CN101488373B - preparation of conductive composite material - Google Patents
preparation of conductive composite material Download PDFInfo
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- CN101488373B CN101488373B CN2009101032901A CN200910103290A CN101488373B CN 101488373 B CN101488373 B CN 101488373B CN 2009101032901 A CN2009101032901 A CN 2009101032901A CN 200910103290 A CN200910103290 A CN 200910103290A CN 101488373 B CN101488373 B CN 101488373B
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- 239000002131 composite material Substances 0.000 title claims abstract description 74
- 238000002360 preparation method Methods 0.000 title claims description 18
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- 238000010438 heat treatment Methods 0.000 claims abstract description 78
- 239000011231 conductive filler Substances 0.000 claims abstract description 72
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- 229910021393 carbon nanotube Inorganic materials 0.000 description 37
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Abstract
The invention discloses a conductive composite material and a manufacturing method and an application thereof, comprising a second polymer and the conductive composite which is combined with the second polymer and is provided with continuous phase, the conductive composite is composed of a first polymer and conductive filler which is contained in the first polymer and forms a conductive network, fusion temperature of the second polymer is higher than the fusion temperature of the first polymer, the invention adopts the manufacturing methods of stretching and heat treatment, so that the conductive composite material has relatively low percolation threshold after processing and forming, in addition, in the process of the processing, the conductive composite material can still maintain most of the mechanical properties after the heat treatment at relatively high temperature, thus ensuring that the whole material has fine conductivity and mechanical properties and can be applied to anti-static products, electromagnetic shielding products or circuits. The invention features easy operation of the manufacturing method, good universality and relatively easy recovery of the conductive composite material, in addition, the invention eliminates the problem in the prior art that the recovery of the composite material is difficult as the high strength fiber is added to the composite material to increase strength of the composite material.
Description
Technical field
The present invention relates to a kind of conducing composite material, particularly a kind of conducing composite material and its production and application.
Background technology
Conducting polymer composite is the polymeric material with conducting function.But having little, the easy processing of density, corrosion-resistant large tracts of land film forming and conductivity, macromolecule conducting material characteristics such as can regulate, not only can be used as the substitute of multiple metal material and inorganic conductive material, and become the indispensable class material of many advanced industrial departments and sophisticated technology field.
Because conducting polymer composite has very wide industrial use, therefore, need make different shapes and through different procedure of processings, as injection mo(u)lding, spinning is extruded or is stretched.In the above course of processing, conductive network can be subjected to influence in various degree, and in the processed process of the polymer of macromolecule and conductive filler, conductivity can reduce, though the recovery that conductivity can be slowly under molten condition, it is longer to recover time of needing.
Facts have proved that near high-temperature heat treatment (melt temperature of high temperature sweep limits from room temperature to this material) can improve the conductance of macromolecule conducting material.Carry out at glass transition temperature (T
g) and melt temperature (T
m) heat treatment can significantly increase the conductance of conducting polymer fiber.But heat treatment has adverse effect to the mechanical property of conducting polymer composite, thereby at high temperature molecules align can the out-of-sequence mechanical property that reduces material.
The unexpected increase that the conducting polymer composite conductivity can occur in the process that increases the conductive filler amount, the amount of the particular conductivity filler that this occurs when the conductance that increases suddenly is known as percolation threshold, and percolation threshold reduces gradually along with the increase of filler length-width ratio; If conductive filler can have bigger length-width ratio, conductive filler has less percolation threshold and can add less amount and just can make it in certain material like this, thereby can suitably increase the mechanical performance of material.
Therefore, need a kind of conducting polymer, have lower percolation threshold after the machine-shaping, and in the course of processing, can after than the heat treatment of higher temperature, still keep its most of mechanical performance.
Summary of the invention
In view of this, the purpose of this invention is to provide a kind of conducing composite material and its production and application, conductive filler can have bigger length-width ratio and add less amount, has lower percolation threshold after the machine-shaping, and in the course of processing, can after than the heat treatment of higher temperature, still keep its most of mechanical performance, the preparation method is simple, highly versatile, and cost is low.
Conducing composite material of the present invention, comprise second polymer and merge electrically conductive composition with continuous phase with second polymer scale, described electrically conductive composition is by first polymer and be contained in first polymer and the conductive filler that forms conductive network is formed, and the melt temperature of described second polymer is higher than the melt temperature of first polymer.
Further, serve as reasons one deck electrically conductive composition at least and the layer structure that constitutes of one deck second polymer at least of described conducing composite material;
Further, described conductive filler is material with carbon element or metal material;
Further, described conductive filler is a material with carbon element, and described material with carbon element is carbon nano-tube or carbon black;
Further, described material with carbon element is a carbon nano-tube, and described carbon nano tube surface is through oxidation processes or have polymer coating;
Further, first polymer is one or more the mixture in polyolefin, polyester, polyamide, Merlon and the polymethyl methacrylate; Second polymer is one or more the mixture in polyolefin, polyester, polyamide and the Merlon;
Further, first polymer is one or more the mixture in the different amount Molecularly Imprinted Polymer of polypropylene, the different amount Molecularly Imprinted Polymer of polyamide, the different amount Molecularly Imprinted Polymer of polyphenyl dioctyl phthalate glycol ester, high density polyethylene (HDPE) and the low density polyethylene (LDPE); Second polymer is one or more the mixture in the different amount Molecularly Imprinted Polymer of polypropylene, polyethylene, PETG, polyamide 6, high density polyethylene (HDPE) and polyamide 6;
Further, layered structure is the film or the band shape of flat bed structure; The fibre layered structure that at least one sheath layer and at least one core layer of perhaps serving as reasons formed;
Further, layered structure is two-layer flat bed structure, being combined as of first polymer and second polymer: the different amount Molecularly Imprinted Polymer/polypropylene of polypropylene, low density polyethylene (LDPE)/high density polyethylene (HDPE), the different amount Molecularly Imprinted Polymer/polyamide 6 of polyamide 6, the different amount Molecularly Imprinted Polymer/PETG of PETG, low density polyethylene (LDPE)/polypropylene, high density polyethylene (HDPE)/polypropylene, low density polyethylene (LDPE)/polyamide 6 or the different amount Molecularly Imprinted Polymer/PETG of polyamide 6;
Perhaps layered structure adopts two-layer first polymer with three layers the flat bed structure that second polymer is clipped in the middle, and is combined as: the different amount Molecularly Imprinted Polymer of low density polyethylene (LDPE)/polyamide 6/PETG, the different amount Molecularly Imprinted Polymer/PETG of the PETG/different amount Molecularly Imprinted Polymer of polyamide 6, the different amount Molecularly Imprinted Polymer of the different amount Molecularly Imprinted Polymer/polypropylene/polypropylene of polypropylene, the different amount Molecularly Imprinted Polymer/polyamide 6 of the PETG/different amount Molecularly Imprinted Polymer of polyamide 6, the different amount Molecularly Imprinted Polymer/polyamide 6 of the polyamide 6/different amount Molecularly Imprinted Polymer of polyamide 6, different amount Molecularly Imprinted Polymer of low density polyethylene (LDPE)/PETG/PETG or the different amount Molecularly Imprinted Polymer of low density polyethylene (LDPE)/PETG/polyamide 6;
Further, be added with conductive filler in described second polymer.
The invention also discloses a kind of preparation method of conducing composite material, may further comprise the steps:
A. conductive filler is sneaked into the first polymer manufacture electrically conductive composition, electrically conductive composition and the combination of second polymer are processed into level composite material just;
B. with first level composite material stretch forming and heat treatment, described heat treatment temperature is more than or equal to the melt temperature of first polymer, and the conducing composite material conductance of cooling forming is at least 10 after the heat treatment
-9S/m, hot strength 20MPa-20000MPa, Young's modulus is 100MPa-300GPa.
Further, the addition of conductive filler accounts for 0.0001% to 50% of first polymer by mass percentage in the electrically conductive composition;
Further, the addition of conductive filler accounts for 1% to 30% of first polymer by mass percentage in the electrically conductive composition;
Further, among the step a, the length-width ratio of conductive filler is more than or equal to 100, and the addition of conductive filler accounts for 1% to 6% of first polymer by mass percentage in the electrically conductive composition; Perhaps the length-width ratio of conductive filler is less than 100, and the addition of conductive filler accounts for 5% to 30% of first polymer by mass percentage in the electrically conductive composition;
Further, the melt temperature of second polymer is higher than at least 20 ℃ in first polymer;
Further, among the step b, heat treatment temperature is greater than at least 20 ℃ of the melt temperatures of first polymer, and the melt temperature that is lower than second polymer adds 80 ℃;
Further, among the step a, the electrically conductive composition and second polymer comprise compound extruding method, pressure sintering or co-blended spinning method in conjunction with processing method, form the first level composite material of layer structure in conjunction with processing back; Among the step b, form film, belt or the fiber of layer structure after stretching and the heat treatment;
Further, among the step b, the conducing composite material conductance of cooling forming is 10 after the heat treatment
-8S/m-1000S/m; The conducing composite material of cooling forming is fiber or belt, and hot strength is 100MPa-3GPa, and Young's modulus is 2GPa-180GPa; Perhaps the conducing composite material of cooling forming is a film, hot strength 20MPa-100MPa, yang type modulus 100MPa-2GPa.
The invention also discloses the application of a kind of conducing composite material in anti-static product, electromagnetic shielding product or circuit.
The invention has the beneficial effects as follows: conducing composite material of the present invention and its production and application, conducing composite material adopts the composition of multiple different melt temperatures, has lower percolation threshold after the machine-shaping, and in the course of processing, can after than the heat treatment of higher temperature, still keep its most of mechanical performance, thereby guarantee that whole material has good electrical conductivity and has the favorable mechanical performance;
Preparation method of the present invention is simple to operate, highly versatile, prospect with large-scale production, composite material favorable mechanical performance of the present invention is to be guaranteed by the component that has higher melt in the material, among the preparation method, thereby solid state drawing makes the molecular assembly arrangement of the part of higher melt provide the favorable mechanical performance for whole composite material; Heat treated temperature is higher than the lower part of fusing point, makes macromolecule that composite material the increases activity at high temperature under the state that melts, thereby causes the activity of conductive filler to increase, thereby guarantee the electric conductivity of composite material;
Conducing composite material of the present invention reclaims than being easier to, eliminated the problem of in composite material, adding high strength fibre enhancing intensity in the prior art and reclaiming difficulty, and the close material of composite material do as one likes matter of the present invention is formed, less conductive filler does not have materially affect to the recovery of whole material, material can simply be melted then to be reused, reclaim simply, save manufacturing cost.
Description of drawings
Below in conjunction with drawings and Examples the present invention is further described.
Fig. 1 is the schematic diagram of first kind of embodiment of flat bed structure of the present invention;
Fig. 2 is the schematic diagram of second kind of embodiment of flat bed structure of the present invention;
Fig. 3 is the schematic diagram of first kind of embodiment of the fibre layered structure of the present invention;
Fig. 4 is the schematic diagram of second kind of embodiment of the fibre layered structure of the present invention;
Fig. 5 is the schematic diagram of fibre layered the third embodiment of structure of the present invention;
Fig. 6 is a manufacture method flow chart of the present invention.
Embodiment
Fig. 1 is the schematic diagram of first kind of embodiment of flat bed structure of the present invention, as shown in the figure: the conducing composite material of present embodiment, comprise second polymer 1 and the electrically conductive composition 2 that combines and have continuous phase with second polymer 1, in the present embodiment, second polymer 1 is a polypropylene; Described electrically conductive composition 2 is by first polymer 21 and be contained in first polymer 21 and the conductive filler 22 that forms conductive network is formed, first polymer 21 is the different amount Molecularly Imprinted Polymer of polypropylene in the present embodiment, and the melt temperature that satisfies second polymer 1 is higher than the requirement of the melt temperature of first polymer 21;
In the present embodiment, conducing composite material is for being made of the banded layer structure of flat bed structure by hot pressing one deck electrically conductive composition 2 and one deck second polymer; Can certainly be membrane structure, can both reach goal of the invention;
Conductive filler is material with carbon element or metal material, conductive filler is a material with carbon element in the present embodiment, in light weight, associativity is good, and material with carbon element is a carbon nano-tube, has lower percolation threshold, conduct electricity very well, carbon nano-tube in the material with carbon element is better than metal material on electric conductivity, and because carbon nano-tube is a nano particle, common needed amount of filler is also fewer; In the present embodiment, the length-width ratio of used carbon nano-tube is all more than or equal to 100, and the addition of conductive filler accounts for 1% to 6% of first polymer by mass percentage in the electrically conductive composition; There is polymeric coating layer the carbon nano-tube outside, can strengthen the combination of carbon nanometer about macromolecule matrix, can be used for strengthening the dispersion of carbon nano-tube, also can form oxide layer in carbon nano tube surface, also can reach goal of the invention; Certainly, conductive filler also can be material with carbon elements such as carbon black or graphite, can both reach goal of the invention behind the adjustment addition, carbon black is the same with carbon nano-tube, better than metal material on electric conductivity, and because carbon black also is a nano particle, common needed amount of filler is also fewer;
Certainly, the kind that first polymer and second polymer are not limited to limit in the present embodiment, first polymer can also be one or more the mixtures in the different amount Molecularly Imprinted Polymer of polypropylene, the different amount Molecularly Imprinted Polymer of polyamide, the different amount Molecularly Imprinted Polymer of polyphenyl dioctyl phthalate glycol ester, high density polyethylene (HDPE) and the low density polyethylene (LDPE); Second polymer can also be a kind of in the different amount Molecularly Imprinted Polymer of polyethylene, PETG, polyamide 6, high density polyethylene (HDPE) and polyamide 6; Certainly, above material also can be more than one mixture, can both realize goal of the invention; Selected first polymer of above polymer and second polymer have enough melt temperature differences between them, are of value to heat treatment like this; And above polymer all has certain stretch capability, and industrial had very widely use, so their made conductive fiber has very wide application prospect;
In the present embodiment, the compound mode of first polymer and second polymer also can change with the different of material category, such as: low density polyethylene (LDPE)/high density polyethylene (HDPE), the different amount Molecularly Imprinted Polymer/polyamide 6 of polyamide 6, the different amount Molecularly Imprinted Polymer/PETG of PETG, low density polyethylene (LDPE)/polypropylene, high density polyethylene (HDPE)/polypropylene, low density polyethylene (LDPE)/polyamide 6 or the different amount Molecularly Imprinted Polymer/PETG of polyamide 6; Can both be to goal of the invention, more than combination can have different ratios according to different actual needs, the occasion higher to requirement of mechanical strength, the ratio of second polymer should suitably be higher than first polymer; These combinations guarantee that first polymer and second polymer have enough melt temperature differences between them, are of value to heat treatment like this; And above polymer all has certain stretch capability, and industrial had very widely use, can reduce experimentation cost and manufacturing cost.
In addition, first polymer and second polymer are not limited to have only separately one deck, can be multilayers, and every layer material can be different; That is to say that first polymer among the present invention and second polymer are not only to refer to certain particular polymers, and might multilayer composition first polymer or the second different polymer of multilayer composition inequality.
Fig. 6 is a manufacture method flow chart of the present invention, and the preparation method of present embodiment conducing composite material may further comprise the steps:
A. conductive filler is sneaked into the first polymer manufacture electrically conductive composition, in the present embodiment, the different amount Molecularly Imprinted Polymer of carbon nano-tube and polypropylene is extruded after 200 ℃ of mixing, and the film of thickness about 150 microns made in hot pressing in 5 minutes under 200 ℃ of conditions, forms electrically conductive composition; The heat pressure film under 155 ℃ of conditions with electrically conductive composition film and second polymer (polypropylene) film forms multicomponent level composite material just; In the present embodiment, the length-width ratio of used carbon nano-tube is more than or equal to 100, carbon nano-tube addition account for the 1%-6% (seeing Table 3) of the different amount Molecularly Imprinted Polymer of propylene by mass percentage;
B. first level composite material is stretched down at 120 ℃, the draw ratio different with different structure controls according to different materials, film is compared draw ratio with strap configurations relative less, present embodiment adopts strap configurations, draw ratio is 6-20 (seeing Table 4), heat-treat in ℃ down heating 0-400 minute of room temperature-165 (see Table 4 and table 5) back that stretches, (melt temperature is the starting point that polymer melts the peak to heat treatment temperature in the presents greater than the melt temperature of first polymer (the different amount Molecularly Imprinted Polymer of polypropylene), also comprise glass transition temperature for the amorphous polymer that does not have fusion temperature), less than polyacrylic melt temperature (167 ℃); Certainly, no matter be material or other material that adopts in the present embodiment, heat treatment temperature is greater than at least 20 ℃ of the melt temperatures of first polymer, and the melt temperature that is lower than second polymer adds 80 ℃, is beneficial to the mechanical performance that keeps material and strengthens electric conductivity; In the present embodiment, the melt temperature of the different amount Molecularly Imprinted Polymer of polypropylene is lower than polyacrylic melt temperature above 20 ℃, can make full use of temperature difference heat-treats, be beneficial to and guarantee electric conductivity of the present invention, if this difference is equal to or greater than 20 ℃, that stays enough processing spaces will in heat treatment process the whole course of processing, mean that heat treatment time can be longer, heat treatment temperature can be higher, bring higher conductance to material, simultaneously, after heat treatment, the mechanical performance of material also is not easy impaired more; In the practice, as long as there is temperature difference, all be beneficial to the realization of the object of the invention, and the melt temperature of second polymer is higher than first polymer above 20 ℃, but and be no more than 80 ℃ of second polymer melting temperatures, be selection indicators, not only guarantee electric conductivity, can also guarantee the mechanical performance of material to greatest extent;
The conducing composite material performance index of cooling forming are seen following form after the heat treatment:
Table 1: get 5 samples the conductive composite material resistance rate compared detection, sample 1 to the sample 5 in the electrically conductive composition addition of conductive filler account for 0.0001% to 50% of first polymer by mass percentage:
| ? | |
Sample 2 | Sample 3 | Sample 4 | Sample 5 |
| Resistivity [Ohm.m] before stretching | 2.6 | 3.4 | 530 | 5800 | Non-conductive |
| Resistivity behind the solid state drawing [Ohm.m] | Non-conductive | Non-conductive | Non-conductive | Non-conductive | Non-conductive |
| Resistivity after solid state drawing and the heat treatment [Ohm.m] | 0.065 | 0.065 | 0.65 | 0.4 | 0.35 |
As can be seen from the above table, solid state drawing has destroyed the conductive network that conductive filler is formed, and conductive network has been repaired in heat treatment, and the later conductive network of solid state drawing of the present invention and heat treatment is stronger than the former conductivity of solid state drawing, and therefore, percolation threshold is also just less; And according to the material difference, the conductance of conducing composite material is at least 10
-9S/m;
Table 2: the second polymer layer measuring mechanical property in the conducing composite material of the present invention (draw ratio is 20)
| ? | Behind the solid state drawing | Stretched the back 165 ℃ of following heat treatments 1000 seconds | Stretched the back 165 ℃ of following heat treatments 4000 seconds |
| Yang type modulus [GPa] | 10.5±0.4 | 9.8±0.4 | 9.4±1.0 |
| Tensile strength [MPa] | 472±24 | 425±6.9 | 435±28 |
| Fracture elongation strain [%] | 8.7±0.5 | 9.6±1.6 | 12±1.4 |
The mechanical property of conducing composite material of the present invention is mainly guaranteed by second polymer (polypropylene), and the first polymeric layer common mechanical poor-performing, because being higher than macromolecule obtained being oriented in the heat treatment process under solid state drawing first polymeric layer there, heat treatment temperature lost, so their mechanical performance also can be lower.As can be seen from the above table, the tensile strength of yang type modulus has faint reduction after heat treatment, and the fracture elongation strain has slight rising, and overall mechanical properties is better; And according to the difference of material,, the hot strength 20MPa-20000MPa of the conducing composite material of cooling forming after the heat treatment, Young's modulus is 100MPa-300GPa, can reach goal of the invention;
Table 3: the carbon nano-tube addition is to the influence of electric conductivity, and heat treatment temperature is 155 ℃, and the time is 15 minutes, and mass percent is the mass percent that conductive filler accounts for first polymer;
| The multi-walled carbon nano-tubes mass percent | ?1 | 1.44 | 1.82 | 2.3 | 3.1 | 6 |
| Resistivity [Ohm.m] before stretching | Non-conductive | 3030 | 188 | 8 | 3.9 | 0.11 |
| Resistivity after the stretching [Ohm.m] | Non-conductive | Non-conductive | Non-conductive | Non-conductive | Non-conductive | 17.8 |
| Resistivity after solid-state stretching down and the heat treatment: [Ohm.m] | 34400 | 0.5 | 0.40 | 0.14 | 0.2 | 0.014 |
As can be seen from the above table,, be beneficial to the raising of the electric conductivity that increases material, and heat treatment strengthened the electric conductivity of material, and be suitable for adding the electric conducting material of any ratio conductive filler along with the increase of content of carbon nanotubes.
Table 4: heat treatment time and draw ratio are to the influence (carbon nano-tube is 5.3% with respect to the quality percentage composition of first polymer) of electric conductivity
| Heat treatment time [second] | Temperature [℃] | Draw ratio is 6 resistivity Ohm.m] | Draw ratio is 8 resistivity [Ohm.m] | Draw ratio is 13 resistivity [Ohm.m] | Draw ratio is 20 resistivity [Ohm.m] |
| 0 | Room temperature | 0.53 | 3.06 | 8830 | 1.14E6 |
| 500 | 165 | 0.063 | 0.34 | 18 | 930 |
| 1000 | 165 | 0.0093 | 0.0096 | 0.007 | 0.03 |
| 1500 | 165 | 0.0074 | 0.0076 | 0.0038 | 0.006 |
| 2000 | 165 | 0.008 | 0.01 | 0.004 | 0.0054 |
| 2500 | Room temperature | 0.009 | 0.01 | 0.0044 | 0.0064 |
As can be seen from the above table, draw ratio increases can reduce conductivity of electrolyte materials, and still along with the prolongation of heat treatment time, conductivity can increase, and the conducing composite material that heat treatment is suitable for any draw ratio improves electric conductivity;
Table 5: heat treatment temperature and time are to the influence (draw ratio is 21) of electric conductivity
| Heat treatment time [second] | Heat treatment temperature [℃] | Resistivity [Ohm.m] |
| 0 | Room temperature | 1.4E7 |
| 2000 | 80 | 1.76E6 |
| 4000 | 80 | 1.3E6 |
| 6000 | 80 | 1.6E6 |
| 8000 | 80 | 1.2E6 |
| 10000 (about 8400 seconds, oven temperature is upgraded to 100 ℃) | 100 | 1.14E6 |
| 12000 | 100 | 542000 |
| 14000 | 100 | 541000 |
| 16000 | 100 | 330000 |
| 18000 (about 16000 seconds, oven temperature is upgraded to 120 ℃) | 120 | 290000 |
| 18535 (about 18500 seconds, oven temperature is upgraded to 155 ℃) | 155 | 270000 |
| 19000 | 155 | 3.9 |
| 20000 | 155 | 0.2 |
| 22000 | 155 | 0.12 |
| 25000 (about 23000 seconds, baking oven begins cooling) | Room temperature | 0.14 |
As can be seen from the above table, along with the rising of heat treatment temperature and the prolongation of heat treatment time, the electric conductivity of material improves; Heat treatment can be carried out in the relatively low temperature melt temperature height of first polymer (still than), but the time that needs is longer relatively; Perhaps heat treatment also can be carried out at higher temperature, like this time of usefulness shorter relatively, can both realize the object of the invention;
Can illustrate that by data in the above form conducing composite material of the present invention not only has conductivity preferably, also keep the favorable mechanical performance.
Fig. 2 is the schematic diagram of second kind of embodiment of flat bed structure of the present invention, as shown in the figure: the difference of present embodiment and first kind of embodiment of flat bed structure is: present embodiment is the three-decker of flat bed, and the second polymer layer forms three layers of flat bed structure in the middle of being clipped in two electrically conductive composition layers; Be applicable to that the material of first kind of embodiment and stretching and heat treatment method all are applicable to present embodiment.
Certainly, first kind of embodiment is the same for present embodiment and flat bed structure, the kind that first polymer and second polymer are not limited to limit in the present embodiment, first polymer can also be one or more the mixtures in the different amount Molecularly Imprinted Polymer of polypropylene, the different amount Molecularly Imprinted Polymer of polyamide, the different amount Molecularly Imprinted Polymer of polyphenyl dioctyl phthalate glycol ester, high density polyethylene (HDPE) and the low density polyethylene (LDPE); Second polymer can also be a kind of in the different amount Molecularly Imprinted Polymer of polyethylene, PETG, polyamide 6, high density polyethylene (HDPE) and polyamide 6; Certainly, above material also can be more than one mixture, and the melt temperature that satisfies second polymer is higher than at least 5 ℃ of the melt temperatures of first polymer; Best, the melt temperature of second polymer is higher than at least 30 ℃ in first polymer;
In the present embodiment, the compound mode of first polymer and second polymer also can change with the different of material category, first type of polymer of forming two-layer electrically conductive composition layer can be the same or different, combination can be low density polyethylene (LDPE)/polyamide 6/PETG different amount Molecularly Imprinted Polymer, the different amount Molecularly Imprinted Polymer/PETG of the PETG/different amount Molecularly Imprinted Polymer of polyamide 6, the different amount Molecularly Imprinted Polymer of the different amount Molecularly Imprinted Polymer/polypropylene/polypropylene of polypropylene, the different amount Molecularly Imprinted Polymer/polyamide 6 of the PETG/different amount Molecularly Imprinted Polymer of polyamide 6, the different amount Molecularly Imprinted Polymer/polyamide 6 of the polyamide 6/different amount Molecularly Imprinted Polymer of polyamide 6, different amount Molecularly Imprinted Polymer of low density polyethylene (LDPE)/PETG/PETG or the different amount Molecularly Imprinted Polymer of low density polyethylene (LDPE)/PETG/polyamide 6 can both be realized goal of the invention;
Make the carbon nano-tube among second kind of embodiment of flat bed structure into carbon black, can obtain the influence of content of carbon black to the conducing composite material electric conductivity, according to the physical property of carbon black, the length-width ratio of used carbon black is all less than 100;
Table 6: heat treatment is the influence of the conductivity of composite material energy of carbon black to conductive filler, and mass percent is the mass percent that conductive filler accounts for first polymer;
| The carbon black mass percent | 5 | 10 | 11 | 13 | 15 | 30 |
| The resistivity [Ohm.m] of sandwich belt before stretching | 2.4 | 0.08 | 0.08 | 0.06 | 0.05 | 0.025 |
| The resistivity of sandwich belt behind the solid state drawing (draw ratio 8): [Ohm.m] | Non-conductive | 566 | 1.3 | 0.66 | 0.5 | 0.2 |
| The resistivity [Ohm.m] of the sandwich belt after solid state drawing and the heat treatment | 3.8 | 0.13 | 0.08 | 0.06 | 0.06 | 0.03 |
As can be seen from the above table,, be beneficial to the raising of the electric conductivity of material, and heat treatment strengthened the electric conductivity of back material that stretches, and be suitable for adding the electric conducting material of any ratio conductive filler along with the increase of content of carbon black.
The material that adds carbon black has similar technical characterictic because of preparation process with material character with the mechanical performance of the material that adds carbon nano-tube, thereby, have similar rule to embodiment shown in Figure 1;
Heat treatment temperature and time, extensibility also have similar rule to embodiment shown in Figure 1 to the influence of conducing composite material electric conductivity, and is not giving unnecessary details at this place.
Certainly, add the general property of conductive filler in the polymer, in laboratory and the actual production, the addition of conductive filler accounts for 0.0001% to 50% of first polymer by mass percentage in the electrically conductive composition, can both reach goal of the invention; And the preferable result that obtains of chamber and half suitability for industrialized production is by experiment: the addition of conductive filler accounts for 1% to 30% of first polymer by mass percentage in the electrically conductive composition; Can reach higher conductance like this, and don't can add too many conductive filler and lose good processing properties, thereby cause the processing technology complexity, the product cost height;
Best, the length-width ratio of conductive filler is more than or equal to 100 (such as carbon nano-tube), and the addition of conductive filler accounts for 1% to 6% of first polymer by mass percentage in the electrically conductive composition; Perhaps the length-width ratio of conductive filler is less than 100 (such as carbon black or graphite), and the addition of conductive filler accounts for 5% to 30% of first polymer by mass percentage in the electrically conductive composition; The length-width ratio of conductive filler has crucial effects to the amount of needed conductive filler in the electric conducting material, and length-width ratio is long more, and needed conductive filler is just few more, thereby conductive filler is just few more to the processing characteristics and the mechanical performance influence of final material.So the amount of the conductive filler that needed length-width ratio is different in conducting polymer is also different.
Fig. 3 is the schematic diagram of first kind of embodiment of the fibre layered structure of the present invention, as shown in the figure: present embodiment is by second polymer 1 and the electrically conductive composition 2 that combines and have continuous phase with second polymer 1, is sheath layer that is made of electrically conductive composition 2 and the fibre layered structure of being made up of the core layer that second polymer 1 constitutes in the present embodiment; In the present embodiment, second polymer 1 is a polyamide 6; Electrically conductive composition 2 is by first polymer and be contained in first polymer and the conductive filler that forms conductive network is formed, and the cross section of core layer is a circle; First polymer 21 is a low density polyethylene (LDPE) in the present embodiment, and the melt temperature that satisfies second polymer 1 is higher than the requirement of the melt temperature of first polymer;
Conductive filler is material with carbon element or metal material, and conductive filler is material with carbon element in the present embodiment, and is in light weight, and associativity is good; Material with carbon element is a carbon nano-tube, has lower percolation threshold, conducts electricity very well; In the present embodiment, the length-width ratio of used carbon nano-tube is all more than or equal to 100, and the addition of conductive filler accounts for 5% of first polymer by mass percentage in the electrically conductive composition; Carbon nano-tube has polymeric coating layer outward, mainly is in order to strengthen the combination of carbon nanometer about macromolecule matrix, to can be used for strengthening the dispersion of carbon nano-tube, and is surperficial certainly through oxidation processes, also can reach goal of the invention; Certainly, conductive filler also can be material with carbon elements such as carbon black or graphite, can both reach goal of the invention behind the adjustment addition;
During preparation, at first carbon nano-tube and low density polyethylene (LDPE) are made electrically conductive composition, then electrically conductive composition and polyamide 6 are made blend, blend is spun into fibre structure, with the solid state drawing of fiber, draw ratio is 4.5, and draft temperature is 80 ℃; Heat-treat is by allowing fibre high-speed (100 meters per minutes) realize by 1 meter long baking oven (it is provided with temperature is 280 ℃);
Table 7: for the contrast of the electric conductivity of present embodiment detects
| ? | Extruded stock | Behind the solid state drawing | The stretching after-baking |
| Resistivity [Ohm.m] | 0.26 | Non-conductive | 20.1 |
As can be seen from the above table, heat treatment has very significantly improved the conductivity of fiber behind the solid state drawing;
The mechanical performance of present embodiment because preparation process and material form to the flat bed structure in first kind of embodiment have similar technical characterictic, thereby, have similar rule to first kind of embodiment in the flat bed structure;
Heat treatment temperature and time, extensibility, content of carbon nanotubes also have similar rule to embodiment one to the influence of conducing composite material electric conductivity, and is not giving unnecessary details at this place.
Fig. 4 is the schematic diagram of second kind of embodiment of the fibre layered structure of the present invention, as shown in the figure: the difference of present embodiment and first kind of embodiment of fibre layered structure shown in Figure 3 is: the cross section of core layer is a Y shape, the present embodiment core layer adopts Y shape cross-sectional structure, increase the contact area of sheath layer and core layer, be beneficial to the enhancing bond strength.
Fig. 5 is the schematic diagram of fibre layered the third embodiment of structure of the present invention, and as shown in the figure: present embodiment is with the difference of first kind of embodiment of fibre layered structure shown in Figure 3: the sheath layer is evenly distributed on the circumference of core layer for individual.
Fibre layered structure is not limited to the structure that above embodiment narrates, core layer and sheath layer can be multilayer, the core layer of different layers can be different types of polymer, the sheath layer of different layers also can be different types of polymer, core layer can also be ellipse, H shape, X-shaped or the like, can both realize goal of the invention.
Through laboratory sample and the sampling of the product that partly industrially produces are detected, among the present invention, the conducing composite material conductance of cooling forming is 10 after the heat treatment
-8S/m-1000S/m; If the conducing composite material of cooling forming is fiber or belt, hot strength is 100MPa-3GPa, and Young's modulus is 2GPa-180GPa; If the conducing composite material of cooling forming is a film, hot strength 20MPa-100MPa, yang type modulus 100MPa-2GPa all can satisfy actual needs.
Below be the three layers of flat bed structure and the two-layer flat bed structure belt electric conductivity experimental data of different first polymer and second combination of polymers:
In the following form, the percentage composition of conductive filler is the mass percent that conductive filler accounts for first polymer;
Table 8:
Electrically conductive composition layer (two-layer) comprising: conductive filler: 5% carbon nano-tube, first polymer: the different amount Molecularly Imprinted Polymer of polyamide 6; Second polymer: polyamide 6;
Belt thickness ratio: 1: 4: 1, draw ratio 4.19,140 ℃ of draft temperatures
| ? | Extruded stock | Behind the solid state drawing | 170 ℃ of following heat treatments 20 minutes | 200 ℃ of following heat treatments 30 minutes |
| Resistivity [Ohm.m] | 3.5 | 1.7E7 | 840360.9 | 204.1 |
Table 9:
Electrically conductive composition layer (two-layer) comprising: conductive filler: 5wt.% carbon nano-tube, first polymer: the different amount Molecularly Imprinted Polymer of polyamide 6; Second polymer: polyamide 6;
Multicomponent belt thickness ratio: 1: 48: 1, draw ratio 4.26,140 ℃ of draft temperatures
| ? | Extruded stock | Behind the solid state drawing | 170 ℃ of following heat treatments 20 minutes | 200 ℃ of following heat treatments 30 minutes |
| Resistivity [Ohm.m] | 9.6 | Non-conductive | 113800.6 | 3340.6 |
Table 10:
Electrically conductive composition layer (one deck) comprising: conductive filler: 5% carbon nano-tube, first polymer: the different amount Molecularly Imprinted Polymer of PETG; Second polymer: PETG
Multicomponent belt thickness is than 1: 10, draw ratio 5.27,80 ℃ of draft temperatures
| ? | Extruded stock | Behind the solid state drawing | 120 ℃ of heat treatment temperatures | 150 ℃ of heat treatment temperatures |
| Resistivity [Ohm.m] | 0.11 | 3.3*10 7 | 1030.60 | 9.2 |
Table 11
Electrically conductive composition layer (two-layer) comprising: conductive filler: 5% carbon nano-tube, first polymer: the different amount Molecularly Imprinted Polymer of polyamide 6; Second polymer: polyamide 6
Multicomponent belt thickness is than 1: 10: 1, draw ratio 4.85,70 ℃ of draft temperatures
| ? | Extruded stock | Behind the solid state drawing | 170 ℃ of heat treatment temperatures | 200 ℃ of heat treatment temperatures |
| Resistivity [Ohm.m] | 0.34 | Non-conductive | 209400 | 241.5 |
Table 12
Electrically conductive composition layer (one deck) comprising: conductive filler: 5% carbon nano-tube, first polymer: low density polyethylene (LDPE); Second polymer: polypropylene
Multicomponent belt thickness is than 1: 4, draw ratio 8,120 ° of draft temperatures
| ? | Extruded stock | Behind the solid state drawing | 150 ℃ of heat treatment temperatures |
| Resistivity [Ohm.m] | 0.3 | Non-conductive | 11.5 |
Table 13
Electrically conductive composition layer (one deck) comprising: conductive filler: 3.5% carbon nano-tube, first polymer: low density polyethylene (LDPE); Second polymer: polyamide 6
Multicomponent belt thickness is than 1: 2, draw ratio 5.8,120 ℃ of draft temperatures
| ? | Extruded stock | Belt behind the solid state drawing | 150 ℃ of heat treatment temperatures |
| Resistivity [Ohm.m] | 40.3 | Non-conductive | 327.1 |
Table 14
Electrically conductive composition layer (two-layer): ground floor electrically conductive composition layer comprises: conductive filler: 5% carbon nano-tube, first polymer: the different amount Molecularly Imprinted Polymer of PETG; Second layer electrically conductive composition layer comprises: conductive filler: 5wt.% carbon nano-tube, first polymer: low density polyethylene (LDPE); Second polymer: polyamide 6;
Multicomponent belt thickness is than 1: 10: 1, draw ratio 5.19,80 ℃ of draft temperatures
| ? | Extruded stock | Belt behind the solid state drawing | 150 ℃ of heat treatment temperatures |
| Resistivity [Ohm.m] | 0.17 | Non-conductive | 120.3 |
Table 15
Electrically conductive composition layer (two-layer): ground floor electrically conductive composition layer comprises: conductive filler: 5% carbon nano-tube, first polymer: the different amount Molecularly Imprinted Polymer of PETG; Second layer electrically conductive composition layer comprises: conductive filler: 2% carbon nano-tube, first polymer: the different amount Molecularly Imprinted Polymer of polyamide 6; Second polymer: PETG
Multicomponent belt thickness is than 1: 10: 1, draw ratio 5.76,80 ℃ of draft temperatures
| ? | Extruded stock | Belt behind the solid state drawing | 150 ℃ of heat treatment temperatures |
| Resistivity [Ohm.m] | 0.17 | Non-conductive | 10.1 |
Table 16
Electrically conductive composition layer (one deck): comprising: conductive filler: 5% carbon nano-tube, first polymer: polymethyl methacrylate; Second polymer: Merlon
Multicomponent belt thickness is than 1: 2, draw ratio 4,120 ℃ of draft temperatures
| ? | Extruded stock | Belt behind the solid state drawing | 160 ℃ of heat treatment temperatures, heat treatment time 20mins |
| Resistivity [Ohm.m] | 30.2 | Non-conductive | 305.5 |
In the above form as can be seen, first polymer in the electrically conductive composition layer can divide two-layer, can certainly be two-layer more than, first type of polymer of different layers can be the same or different, the content of different layers conductive filler can be the same or different, and all can reach goal of the invention;
Different macromolecules is used in the above-mentioned multicomponent belt, and heat treatment process is proved to be the resistivity that significantly reduces the multicomponent belt, yet heat treatment process does not but have big influence to their mechanical performance; Heat treatment process is proved to be and is applicable to these all macromolecules combinations, this comprises polyolefin, polyester, polyamide, indefiniteness polymer or elastomer, the mechanical performance of multicomponent belt is remained after heat treatment in a large number, can guarantee the mechanical performance of conducing composite material of the present invention, and can guarantee that electric conducting material has excellent conducting performance; By above embodiment, structure of the present invention and preparation method go for any macromolecular material.
Certainly, also can in second polymer, add conductive filler, under the prerequisite of considerable influence mechanical performance not, increase electric conductivity, also can realize purpose of the present invention.
Because conducing composite material of the present invention has excellent conducting performance and mechanical performance, the therefore application in anti-static product, electromagnetic shielding product or circuit.
Explanation is at last, above embodiment is only unrestricted in order to technical scheme of the present invention to be described, although the present invention is had been described in detail with reference to preferred embodiment, those of ordinary skill in the art is to be understood that, can make amendment or be equal to replacement technical scheme of the present invention, and not breaking away from the aim and the scope of technical solution of the present invention, it all should be encompassed in the middle of the claim scope of the present invention.
Claims (7)
1. the preparation method of a conducing composite material is characterized in that: may further comprise the steps:
A. conductive filler is sneaked into the first polymer manufacture electrically conductive composition, the electrically conductive composition and second polymer are processed into level composite material just by compound extruding method, pressure sintering or co-blended spinning method; The melt temperature of described second polymer is higher than the melt temperature of first polymer;
B. with first level composite material stretch forming and heat treatment, described heat treatment temperature is more than or equal to the melt temperature of first polymer, and the conducing composite material conductance of cooling forming is at least 10 after the heat treatment
-9S/m, hot strength 20MPa-20000MPa, Young's modulus is 100MPa-300GPa.
2. the preparation method of conducing composite material according to claim 1, it is characterized in that: the addition of conductive filler accounts for 0.0001% to 50% of first polymer by mass percentage in the electrically conductive composition.
3. the preparation method of conducing composite material according to claim 2, it is characterized in that: the addition of conductive filler accounts for 1% to 30% of first polymer by mass percentage in the electrically conductive composition.
4. the preparation method of conducing composite material according to claim 3, it is characterized in that: among the step a, the length-width ratio of conductive filler is more than or equal to 100, and the addition of conductive filler accounts for 1% to 6% of first polymer by mass percentage in the electrically conductive composition; Perhaps the length-width ratio of conductive filler is less than 100, and the addition of conductive filler accounts for 5% to 30% of first polymer by mass percentage in the electrically conductive composition.
5. the preparation method of conducing composite material according to claim 4, it is characterized in that: the melt temperature of second polymer is higher than at least 20 ℃ in first polymer.
6. the preparation method of conducing composite material according to claim 5, it is characterized in that: among the step a, the electrically conductive composition and second polymer comprise compound extruding method, pressure sintering or co-blended spinning method in conjunction with processing method, form the first level composite material of layer structure in conjunction with processing back; Among the step b, form film, belt or the fiber of layer structure after stretching and the heat treatment.
7. the preparation method of conducing composite material according to claim 6, it is characterized in that: among the step b, the conducing composite material conductance of cooling forming is 10 after the heat treatment
-8S/m-1000S/m; The conducing composite material of cooling forming is fiber or belt, and hot strength is 100MPa-3GPa, and Young's modulus is 2GPa-180GPa; Perhaps the conducing composite material of cooling forming is a film, hot strength 20MPa-100MPa, and Young's modulus is 100MPa-2GPa.
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| CN102690528B (en) * | 2012-06-25 | 2014-12-17 | 西南交通大学 | Method for preparing polymer-base conductive composite material by melt blending |
| CN102731994B (en) * | 2012-07-03 | 2014-08-13 | 金发科技股份有限公司 | Nylon composite, preparation method, application thereof and plastic product of nylon composite |
| CN103772977A (en) * | 2013-12-20 | 2014-05-07 | 安徽孟凌精密电子有限公司 | Super-black and bright high-glossiness nylon PA66 nylon gasket composite material combined material |
| CN108353523B (en) * | 2015-11-25 | 2020-02-25 | 株式会社巴川制纸所 | Matching type electromagnetic wave absorber |
| CN105647017B (en) * | 2016-04-05 | 2017-09-01 | 四川大学 | Conductive polymer composite with continuous isolation structure and preparation method thereof |
| CN106003957A (en) * | 2016-06-28 | 2016-10-12 | 嘉兴市高正高分子材料有限公司 | Antistatic PA (Polyamide) film |
| WO2020145884A1 (en) * | 2019-01-10 | 2020-07-16 | Sembcorp Industries Ltd | A method of forming a stretchable conductive carbon nanofilm |
| CN113045813B (en) * | 2021-04-16 | 2021-12-31 | 四川大学 | High-molecular composite material with high mechanical strength and high bidirectional thermal conductivity and preparation thereof |
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