washing, and table is obtained
The CNT of face modification, the CNT for taking surface modification is placed in absolute ethyl alcohol, grinds 2h, and carbon nanotube mass point is obtained
Number is 5% carbon nano tube dispersion liquid；
(2) 2000g solid-states PLA is heated at 250 DEG C and is melted, and add a small amount of DMF to carry out in melting process
Stirring and viscosity are adjusted, and obtain the PLA of the suitable molten state of viscosity；
(3) carbon nano tube dispersion liquid is added in the PLA of molten state, heating evaporation is carried out at 250 DEG C and stirs mixed
Close, to remove most of solvent, the weight of CNT is the 5% of PLA weight, and mixing time is 4h, and mixing speed is
1000rpm, obtains the mixing material of molten state；
(4) mixing material of molten state is poured in mould, is subsequently added deionized water and alcohol is allowed to cool completely simultaneously
Separate out remaining solvent, the demoulding is obtained carbon nanotube/polylactic acid based composites, in conductive carbon/polymer matrix composite
The weight of conductive carbon is the 5% of polymer weight.
Conductive carbon/polymer matrix composite obtained in the embodiment of the present invention is observed, it is found that conductive carbon mixing is equal
Even, each material of incision position of conductive carbon/polymer matrix composite is also well mixed.
Resistivity measurement is carried out to conductive carbon/polymer matrix composite obtained in the present embodiment, test result is：Pure
PLA insulate, and resistivity is infinitely great；And carbon nanotube/polylactic acid based composites (CNT/PLA) obtained in the present embodiment are no
It is 180 ± 10 Ω cm with the resistivity value at position, each position resistivity deviation value is 10 Ω cm to the maximum, it is known that CNT exists
It is well mixed in composite, and with good electric conductivity.
Embodiment two
A kind of preparation method of conductive carbon/polymer matrix composite, comprises the following steps：
(1) 100g CNTs are taken to be placed in the 1000mL concentrated sulfuric acids, 5h is reacted at 25 DEG C, then filtered, by filter residue water
Wash repeatedly until after water lotion is in neutral, being vacuum dried and being ground, the CNT of prepared surface modification takes surface modification
CNT be placed in 1-METHYLPYRROLIDONE (NMP), ball milling 2h, be obtained carbon nanotube mass fraction be 5% carbon nanometer
Pipe dispersion liquid；
(2) 2000g solid-states polycaprolactone is heated at 120 DEG C and is melted, add NMP to carry out viscosity in melting process
Adjust, and stirring obtains the PLA of the molten state of appropriate viscosity；
(3) carbon nano tube dispersion liquid is added in the polycaprolactone of molten state (PCL), at 120 DEG C heating evaporation is carried out
And mixing is stirred, to remove most of solvent, the weight of CNT is the 5% of polycaprolactone weight, and mixing time is 12h,
Mixing speed is 100rpm, obtains the mixing material of molten state；
(4) mixing material of molten state is poured in mould, is subsequently added deionized water and alcohol is allowed to cool completely simultaneously
Separate out remaining solvent, the demoulding is obtained conductive carbon/polymer matrix composite, carbon nano-tube/poly caprolactone based composites
The weight of middle conductive carbon is the 5% of polymer weight.
Conductive carbon/polymer matrix composite obtained in the embodiment of the present invention is observed, finds to be well mixed, it is conductive
The each material of incision position of carbon/polymer matrix composite is also well mixed.
Resistivity measurement is carried out to conductive carbon/polymer matrix composite obtained in the present embodiment, test result is：
Pure polycaprolactone insulation, resistivity is infinitely great；And carbon nano-tube/poly caprolactone base obtained in the present embodiment is compound
The resistivity value of material (CNT/PCL) different parts is 120 ± 20 Ω cm, and each position resistivity deviation value is 20 to the maximum
Ω cm, it is known that CNT is well mixed in the composite, each position resistivity value gap is little, and with good conduction
Performance.
Embodiment three
A kind of preparation method of conductive carbon/polymer matrix composite, comprises the following steps：
(1) 100g conductive black SP are taken to be placed in the 100mL concentrated sulfuric acids, 1h is reacted at 90 DEG C, then filtered, by filter residue water
Wash repeatedly until after water lotion is in neutral, being vacuum dried and being ground, the conductive black SP of prepared surface modification takes surface and repaiies
The conductive black SP of decorations is placed in dimethylformamide, ball milling 3h, and the conductive black that conductive black SP mass fractions are 5% is obtained
SP dispersion liquids；
(2) 500g solid-states polycaprolactone is heated at 100 DEG C and is melted, obtain the polycaprolactone of molten state；
(3) conductive black SP dispersion liquids are added in the polycaprolactone of molten state (PCL), at 110 DEG C heating steaming is carried out
Mixing is sent out and stirs, to remove most of solvent, the weight of conductive black SP is the 20% of polycaprolactone weight, and mixing time is
10h, mixing speed is 800rpm, obtains the mixing material of molten state；
(4) mixing material of molten state is poured in mould, is subsequently added deionized water and alcohol is allowed to cool completely simultaneously
Separate out remaining solvent, the demoulding is obtained conductive black SP/ polycaprolactone based composites, conductive black SP/ polycaprolactone-baseds
The weight of conductive black SP is the 20% of polycaprolactone weight in composite.
Conductive carbon/polymer matrix composite obtained in the embodiment of the present invention is observed, finds to be well mixed, it is conductive
The each material of incision position of carbon/polymer matrix composite is also well mixed.
Resistivity measurement is carried out to conductive carbon/polymer matrix composite obtained in the present embodiment, test result is：
Pure polycaprolactone insulation, resistivity is infinitely great；Conductive black SP/ polycaprolactone-baseds obtained in the present embodiment are combined
The resistivity value of material (SP/PCL) different parts is 60 ± 8 Ω cm, and each position resistivity deviation value is 8 Ω to the maximum
Cm, it is known that conductive black SP is well mixed in the composite, each position resistivity value gap less, and is led with good
Electrical property.
Example IV
A kind of preparation method of conductive carbon/polymer matrix composite, comprises the following steps：
(1) take 10g conductive black SP to be placed in the aqueous solution containing 8g lauryl sodium sulfate (SDS), ultrasound under room temperature
Dispersion 2h, obtains the conductive black SP solution of surface modification；The conductive black SP solution of surface modification is placed in NMP, sand milling
3h, is obtained the conductive black SP dispersion liquids that conductive black SP mass fractions are 10%；
(2) 1000g solid-states polycaprolactone is heated into 100 DEG C to be melted, obtains the polycaprolactone of molten state；
(3) conductive black SP dispersion liquids are added in the polycaprolactone of molten state (PCL), at 100 DEG C decompression steaming is carried out
Mixing is evaporated and stirs, to remove most of solvent, the weight of conductive black SP is the 1% of polycaprolactone weight, and mixing time is
4h, mixing speed is 1000rpm, obtains the mixing material of molten state；
(4) mixing material of molten state is poured in mould, is put in freeze drier and is quickly cooled in -5 DEG C
Type, separates out remaining solvent, and the demoulding is obtained conductive black SP/ polycaprolactone based composites, and conductive carbon/polymer matrix is multiple
The weight of conductive black SP is the 1% of polycaprolactone weight in condensation material.
Conductive carbon/polymer matrix composite obtained in the embodiment of the present invention is observed, finds to be well mixed, it is conductive
The each material of incision position of carbon/polymer matrix composite is also well mixed.
Resistivity measurement is carried out to conductive carbon/polymer matrix composite obtained in the present embodiment, test result is：
Pure polycaprolactone insulation, resistivity is infinitely great；And conductive black SP/ polycaprolactones obtained in the present embodiment are compound
The resistivity value of material (SP/PCL) different parts is 500 ± 10 Ω cm, and each position resistivity deviation value is 10 to the maximum
Ω cm, it is known that conductive black SP is well mixed in the composite, each position resistivity value gap is little, and with good
Electric conductivity.
Embodiment five
A kind of preparation method of conductive carbon/polymer matrix composite, comprises the following steps：
(1) 35g carbon fiber SP are taken to be placed in the aqueous solution containing 1.75g dialkyl benzene sulfonic acids sodium (SDBS), is surpassed under room temperature
Sound disperses 2h, obtains the carbon fiber solution of surface modification；The carbon fiber solution of surface modification is placed in NMP, sand milling 3h, is obtained
Carbon fiber mass fraction is 26% carbon fiber dispersion liquid；
(2) 100g solid-states polycaprolactone is heated at 100 DEG C and is melted, obtain the polycaprolactone of molten state；
(3) carbon fiber dispersion liquid is added in the polycaprolactone of molten state (PCL), vacuum distillation is carried out simultaneously at 110 DEG C
Stirring mixing, to remove most of solvent, the weight of carbon fiber is the 35% of polycaprolactone weight, and mixing time is 4h, stirring
Speed is 1000rpm, obtains the mixing material of molten state；
(4) mixing material of molten state is poured in mould, is put in freeze drier and is quickly cooled in -5 DEG C
Type, separates out remaining solvent, and the demoulding is obtained carbon fiber/polycaprolactone based composites, conductive carbon/polymer matrix composite wood
The weight of carbon fiber is the 35% of polycaprolactone weight in material.
Conductive carbon/polymer matrix composite obtained in the embodiment of the present invention is observed, finds to be well mixed, it is conductive
The each material of incision position of carbon/polymer matrix composite is also well mixed.
Resistivity measurement is carried out to conductive carbon/polymer matrix composite obtained in the present embodiment, test result is：
Pure polycaprolactone insulation, resistivity is infinitely great；Carbon fiber obtained in the present embodiment/polycaprolactone based composites
The resistivity of different parts can reach 15 ± 3 Ω cm.Each position resistivity deviation value is 3 Ω cm to the maximum, it is known that carbon fiber
It is well mixed in the composite, each position resistivity value gap is little, and with good electric conductivity.
Embodiment six
A kind of preparation method of conductive carbon/polymer matrix composite, comprises the following steps：
(1) take 45g Graphenes to be placed in the aqueous solution containing 4.5g Qulas logical -100, ultrasonic disperse 5h under room temperature is obtained
The graphene solution of surface modification；The graphene solution of surface modification is placed in NMP, sand milling 3h, Graphene quality point is obtained
Number is 31% graphene dispersing solution；
(2) 100g polycaprolactones are heated into 100 DEG C to be melted, obtains the polycaprolactone of molten state；
(3) graphene dispersing solution of surface modification is added in the polycaprolactone of molten state (PCL), is carried out at 100 DEG C
Stirring mixing, to remove most of solvent, the weight of Graphene is the 45% of polycaprolactone weight, and mixing time is 4h, is obtained
The mixing material of molten state；
(4) mixing material of molten state is poured in mould, is put in freeze drier and is quickly cooled in -5 DEG C
Type, separates out remaining solvent, and the demoulding is obtained Graphene/polycaprolactone based composites, and Graphene/polycaprolactone-based is combined
The weight of Graphene is the 45% of polymer weight in material.
Conductive carbon/polymer matrix composite obtained in the embodiment of the present invention is observed, finds to be well mixed, it is conductive
The each material of incision position of carbon/polymer matrix composite is also well mixed.
Resistivity measurement is carried out to conductive carbon/polymer matrix composite obtained in the present embodiment, test result is：
Pure polycaprolactone insulation, resistivity is infinitely great；Graphene obtained in the present embodiment/polycaprolactone based composites
The resistivity of different parts can reach 10 ± 2 Ω cm.Each position resistivity deviation value is 2 Ω cm to the maximum, it is known that Graphene
It is well mixed in the composite, each position resistivity value gap is little, and with good electric conductivity.
Comparative example
In order to further verify the beneficial effect of the embodiment of the present invention, the present invention is provided with comparative example.
Contrast test 1：Using melt-blending process prepare conductive carbon/polymer matrix composite, will powder morphology CNT
Directly it is added in the polymer P LA of melting and mixes 4h, obtains conductive carbon/polymer matrix composite, CNT in composite
Weight is the 5% of polymer P LA weight.
Contrast test 2：Using solution blended process prepare conductive carbon/polymer matrix composite, will powder morphology CNT
It is added to solvent dimethylformamide (DMF), after stirring, adds polymer P LA, after stirring 4h, heating evaporation is removed
Solvent, obtains conductive carbon/polymer matrix composite, and the weight of CNT is the 5% of polymer P LA weight in composite.
Conductive carbon/polymer matrix composite that embodiment 1, contrast test 1 and contrast test 2 are obtained carries out resistance
Rate is tested, it is found that the resistivity value gap of the composite different parts of contrast test 1 is larger, is 80～400 Ω cm, and
Which part place insulation, it is seen that conductive carbon mixing is uneven in the composite；It was found that the composite difference portion of contrast test 2
The differential resistivity numerical difference of position, away from larger, is 160～300 Ω cm, and some areas can substantially observe the aggregation of CNT,
It can be seen that conductive carbon mixing is uneven in the composite.
And the different parts of the embodiment of the present invention 1 its resistivity, in 180 ± 10 Ω cm, each position resistivity deviation value is most
Greatly 10 Ω cm, it is known that conductive carbon of the present invention is uniformly dispersed in the composite.Therefore, using the preparation of the embodiment of the present invention
Conductive carbon obtained in method/polymer matrix composite conductive carbon distribution is more uniform.
Presently preferred embodiments of the present invention is the foregoing is only, not to limit the present invention, all essences in the present invention
Any modification, equivalent and improvement made within god and principle etc., all should be included within protection scope of the present invention.
Claims (8)
1. a kind of preparation method of conductive carbon/polymer matrix composite, it is characterised in that comprise the following steps：
(1) conductive carbon is scattered in solvent and obtains conductive carbon dispersion liquid；
(2) solid polymer is carried out heating the polymer for obtaining molten state；In the solid polymer heating process, addition has
Machine solvent, stirs, and obtains the polymer of molten state, and the organic solvent is dimethylformamide and 1-METHYLPYRROLIDONE
In at least one；
(3) the conductive carbon dispersion liquid is added in the polymer of the molten state, the weight of the conductive carbon is described solid
The 1%-45% of state polymer weight, heats and stirs to remove solvent, and the temperature of the heating is described more solid than step (2)
The heating melt temperature of state polymer is high 0-10 DEG C, obtains the mixing material of molten state；
(4) mixing material of the molten state is poured in mould, fast cooling shaping, the demoulding, the conductive carbon/polymerization is obtained
Thing based composites, the method for the fast cooling shaping is：By the mixing material of the molten state carry out freeze-drying or
Deionized water and at least one in alcohol are added in the mixing material of the molten state, makes the mixing material of the molten state fast
Fast cooling shaping；In the conductive carbon/polymer matrix composite, the weight of the conductive carbon is the polymer weight
1%-45%.
2. the preparation method of conductive carbon/polymer matrix composite as claimed in claim 1, it is characterised in that in step (1)
Before the conductive carbon is placed in solvent, first surface modification is carried out to the conductive carbon using acid or surfactant.
3. the preparation method of conductive carbon/polymer matrix composite as claimed in claim 2, it is characterised in that the employing
Acid is to the method that the conductive carbon carries out surface modification：At least one conductive carbon is placed in sulfuric acid, nitric acid and phosphoric acid
In planting acid, 1-5h is reacted at 25-90 DEG C, filtered, be vacuum dried after filter residue is repeatedly washed, ground, table is obtained
The conductive carbon of face modification.
4. the preparation method of conductive carbon/polymer matrix composite as claimed in claim 2, it is characterised in that the employing
Surfactant is to the method that the conductive carbon carries out surface modification：The conductive carbon is placed in containing the molten of surfactant
In liquid, ultrasonic disperse 1h-5h obtains the conductive carbon solution of surface modification.
5. conductive carbon/polymer matrix composite, its feature obtained in a kind of preparation method as described in any one of claim 1-4
It is, including conductive carbon and polymer, the weight of the conductive carbon is the 1%-45% of the polymer weight.
6. conductive carbon/polymer matrix composite as claimed in claim 5, it is characterised in that the weight of the conductive carbon is
The 35%-45% of the polymer weight.
7. conductive carbon/polymer matrix composite as claimed in claim 5, it is characterised in that the polymer is that fusing point is little
In or low melting point polymer equal to 500 DEG C.
8. conductive carbon/polymer matrix composite as claimed in claim 7, it is characterised in that the polymer be PLA,
At least one in polycaprolactone, polyarylate, polystyrene, Merlon and polymethyl methacrylate.
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| CN106633715A (en) * | 2016-10-20 | 2017-05-10 | 青海大学 | Graphene modified carbon black/calcium carbonate/polycaprolactone composite conductive polymeric material and preparation method thereof |
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