CN105647017B - Conductive polymer composite with continuous isolation structure and preparation method thereof - Google Patents
Conductive polymer composite with continuous isolation structure and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to conductive polymer composite field, and in particular to a kind of conductive polymer composite with continuous isolation structure and preparation method thereof.The present invention provides a kind of conductive polymer composite, and its raw material includes polymer 1 and conductive filler, and the conductive polymer composite has continuous isolation structure, and the continuous isolation structure is：Conductive filler in the form of the three-dimensional network that particle layer is constituted to be regularly distributed in polymer 1, while polymer 1 is split by conductive filler particles layer but still keeps continuous structure.Conductive polymer composite of the present invention with new type of continuous isolation structure has extremely low conductive percolation threshold, just there can be higher electrical conductivity when conductive filler content is very low, also there is higher modulus, intensity and toughness simultaneously, with good combination property.
Description
Technical field：
The invention belongs to conductive polymer composite field, and in particular to a kind of conduction with continuous isolation structure is high
Molecular composite material and preparation method thereof.
Background technology：
In recent years, conductive polymer composite is because have low density, easy processing shaping, solvent resistance and electrical conductivity can
The advantages of regulation and control, has a wide range of applications in terms of electrostatic dissipation, electromagnetic shielding, electronic sensor and capacitor.But be
Obtain the conductive polymer composite of high conduction performance, it usually needs the substantial amounts of conductive filler of addition, and substantial amounts of conduction
Filler can increase shaping during cost while can also substantially reduce the mechanical performance of material.Therefore, at present in conductive polymer
The problem of design aspect of sub- composite has two mainly：How to reduce the conductive percolation threshold of material and how to protect
Hold or even improve the mechanical performance of polymeric matrix.
There are many scholars to report a large amount of methods on the conductive percolation threshold of reduction conductive polymer composite, and its
In most effective, simplest method be exactly that the structure for controlling material makes conductive filler form special conductive mesh in polymeric matrix
Network structure.These structures mainly exceed including conductive pair oozes structure, conducting particles selective distribution in boundary and isolation structure
Deng special construction, and the method for most effective in these methods, simplest reduction materials conductive percolation threshold is exactly to build isolation
Structure.However, due to the factors such as the defect between very weak interface binding force and conducting particles and polymeric matrix, these methods
The mechanical performance of obtained conductive material is all excessively poor, particularly the material with isolation structure, the mechanical property such as its rigidity, toughness
Can all extreme differences.This problem significantly limit the application of conducting polymer composite industrially, therefore build a kind of new
With it is low exceed ooze, high electric rate is while the conductive polymer composite with preferable mechanical property is necessary.
The content of the invention：
It is an object of the invention to provide a kind of conductive polymer composite, it has continuous isolation structure, so that
The conductive percolation threshold of conductive material is obtained low, while the composite has stronger mechanical performance.
The invention solves the problems that first technical problem be to provide a kind of conductive polymer composite, its raw material includes poly-
Compound 1 and conductive filler, the conductive polymer composite have continuous isolation structure, and the continuous isolation structure is：It is conductive
Filler in the form of the three-dimensional network that particle layer is constituted to be regularly distributed in polymer 1, also, polymer 1 is by conductive filler
Particle layer is split, but polymer 1 remains in that continuous structure simultaneously.
The polymer 1 is thermoplastic polymer；Further, the polymer 1 is selected from polypropylene, polystyrene, poly- second
One kind in alkene, polyethylene glycol oxide, polyolefin elastomer, polymethyl methacrylate or TPV.The conduction
Filler is in carbon black, multi-walled carbon nanotube, single-walled carbon nanotube, carbon fiber, graphene, metal dust or other conducting particles
At least one.
Further, polymer 1 is PP, when conductive filler is multi-walled carbon nanotube or carbon black, and the conducting polymer is combined
The conductive percolation threshold of material is respectively：(i.e. it is many that the volume of multi-walled carbon nanotube accounts for PP/ to PP/ multi-walled carbon nanotubes 0.26vol%
Wall carbon nano-tube composite material cumulative volume 0.26% when may make up conductive network structure), PP/ carbon blacks 0.37vol%；Or：
Polymer 1 is polyolefin elastomer (POE), when conductive filler is multi-walled carbon nanotube or carbon black, described conductive high
The conductive percolation threshold of molecular composite material is respectively：Polyolefin elastomer/multi-walled carbon nanotube 0.39vol%, polyolefin bullet
Property body/carbon black 0.42vol%.
The invention solves the problems that second technical problem be to provide the preparation method of above-mentioned conductive polymer composite, bag
Include step：
1) forming polymer 1 and conductive filler carrier melt blending has double conductive fillers of polymer 1/ for exceeding and oozing structure
Carrier blend, the blend is designated as M1；Wherein, the conductive filler carrier is that polymer 2 is blended what is formed with conductive filler
The conductive filler composite of polymer 2/, polymer 2 is incompatible with polymer 1；Also, conductive filler selective distribution exists in M1
In polymer 2；In the present invention, if the consumption of polymer 1 and polymer 2 meet polymer 1 pass through with conductive filler carrier it is molten
Co-cable transmission structure can be formed by melting polymer blend 1 and polymer 2, and the addition of conductive filler is used according to actual use
Way and requirement determine its addition；
2) polymer 2 therein is optionally mutually completely dissolved by M1 using solvent soaking method, then through drying, removal
Solvent, obtains the porous conductive filler composite of polymer 1/；
3) by step 2) the porous conductive filler composite of polymer 1/ of gained prepared with company by heat pressing process
The conductive filler composite of polymer 1/ of continuous isolation structure, i.e. conductive polymer composite.
The polymer 2 is thermoplastic polymer；Further, the polymer 2 is selected from polypropylene, polystyrene, poly- second
One kind in alkene, polyethylene glycol oxide, polyolefin elastomer, polymethyl methacrylate or TPV.
Further, in the preparation method of the conducting polymer composite,
The polymer 1 is polypropylene, and polymer 2 is polystyrene；Or：
The polymer 1 is polyethylene, and polymer 2 is polystyrene；Or：
The polymer 1 is polyolefin elastomer, and polymer 2 is polyethylene glycol oxide；Or：
The polymer 1 is polypropylene, and polymer 2 is polymethyl methacrylate；Or：
The polymer 1 is polypropylene, and polymer 2 is TPV.
It is preferred that, step 2) in, solvent selection can dissolve polymer 2, and to the undissolved solvent of polymer 1.Enter one
Step, the solvent is at least one of dimethylbenzene, deionized water, toluene, dichloromethane, chloroform, hexamethylene.
Further, in the preparation method of the conducting polymer composite,
The polymer 1 be polypropylene, polymer 2 be polystyrene, conductive filler be multi-walled carbon nanotube or carbon black, it is molten
Agent is dimethylbenzene, and the mass ratio of polypropylene and polystyrene is 50：50；Or：
The polymer 1 is polyolefin elastomer (POE), and polymer 2 is polyethylene glycol oxide (PEO), and conductive filler is many
Wall carbon nano tube or carbon black, solvent is deionized water, and the mass ratio of polyolefin elastomer and polyethylene glycol oxide is 50：50.
Further, step 1) in, the melt blending is thermally decomposed on the fusing point of polymer 1 and conductive filler carrier
Mechanical blending is carried out below temperature.
Step 1) in, the preparation method of the conductive filler carrier is：By polymer 2 and conductive filler in polymer 2
Machinery is mixed below heat decomposition temperature on fusing point.
Step 3) in, the heat pressing process refers to：By step 2) the porous conductive filler composite of polymer 1/ of gained exists
Certain pressure is utilized under certain temperature, suppresses to the hole made in the porous conductive filler composite of polymer 1/ and merges compacting
；Wherein, certain temperature has certain fluidity for guarantee polymer 1 but keeps the temperature of larger viscosity, its determination simultaneously
Mode is：Below the onset melting temperature melt point above of crystalline polymer, glass transition temperature ± 30 DEG C of amorphous polymer；
Certain pressure is to be not less than the minimum pressure that polymer 1 can be compacted at such a temperature.
The invention solves the problems that the 3rd technical problem be to provide a kind of reduction conductive filler composite of polymer 1/ and lead
The method that electric percolation threshold keeps its mechanical performance simultaneously, i.e. selection and the incompatible polymers 2 of polymer 1, first by polymer 2
Conductive filler carrier is made with conductive filler blending, then is polymerize conductive filler carrier and the melt blending of polymer 1 are obtained
The conductive filler carrier blend of thing 1/；Then the polymer 2 in the conductive filler carrier blend of polymer 1/ is mutually completely dissolved
Remove, obtain the porous conductive filler blend of polymer 1/；The porous conductive filler blend of polymer 1/ is finally passed through into heat
The conductive filler composite of polymer 1/ of low conductive percolation threshold is made in pressure technique；Wherein, polymer 1 and polymer 2 are heat
Thermoplastic polymer.
Beneficial effects of the present invention are：
Conductive polymer composite of the present invention with new type of continuous isolation structure has extremely low conductive percolation threshold,
Can just have higher electrical conductivity when conductive filler content is very low, while also there is higher modulus, intensity and toughness,
With good combination property.And under identical conductive filler content, the conductance of the novel conductive polymer composite
Rate is high compared to traditional conducing composite material.The structure of this special continuous isolation structure is not reported so far.
Brief description of the drawings：
Fig. 1 (a) is the scanning electron microscope diagram of the step one gained PP/PS/CB ternary blends of embodiment 1, Fig. 1 (b)
For Fig. 1 (a) partial enlarged drawing.
Fig. 2 (a) is the scanning electron microscope diagram of porous PP/CB composites obtained by the step 2 of embodiment 1, and Fig. 2 (b) is
Fig. 2 (a) partial enlarged drawing.
Fig. 3 is the optical microscope of the PP/CB composites obtained by the step 3 of embodiment 1 with continuous isolation structure.
Fig. 4 is the light microscope of the PP/MWCNT composites obtained by the step 3 of embodiment 2 with continuous isolation structure
Figure.
Fig. 5 is the POE/MWCNT composite optical microscopes obtained by the step 3 of embodiment 3 with continuous isolation structure
Figure.
Fig. 6 is the optical microscope of the POE/CB composites obtained by the step 3 of embodiment 4 with continuous isolation structure.
Fig. 7 has double SEM for exceeding the PP/PS/CB ternary blends for oozing structure for what comparative example 2 was obtained
Figure.
Fig. 7 (a) has double scanning electron microscopies for exceeding the PP/PS/CB ternary blends for oozing structure for what comparative example 2 was obtained
Mirror figure, Fig. 7 (b) is Fig. 7 (a) partial enlarged drawing.
Embodiment：
The invention solves the problems that first technical problem be to provide a kind of conductive polymer composite, its raw material includes poly-
Compound 1 and conductive filler, the conductive polymer composite have continuous isolation structure, and the continuous isolation structure is：It is conductive
Filler grain is regularly distributed in polymer 1 in the form of the three-dimensional network that particle layer is constituted, while the filled particle of polymer 1
Layer segmentation but still holding continuous structure；The continuous structure of wherein polymer 1 maintains the mechanical property of material, conductive filler structure
Into three-dimensional net structure impart the excellent electric conductivity of material.
The invention solves the problems that second technical problem be to provide the preparation method of above-mentioned conductive polymer composite, institute
State and comprise the following steps：
Step 1: by the use of the two kinds of polymer of co-continuous structure can be formed as matrix, can selectively be dispersed in
Conducting particles in one of which polymer phase is filler, and three is carried out into melt blending, with obtain have it is double exceed ooze structure
Conducing composite material sample；
Step 2: the gathering compound containing nano-particle in the sample of gained in step one is selected using specific solvent
Selecting property is dissolved, and then removes solvent with certain speed, and nano-particle is deposited on the hole left during solvent is removed
Hole surface, obtains the porous material containing conductive filler；
Step 3: the porous material of gained in step 2 is utilized into certain timing of pressure compacting one at a certain temperature
Between, the hole in material is merged compacting, obtain the conducing composite material with continuous isolation structure.
The present invention build it is double exceed ooze structure and isolation structure on the basis of, propose it is a kind of using conducting particles in polymer
Selective distribution in blend, solvent is to the selective dissolution of a certain component in blend polymer and polymeric matrix
High viscosity feature, the method for building the continuous isolation structure of new conduction.
In the present invention, the critical content that conductive filler particles constitute conductive network is defined as conductive percolation threshold.The present invention
In, it is described it is double exceed ooze structure and be：Conductive filler and two kinds of incompatible polymer melt blendings, two kinds of incompatible polymers are formed
Co-continuous structure, a kind of structure of conductive filler selective distribution wherein formed in polymer.
The embodiment of the present invention is further described with reference to embodiment, not therefore by present invention limit
System is among described scope of embodiments.
Embodiment 1PP/CB conducing composite materials and its preparation
Polymer 1 is PP, and conductive filler is carbon black, and it is 50 to introduce the mass ratio that polymer 2 is PS, PP and PS:50；Prepare
Method is as follows：
Step 1: at 190 DEG C, under the conditions of 50rpm, in torque rheometer (XSS-300 types, the production of Shanghai Qing Ji mould factories)
In, first by the CB of PS and different content (CB account for PP/PS blend volume fractions be respectively 0,0.05%, 0.1%, 0.2%,
0.4%th, 1% 3min 6%), 2%, 3%, 4%, 5%, is blended, is subsequently added PP and continues that 5min is blended under the same conditions, obtain
To with it is double exceed ooze the PP/PS/CB ternary blends of structure；The SEM figures of gained ternary blends are as shown in figure 1, can be with by Fig. 1
Find out, PP and PS two-phases are continuous structure, the co-continuous structure that blend is presented, wherein CB particle selections are distributed in PS phases
In, there is no the presence of CB particles in PP, this be it is typical double exceed ooze structure.
Step 2: being soaked using by the PP/PS/CB ternary blends obtained by step one in dimethylbenzene one week, it is ensured that sample
Then sample is put into baking oven at 80 DEG C by complete selective dissolution and is dried 24h, remove completely in sample by PS phases in product
Dimethylbenzene, while CB is deposited on the hole surface left, obtains porous PP/CB composites；The scanning electricity of PP/CB composites
Mirror figure is as shown in Fig. 2 it can be seen from 2 after selective dissolution, PS phases are removed by dimethylbenzene completely, and remaining PP phases are protected
Continuous structure is hold, CB particle depositions form one layer of closely knit CB particle layer on the surface of PP phases.
Step 3: the porous PP obtained by step 2/CB composites are suppressed into 5min under the conditions of 160 DEG C, 10MPa, it is cold
But the PP/CB composites with continuous isolation structure are obtained afterwards, are designated as CS-PP/CB.The optics of gained PP/CB composites
Microscope figure as shown in figure 3, as seen from Figure 3, after compaction treatment, be successfully obtained continuous isolation structure, wherein
PP matrixes remain continuous structure, and CB particles formation conductive layer is with the formal distribution of continuous network structure in PP matrixes.
Among this continuous isolation structure, the continuous structure of PP matrixes can keep the mechanical property of material, the conduction of CB particles formation
Network then imparts the excellent electric conductivity of material.
Embodiment 2PP/MWCNT conducing composite materials and its preparation
Polymer 1 is PP, and conductive filler is multi-walled carbon nanotube, introduces polymer 2 and is for PS, PP and PS mass ratio
50:50；Preparation method is as follows：
Step 1: at 190 DEG C, under the conditions of 50rpm, in torque rheometer (XSS-300 types, the production of Shanghai Qing Ji mould factories)
In, first by the MWCNT of PS and different content (MWCNT account for PP/PS blend volume fractions be respectively 0,0.05%, 0.1%,
0.2%th, 0.4% 3min 6%), 1%, 2%, 3%, 4%, 5%, is blended, is subsequently added PP and continues to be blended under the same conditions
5min, obtains exceeding the PP/PS/MWCNT ternary blends for oozing structure with double, wherein, MWCNT selective distributions are in PS；
Step 2: being soaked using by the PP/PS/MWCNT ternary blends obtained by step one in dimethylbenzene one week, it is ensured that
Then sample is put into baking oven at 80 DEG C by complete selective dissolution and is dried 24h, remove completely in sample by PS phases in sample
Dimethylbenzene, while CB is deposited on the hole surface left, obtain porous PP/MWCNT composites；
Step 3: the porous PP obtained by step 2/MWCNT composites are suppressed into 5min under the conditions of 160 DEG C, 10MPa,
The PP/MWCNT composites with continuous isolation structure are obtained after cooling, CS-PP/MWCNT is designated as.Gained PP/MWCNT is combined
The optical microscope of material is as shown in figure 4, as seen from Figure 4, after compaction treatment, be successfully obtained continuous isolation
Structure, wherein PP matrixes remain continuous structure, and MWCNT particles formation conductive layer is existed with the formal distribution of continuous network structure
In PP matrixes.Among this continuous isolation structure, the continuous structure of PP matrixes can keep the mechanical property of material, MWCNT
The conductive network of particle formation then imparts the excellent electric conductivity of material.
Embodiment 3POE/MWCNT conducing composite materials and its preparation
Polymer 1 is POE, and conductive filler is multi-walled carbon nanotube, introduces the mass ratio that polymer 2 is PEO, POE and PEO
For 50:50；Preparation method is as follows：
Step 1: at 140 DEG C, under the conditions of 50rpm, in torque rheometer (XSS-300 types, the production of Shanghai Qing Ji mould factories)
In, first by the MWCNT of PEO and different content be blended 3min (MWCNT account for PEO/POE blend volume fractions be respectively 0,
0.05%th, 0.1%, 0.2%, 0.4%, 1%, 2%, 3%, 4%, 5%, 6%), it is subsequently added POE and continues under the same conditions
5min is blended, obtains exceeding the PEO/POE/MWCNT ternary blends for oozing structure with double；Wherein MWCNT meeting selective distributions exist
In PEO phases；
Step 2: soaking one in deionized water using by the PEO/POE/MWCNT ternary blends obtained by step one
Week, it is ensured that then sample is put into baking oven at 40 DEG C by complete selective dissolution and is dried 24h, remove completely by PEO phases in sample
The deionized water gone in sample, while MWCNT is deposited on the hole surface left, obtains porous POE/MWCNT composites；
Step 3: the porous POE/MWCNT composites obtained by step 2 are suppressed into 5min under the conditions of 60 DEG C, 10MPa,
The POE/MWCNT composites with continuous isolation structure are obtained after cooling, CS-POE/MWCNT is designated as；Gained POE/MWCNT
The optical microscope of composite is as shown in figure 5, as seen from Figure 5, after compaction treatment, be successfully obtained continuous
Isolation structure, wherein POE matrixes remain continuous structure, and MWCNT particles formation conductive layer is in the form of continuous network structure
It is distributed in POE matrixes.Among this continuous isolation structure, the continuous structure of POE matrixes can keep the mechanical property of material
Can, the conductive network of MWCNT particles formation then imparts the excellent electric conductivity of material.
Embodiment 4POE/CB conducing composite materials and its preparation
Polymer 1 is POE, and conductive filler is carbon black, and it is 50 to introduce the mass ratio that polymer 2 is PEO, POE and PEO:50；
Preparation method is as follows：
Step 1: at 140 DEG C, under the conditions of 50rpm, in torque rheometer (XSS-300 types, the production of Shanghai Qing Ji mould factories)
In, first by the CB of PEO and different content (CB account for PEO/POE blend volume fractions be respectively 0,0.05%, 0.1%, 0.2%,
0.4%th, 1% 3min 6%), 2%, 3%, 4%, 5%, is blended, is subsequently added POE and continues that 5min is blended under the same conditions, obtain
To with it is double exceed ooze the PEO/POE/CB ternary blends of structure；Wherein CB meeting selective distributions are in PEO phases；
Step 2: soaked one week in deionized water using by the PEO/POE/CB ternary blends obtained by step one,
Ensure that sample, by complete selective dissolution, is then put into baking oven at 40 DEG C and dries 24h, remove completely by PEO phases in sample
Deionized water in sample, while CB is deposited on the hole surface left, obtains porous POE/CB composites；
Step 3: the porous POE/CB composites obtained by step 2 are suppressed into 5min under the conditions of 60 DEG C, 10MPa, it is cold
But the POE/CB composites with continuous isolation structure are obtained afterwards, are designated as CS-POE/CB；Gained POE/CB composites are combined
The optical microscope of material is as shown in fig. 6, as seen from Figure 6, after compaction treatment, be successfully obtained continuous isolation
Structure, wherein POE matrixes remain continuous structure, and CB particles formation conductive layer is existed with the formal distribution of continuous network structure
In POE matrixes.In this continuous isolation structure shelves, the continuous structure of POE matrixes can keep the mechanical property of material, CB
The conductive network that son is formed then imparts the excellent electric conductivity of material.
Comparative example 1PP/CB conducing composite materials and its preparation
At 190 DEG C, under the conditions of 50rpm, in torque rheometer (XSS-300 types, the production of Shanghai Qing Ji mould factories), first will
CB (volume fraction is respectively 0,0.4%, 1%, 2%, 3%, 4%, 5%, 6%) the blendings 5min of PP and different content；Blending
Afterwards at 190 DEG C, under 10MPa, PP/CB conducing composite materials are made in hot pressing 5min after cooling.
Comparative example 2PP/PS/CB conducing composite materials and its preparation
At 190 DEG C, under the conditions of 50rpm, in torque rheometer (XSS-300 types, the production of Shanghai Qing Ji mould factories), first will
PS and different content CB (volume fraction that CB accounts for PP/PS blends is respectively 0,0.4%, 1%, 2%, 3%, 4%, 5%,
6%) 3min is blended, is subsequently added PP and continues that 5min is blended under the same conditions, obtains exceeding the PP/PS/CB for oozing structure with double
(PP and PS mass ratio are 50 to conducing composite material:50)；Wherein CB meeting selective distributions are in PS phases.Gained composite
SEM is schemed as shown in fig. 7, as seen from Figure 7, PP and PS two-phases are continuous structure, the co-continuous structure that blend is presented, its
Middle CB particle selections are distributed in PS phases, do not have the presence of CB particles in PP, this be it is typical double exceed ooze structure.
Comparative example 3PP/MWCNT conducing composite materials and its preparation
At 190 DEG C, under the conditions of 50rpm, in torque rheometer (XSS-300 types, the production of Shanghai Qing Ji mould factories), first will
MWCNT (volume fraction is respectively 0,0.4%, 1%, 2%, 3%, 4%, 5%, 6%) the blendings 5min of PP and different content.Altogether
At 190 DEG C after mixed, under 10MPa, PP/MWCNT conducing composite materials are made in hot pressing 5min after cooling.
Comparative example 4PP/PS/MWCNT conducing composite materials and its preparation
At 190 DEG C, under the conditions of 50rpm, in torque rheometer (XSS-300 types, the production of Shanghai Qing Ji mould factories), first will
PS and different content MWCNT (volume fraction that MWCNT accounts for PP/PS blends is respectively 0,0.4%, 1%, 2%, 3%,
4%th, 5% 3min, 6%) is blended, is subsequently added PP and continues that 5min is blended under the same conditions, obtain having it is double exceed ooze structure
(PP and PS mass ratio are 50 to PP/PS/MWCNT conducing composite materials:50), wherein MWCNT meetings selective distribution is in PS phases.
Comparative example 5POE/MWCNT conducing composite materials and its preparation
At 140 DEG C, under the conditions of 50rpm, in torque rheometer (XSS-300 types, the production of Shanghai Qing Ji mould factories), first will
MWCNT (volume fraction is respectively 0,1%, 4%, 6%, 8%, 10%, 12%, 14%) the blendings 5min of POE and different content.
At 140 DEG C after blending, under 10MPa, POE/MWCNT conducing composite materials are made in hot pressing 5min after cooling.
Comparative example 6PEO/POE/MWCNT conducing composite materials and its preparation
At 140 DEG C, under the conditions of 50rpm, in torque rheometer (XSS-300 types, the production of Shanghai Qing Ji mould factories), first will
PEO and different content MWCNT (volume fraction that MWCNT accounts for PEO/POE blends is respectively 0,0.4%, 1%, 2%, 3%,
4%th, 5% 3min, 6%) is blended, is subsequently added POE and continues that 5min is blended under the same conditions, obtain having it is double exceed ooze structure
(PEO and POE mass ratio are 50 to PEO/POE/MWCNT conducing composite materials:50), wherein MWCNT meetings selective distribution is in PEO
Xiang Zhong.
Comparative example 7POE/CB conducing composite materials and its preparation
At 140 DEG C, under the conditions of 50rpm, in torque rheometer (XSS-300 types, the production of Shanghai Qing Ji mould factories), first will
CB (volume fraction is respectively 0,1%, 4%, 6%, 8%, 10%, 12%, 14%) the blendings 5min of POE and different content；Altogether
At 140 DEG C after mixed, under 10MPa, POE/CB conducing composite materials are made in hot pressing 5min after cooling.
Comparative example 8PEO/POE/CB conducing composite materials and its preparation
At 140 DEG C, under the conditions of 50rpm, in torque rheometer (XSS-300 types, the production of Shanghai Qing Ji mould factories), first will
PEO and different content CB (volume fraction that CB accounts for PEO/POE blends is respectively 0,0.4%, 1%, 2%, 3%, 4%,
5%th, 3min 6%) is blended, is subsequently added POE and continues that 5min is blended under the same conditions, obtains exceeding the PEO/ for oozing structure with double
(PEO and POE mass ratio are 50 to POE/CB conducing composite materials:50), wherein CB meetings selective distribution is in PEO phases.
The electrical property of all embodiments and comparative example is tested as follows：
When resistivity is less than 106During Ω m：Print is cut into 1.2mm × 10mm × 30mm sample, sample two ends are applied
Upper elargol, to reduce contact resistance.Sample electricity is measured using digital multimeter (6517B types, Keithley instrument companies of the U.S.)
Resistance, and calculate resistivity.
When resistivity is higher than 106During Ω m：Sample is cut into 1.2mm × 200mm × 200mm, high resistivity instrument is used
(ZC36, Shanghai precision instrument Co., Ltd) measures sample resistance, and calculates resistivity.
The tensile property of all embodiments and comparative example is tested by ASTM D638.Wherein embodiment 1, embodiment 2 with
Comparative example 1, the rate of extension of comparative example 2 are 10mm/min；Embodiment 3, embodiment 4 and comparative example 3, the stretching speed of comparative example 4
Rate is 100mm/min.
The electrical property result of embodiment and comparative example is listed in table 1 and table 2.
From Tables 1 and 2, in the case of conductive filler content identical, the conduction with continuous isolation structure is combined
The resistivity of material is well below traditional polymer based conductive composite material.Illustrate, using method of the present invention, to pass through structure
This continuous isolation structure of special conduction is built, more conductive filler particles can be made to effectively join in conductive mesh, pole
The earth reduces composite material conductive percolation threshold, improves the electrical conductivity of guided missile composite.
The embodiment of table 1 and the test result 1 of comparative example sample
The embodiment of table 2 and the test result 2 of comparative example sample
Table 3 lists embodiment and mechanical property of the comparative example sample when filer content reaches percolation threshold, can see
Arrive, the novel conductive polymer composite of the present invention with continuous isolation structure reaches that exceeding for material oozes in filer content
During threshold value, its stretch modulus and tensile strength are above comparative example, while its elongation at break and tensile toughness are even more much
Higher than comparative example.It can be seen that, comparative example is in conductive energy, and its mechanical property is very big because of the presence of substantial amounts of filler
Ground is reduced, and this greatly limits its application；And novel conductive composite of the present invention, because continuous isolation structure
In the presence of the conductive percolation threshold for not only significantly reducing material improves the electric conductivity of material, also makes material with good
Also there is good mechanical property while good electric conductivity.The present invention is that a kind of simple and effective balance polymer conduction is compound
The method of materials conductive performance and mechanical property, it should be appreciated that to those skilled in the art, can basis
Described above is improved or converted, and all these modifications and variations should all belong to the protection model of appended claims of the present invention
Enclose.
The embodiment of table 3 and mechanical property of the comparative example sample when filer content reaches percolation threshold
| Stretch modulus (MPa) | Tensile strength (MPa) | Elongation at break (%) | Tension failure uptake and cumulate (103KJ/m3) | |
| Embodiment 1 | 242.6 | 27.4 | 834.1 | 188.6 |
| Comparative example 1 | 165.1 | 21.9 | 15.1 | 2.1 |
| Comparative example 2 | 151.7 | 29.6 | 71.3 | 4.8 |
| Embodiment 2 | 289.1 | 32.6 | 931.2 | 219.8 |
| Comparative example 3 | 276.3 | 31.5 | 36.6 | 4.1 |
| Comparative example 4 | 176.2 | 30.3 | 85.6 | 5.7 |
| Embodiment 3 | 15.3 | 20.4 | 1574.4 | 114.3 |
| Comparative example 5 | 14.6 | 19.7 | 142.5 | 5.2 |
| Comparative example 6 | 34.0 | 2.5 | 303.2 | 7.7 |
| Embodiment 4 | 16.8 | 21.6 | 1360.1 | 105.9 |
| Comparative example 7 | 15.2 | 20.3 | 134.4 | 4.8 |
| Comparative example 8 | 38.4 | 1.9 | 275.3 | 6.5 |
Claims (14)
1. conductive polymer composite, it is characterised in that its raw material includes polymer 1 and conductive filler, the conducting polymer
Composite has continuous isolation structure, and the continuous isolation structure is：The three-dimensional network that conductive filler is constituted with particle layer
Form is regularly distributed in polymer 1, also, polymer 1 is split by conductive filler particles layer, but polymer 1 is still simultaneously
Keep continuous structure；
The conductive polymer composite is prepared using following methods：
1) forming polymer 1 and conductive filler carrier melt blending has double conductive filler carriers of polymer 1/ for exceeding and oozing structure
Blend, the blend is designated as M1；Wherein, the conductive filler carrier is that polymerizeing of being formed is blended with conductive filler for polymer 2
The conductive filler composite of thing 2/, the polymer 2 is incompatible with polymer 1；Also, conductive filler selective distribution exists in M1
In polymer 2；
2) polymer 2 therein is optionally mutually completely dissolved removing by M1 using solvent soaking method, then through drying, removal
Solvent, obtains the porous conductive filler composite of polymer 1/；
3) by step 2) the porous conductive filler composite of polymer 1/ of gained by heat pressing process prepare with continuously every
From the conductive filler composite of polymer 1/ of structure, i.e. conductive polymer composite.
2. conductive polymer composite according to claim 1, it is characterised in that the polymer 1 is thermoplasticity polymerization
Thing；The conductive filler is in carbon black, multi-walled carbon nanotube, single-walled carbon nanotube, carbon fiber, graphene or metal dust
It is at least one.
3. conductive polymer composite according to claim 2, it is characterised in that the polymer 1 is selected from polypropylene, poly-
One in styrene, polyethylene, polyethylene glycol oxide, polyolefin elastomer, polymethyl methacrylate or TPV
Kind.
4. conductive polymer composite according to claim 3, it is characterised in that polymer 1 is polypropylene, conductive filler
During for multi-walled carbon nanotube or carbon black, the conductive percolation threshold of the conductive polymer composite is respectively：Polypropylene/many walls
CNT 0.26vol%, polypropylene/carbon black 0.37vol%；Or：
Polymer 1 is polyolefin elastomer, when conductive filler is multi-walled carbon nanotube or carbon black, the conducting polymer composite wood
The conductive percolation threshold of material is respectively：Polyolefin elastomer/multi-walled carbon nanotube 0.39vol%, polyolefin elastomer/carbon black
0.42vol%.
5. the preparation method of any one of Claims 1 to 4 conductive polymer composite, it is characterised in that methods described
Including step：
1) forming polymer 1 and conductive filler carrier melt blending has double conductive filler carriers of polymer 1/ for exceeding and oozing structure
Blend, the blend is designated as M1；Wherein, the conductive filler carrier is that polymerizeing of being formed is blended with conductive filler for polymer 2
The conductive filler composite of thing 2/, the polymer 2 is incompatible with polymer 1；Also, conductive filler selective distribution exists in M1
In polymer 2；
2) polymer 2 therein is optionally mutually completely dissolved removing by M1 using solvent soaking method, then through drying, removal
Solvent, obtains the porous conductive filler composite of polymer 1/；
3) by step 2) the porous conductive filler composite of polymer 1/ of gained by heat pressing process prepare with continuously every
From the conductive filler composite of polymer 1/ of structure, i.e. conductive polymer composite.
6. the preparation method of conductive polymer composite according to claim 5, it is characterised in that the polymer 2 is
Thermoplastic polymer；Or：
Step 2) in, solvent selection can dissolve polymer 2, and to the undissolved solvent of polymer 1.
7. the preparation method of conductive polymer composite according to claim 6, it is characterised in that the polymer 2 is selected
From polypropylene, polystyrene, polyethylene, polyethylene glycol oxide, polyolefin elastomer, polymethyl methacrylate or thermoplastic vulcanizates
One kind in rubber；Or：
Step 2) in, the solvent is at least one in dimethylbenzene, deionized water, toluene, dichloromethane, chloroform or hexamethylene
Kind.
8. the preparation method of conductive polymer composite according to claim 7, it is characterised in that in preparation method,
The polymer 1 is polypropylene, and polymer 2 is polystyrene；Or：
The polymer 1 is polyethylene, and polymer 2 is polystyrene；Or：
The polymer 1 is polyolefin elastomer, and polymer 2 is polyethylene glycol oxide；Or：
The polymer 1 is polypropylene, and polymer 2 is polymethyl methacrylate；Or：
The polymer 1 is polypropylene, and polymer 2 is TPV.
9. the preparation method of conductive polymer composite according to claim 8, it is characterised in that the conducting polymer
In the preparation method of material,
The polymer 1 is polypropylene, and polymer 2 is polystyrene, and conductive filler is multi-walled carbon nanotube or carbon black, and solvent is
The mass ratio of dimethylbenzene, polypropylene and polystyrene is 50：50；Or：
The polymer 1 is polyolefin elastomer, and polymer 2 is polyethylene glycol oxide, and conductive filler is multi-walled carbon nanotube or charcoal
Black, solvent is deionized water, and the mass ratio of polyolefin elastomer and polyethylene glycol oxide is 50：50.
10. the preparation method of conductive polymer composite according to claim 5, it is characterised in that step 1) in, it is described
Melt blending is carrying out mechanical blending below heat decomposition temperature on the fusing point of polymer 1 and conductive filler carrier；It is described to lead
The preparation method of electric filling carrier is：By polymer 2 and conductive filler on the fusing point of polymer 2 the following machine of heat decomposition temperature
Tool is mixed.
11. according to the preparation method of any one of claim 6~9 conductive polymer composite, it is characterised in that step
1) in, the melt blending is carrying out machinery altogether below heat decomposition temperature on the fusing point of polymer 1 and conductive filler carrier
It is mixed；The preparation method of the conductive filler carrier is：Polymer 2 and conductive filler are thermally decomposed on the fusing point of polymer 2
Machinery is mixed below temperature.
12. the preparation method of conductive polymer composite according to claim 5, it is characterised in that step 3) in, it is described
Heat pressing process refers to：By step 2) the porous conductive filler composite of polymer 1/ of gained utilizes a level pressure at a certain temperature
Power, suppresses to the hole made in the porous conductive filler composite of polymer 1/ and merges compacting；Wherein, certain temperature is
Ensure that polymer 1 has mobility but keeps the temperature of larger viscosity simultaneously, its determination mode is：The starting of crystalline polymer is melted
Melt below temperature melt point above, glass transition temperature ± 30 DEG C of amorphous polymer；Certain pressure exists to be not less than polymer 1
The minimum pressure that can be compacted at this temperature.
13. according to the preparation method of any one of claim 6~10 conductive polymer composite, it is characterised in that step
It is rapid 3) in, the heat pressing process refers to：By step 2) the porous conductive filler composite of polymer 1/ of gained is at a certain temperature
Using certain pressure, suppress to the hole made in the porous conductive filler composite of polymer 1/ and merge compacting；Wherein,
Certain temperature has mobility for guarantee polymer 1 but keeps the temperature of larger viscosity simultaneously, and its determination mode is：Crystalline polymeric
Below the onset melting temperature melt point above of thing, glass transition temperature ± 30 DEG C of amorphous polymer；Certain pressure is not low
The minimum pressure that can be compacted at such a temperature in polymer 1.
14. a kind of reduce the method that the conductive filler composite material conductive percolation threshold of polymer 1/ keeps its mechanical performance simultaneously,
Characterized in that, polymer 2 and the conductive filler, are first blended and conduction are made by selection and the incompatible polymers 2 of polymer 1
Filling carrier, then the conductive filler carrier blend of polymer 1/ is made in conductive filler carrier and the melt blending of polymer 1；Then
Polymer 2 in the conductive filler carrier blend of polymer 1/ is mutually completely dissolved removing, the porous conduction of polymer 1/ is obtained and fills out
Expect blend；The porous conductive filler blend of polymer 1/ is finally passed through into the heat pressing process system described in claim 12 or 13
Obtain the conductive filler composite of polymer 1/ of low conductive percolation threshold；Wherein, polymer 1 and polymer 2 polymerize for thermoplasticity
Thing.
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