CN102899742A - Electrically conductive composite fiber containing carbon nanotubes and preparation method of fiber - Google Patents
Electrically conductive composite fiber containing carbon nanotubes and preparation method of fiber Download PDFInfo
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Abstract
The invention relates to an electrically conductive composite fiber containing carbon nanotubes and a preparation method of the fiber. The electrically conductive composite fiber containing the carbon nanotubes comprises the components of the carbon nanotubes, dispersant polymer and matrix polymer. The preparation method comprises the following steps: mixing and stirring the carbon nanotubes, resin slices of the dispersant polymer and slices of the matrix polymer; then fusing, filtering, spinning, cooling and molding by using a double-screw extruder; and preparing the electrically conductive composite fiber through stretching and thermal forming. The electrically conductive composite fiber containing the carbon nanotubes prepared by the method has the advantages of being high in content of carbon nanotubes, good in dispersivity, high in electrical conductivity, simple in manufacturing technology, low in cost, and the like.
Description
Technical field
The present invention relates to electrically conductive composite fibre of a kind of carbon nanotubes and preparation method thereof, particularly relate to and utilize a polymer that contains aromatic ring and itrile group roughly the same the time as dispersant CNT to be scattered in the matrix polymer equably, thereby prepare the method for the electrically conductive composite fibre of high content of carbon nanotubes.
Background technology
1991, doctor Iijima found CNT (CNTs), because it has the performances such as unique mechanics, electricity, just became at once a study hotspot of chemistry, physics and material science.
But the structure of CNT has also determined its limitation in application process when giving its excellent properties.The CNTs surface has large π key, and few surface defects lacks active group, makes neither hydrophilic also oleophylic not of its surface, is difficult to disperse in various solvents and dissolving (Xu G.D., Zhu B., Han Y., et al.Polym., 2007,48:7510-7515; Dang Z.M., Wang L., Zhang L.P.J.Nanom, 2006,2006:1-5).In addition, CNTs has large specific area, draw ratio and stronger Van der Waals force, and it is easily reunited or winding, destroys the excellent properties of single CNTs.Therefore, to CNTs carry out modification with improve its dispersiveness and become its research and use in a key.
Common carbon nano-tube modification method has two kinds.A kind of is covalent modified, normally utilizes the defective generation chemical reaction on CNTs surface or the terminal position, forms specific functional group or connects functional molecular.Covalent modified oxidation (the Chinese patent ZL200610118122.6 that comprises of CNTs; Zhao X.D., Lin W.R., Song N.H., et al., J.Mater.Chem., 2006,16:4619-4625; Chinese patent application publication number: CN 101970550), fluoridize (Im J.S., Kang S.C., Bai B.C., et al., Carbon, 2011,49:2235-2244.) and polymer graft etc. (Chinese patent ZL200410028338.4).Another kind of right and wrong are covalent modified, namely utilize the hydrophobic surface on CNTs surface and pi-electron structure and other molecule to be combined by weak interactions such as hydrophobic force, π-π are stacking, make the organic molecule winding of solubility or are adsorbed on the surface of CNTs.The material that is used for non-covalent modification mainly comprises: surfactant, such as (Chinese patent application publication numbers: CN 102275899A such as DTABs; Chinese patent ZL 200810159180.2); The aromatic ring base polymer is such as dissaving polymer (the Chinese patent ZL 200510101253.9 of poly-p styrene sulfonic acid and triarylamine; Chinese patent application publication number: CN 101679039A).
Because synthetic fiber belong to the dielectric category, its resistance is very large, and electrical conductivity is very little, therefore is easy to gather static.The static that gathers not only makes textile processing be difficult to carry out smoothly, and brings inconvenience for people's life.In order to eliminate the static of fiber and fabric thereof, prevent the generation that endangers, humanly just begin to develop antistatic, conductive fiber from the sixties in 20th century.Because CNTs has superior electric property, the researcher is applied to prepare electrically conductive composite fibre.At present, the preparation method of CNTs/ conducting polymer composite fibre mainly contains solution spinning, method of electrostatic spinning and melt spinning method.
Chinese patent ZL 200710036886.5 provides a kind of preparation method of Lyocell fiber of carbon nanotubes, first with CNTs pickling purifying, with surfactant it is carried out functionalization again, then utilizing ultrasonic wave that the CNTs of functionalization is dispersed in moisture is in 20 ~ 30% N-methylmorpholine-N-oxide water solution, adopt conventional Lyocell technique dry-wet spinning, preparing CNTs content is the CNTs/Lyocell composite fibre of 0.1 ~ 10wt.%.The method has realized the Uniform Dispersion of CNTs in the Lyocell fiber, has significantly improved mechanical property and the electrical conductivity of Lyocell fiber.Chinese patent ZL200510029612.4 is made into co-blended spinning solution with surface-functionalized CNTs and polymer, makes composite fibre through method of electrostatic spinning.
Skrifvars etc. (Skrifvars S., Soroudi, A., Solid State Phenomena, 2009,151:43-47) adopt melt spinning method, MWNT-PP master batch and PP are carried out co-blended spinning, prepare electrically conductive composite fibre.When MWCNT content was 1.5wt%, the electrical conductivity of fiber reached 10
-5S/cm illustrates that its percolation threshold is lower than 1.5wt%; When MWCNT content was 7.5wt%, the electrical conductivity of fiber was 10
-3S/cm, but the diameter thickness of fiber is uneven at this moment, widely different; When MWCNT content further is increased to 15wt%, although the electrical conductivity of fiber can reach 2.8S/cm, the non-constant of fibre property, frequent fracture of wire causes difficulty in spinning during spinning.(the Hooshmand S. such as Hooshmand, Soroudi A., Skrifvars M., SyntheticMetals, 2011,161 (15-16): 1731-1737) adopt melt spinning method, MWNT-PP master batch and PA, PP are carried out co-blended spinning prepare electrically conductive composite fibre, research is found: increase the temperature of content or the raising melt blending of PA, all can effectively improve electric conductivity and the mechanical property of fiber.When sample composition is 30wt%PP, 65wt%PA, 5wt%CNT and 1phr compatilizer, the as-spun fibre that obtains after 3 times of drawing-offs, though the mechanical property of fiber be improved, but electrical conductivity only is 10
-6S/cm.
More than prepare in the polymer composite fibrous method of CNTs/, adopt solution spinning and method of electrostatic spinning to exist to need and CNTs carried out the shortcoming such as covalent modified, complicated process of preparation, and method of electrostatic spinning is also far from industrialization at present.Melt spinning method technique is simple and cost is lower, but existing method needs first preparation or buy to contain the master batch of CNTs, and has the shortcomings such as CNTs content is low, bad dispersibility, and the electric conductivity of the composite fibre for preparing is also relatively poor.Therefore adopt one to contain the polymer of aromatic ring and itrile group as dispersant roughly the same the time, can significantly improve the dispersive property of CNTs in the fibrous matrix polymer by non-covalent modification, CNTs content is high, the excellent composite fibre of electric conductivity is very significant thereby prepare.
Summary of the invention
The present invention aims to provide a kind of method that adopts melt spinning method to prepare the electrically conductive composite fibre of high CNTs content.The present invention utilize a polymer that contains phenyl ring and itrile group roughly the same the time as dispersant improving the dispersiveness of CNTs in the fibrous matrix polymer, thereby prepare the composite fibre of CNTs content height, good dispersion, good conductivity.
The electrically conductive composite fibre of a kind of carbon nanotubes of the present invention, comprise CNT (CNTs), polymer dispersant and matrix polymer in the described electrically conductive composite fibre, described CNTs is embedded in polymer dispersant and the matrix polymer equably, forms conductive network; Described CNTs content is 3.0 ~ 8.0wt.%; Polymer dispersant content is 3.0 ~ 40.0wt.%; Matrix polymer content is 94.0 ~ 52.0wt.%;
Described CNT is Single Walled Carbon Nanotube (SWCNT) or multi-walled carbon nano-tubes (MWCNT);
Described polymer dispersant is styrene-acrylonitrile copolymer (SAN), Acrylnitrile-Butadiene-Styrene (ABS) or poly (arylene ether nitrile) (PEN) for containing simultaneously the polymer of phenyl ring and itrile group;
Described matrix polymer is polyethylene (PE), polypropylene (PP), PLA (PLA), polyformaldehyde (POM), polyester (PET) or polyamide (PA).
As preferred technical scheme:
The electrically conductive composite fibre of aforesaid a kind of carbon nanotubes, the electrical conductivity of the electrically conductive composite fibre of described carbon nanotubes are 2.1 * 10
-4~ 8.0 * 10
-2S/cm, fracture strength is 2.20 ~ 6.20cN/dtex.
The electrically conductive composite fibre of aforesaid a kind of carbon nanotubes, described CNTs diameter and length are respectively 0.75 ~ 30nm and 0.1 ~ 50 μ m;
The electrically conductive composite fibre of aforesaid a kind of carbon nanotubes, the melt index of described polymer dispersant are 2.0 ~ 10.0g/10min.
The electrically conductive composite fibre of aforesaid a kind of carbon nanotubes, the melt index of described matrix polymer are 3.0 ~ 80.0g/10min.
The present invention also provides a kind of preparation method of electrically conductive composite fibre of carbon nanotubes, with CNTs, polymer dispersant resin slicer and matrix polymer section mix and blend, then with double screw extruder its melting, filtration, spinning, cooling forming, stretching and HEAT SETTING are prepared electrically conductive composite fibre in proportion;
Described CNTs content is 3.0 ~ 8.0wt.%; Polymer dispersant content is 3.0 ~ 40.0wt.%; Matrix polymer content is 52.0 ~ 94.0wt.%;
The rotating speed of described double screw extruder is 35 ~ 200rpm, and pressure is 25 ~ 180kg/cm
2, the twin-screw regional Zhong Yi district temperature of heating is 190 ~ 305 ℃, and two district's temperature are 190 ~ 305 ℃, and three district's temperature are 190 ~ 305 ℃, and four district's temperature are 200 ~ 315 ℃;
Described spinning speed is 450 ~ 4200m/min;
Described drawing process is: temperature of heat plate is 60 ~ 110 ℃, and hot plate temperature is 115 ~ 165 ℃; Stretching ratio is 1.5 ~ 6.0 times, and drafting rate is 80 ~ 250m/min.
The preparation method of the electrically conductive composite fibre of aforesaid a kind of carbon nanotubes, described CNTs are Single Walled Carbon Nanotube or multi-walled carbon nano-tubes; Described CNTs diameter and length are respectively 0.75 ~ 30nm and 0.1 ~ 50 μ m.
The preparation method of the electrically conductive composite fibre of aforesaid a kind of carbon nanotubes, described polymer dispersant is styrene-acrylonitrile copolymer (SAN), Acrylnitrile-Butadiene-Styrene (ABS) or poly (arylene ether nitrile) (PEN) for containing simultaneously the polymer of phenyl ring and itrile group; The melt index of described polymer dispersant is 2.0～10.0g/10min;
The preparation method of the electrically conductive composite fibre of aforesaid a kind of carbon nanotubes, described matrix polymer is polyethylene (PE), polypropylene (PP), PLA (PLA), polyformaldehyde (POM), polyester (PET) or polyamide (PA), and the melt index of described matrix polymer is 3.0 ~ 80.0g/10min.
Beneficial effect:
(1) acts synergistically with CNTs by π-π is stacking as the phenyl ring in the polymer of dispersant and itrile group, can significantly improve the dispersiveness of CNTs, thereby improve the content of CNTs in composite fibre.
(2) need not CNTs is carried out covalent modified, can not destroy the structure of CNTs, and need not to add the auxiliary agent such as coupling agent, only need to reach the purpose of improving CNTs dispersive property in the fibrous matrix polymer by non-covalent modification.
(3) need not to prepare master batch, only need CNTs, polymer dispersant and matrix polymer melt blending, spinning can be prepared electrically conductive composite fibre, this preparation method's technique is simple, cost is low, the electric conductivity of gained composite fibre excellent.
The specific embodiment
Below in conjunction with the specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used for explanation the present invention and be not used in and limit the scope of the invention.Should be understood that in addition those skilled in the art can make various changes or modifications the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims limited range equally.
Embodiment 1
The styrene-acrylonitrile copolymer (SAN) that adopts diameter and length to be respectively Single Walled Carbon Nanotube (SWCNT), the MFI=5.0g/10min of 0.75nm and 0.1 μ m prepares electrically conductive composite fibre as the polypropylene (PP) of polymer dispersant and MFI=26.0g/min as matrix polymer.Preparation process is as follows:
(1) preparation of as-spun fibre: with SWCNTs, SAN section and the PP in mass ratio 3:3:94 mix and blend of cutting into slices, then with double screw extruder its melting, filtration, spinning, cooling forming are obtained conducting electricity compound as-spun fibre.Wherein the rotating speed of double screw extruder is 35rpm; Pressure is 25kg/cm
2The twin-screw regional Zhong Yi district temperature of heating is 190 ℃, and two district's temperature are 190 ℃, and three district's temperature are 190 ℃, and four district's temperature are 200 ℃; Spinning speed is 1500m/min.
(2) stretching of as-spun fibre and HEAT SETTING: as-spun fibre drawn and HEAT SETTING are prepared electrically conductive composite fibre, and wherein temperature of heat plate is 60 ℃, and hot plate is 115 ℃; Stretching ratio is 4.0 times, and drafting rate is 100m/min.
Content of carbon nanotubes is 3.0wt% in the electrically conductive composite fibre for preparing, and electrical conductivity is 2.1 * 10
-4S/cm, fiber linear density are 8.6dtex, and fracture strength is 2.70cN/dtex, and elongation at break is 18.5%.
Embodiment 2
The styrene-acrylonitrile copolymer (SAN) that adopts diameter and length to be respectively multi-walled carbon nano-tubes (MWCNT), the MFI=3.5g/10min of 30nm and 50 μ m prepares electrically conductive composite fibre as the polyethylene (PE) of polymer dispersant and MFI=40.0g/min as matrix polymer.Preparation process is as follows:
(1) preparation of as-spun fibre: with MWCNTs, SAN section and the PE in mass ratio 8:8:84 mix and blend of cutting into slices, then with double screw extruder its melting, filtration, spinning, cooling forming are obtained conducting electricity compound as-spun fibre.Wherein the rotating speed of double screw extruder is 110rpm; Pressure is 90kg/cm
2The twin-screw regional Zhong Yi district temperature of heating is 190 ℃, and two district's temperature are 190 ℃, and three district's temperature are 190 ℃, and four district's temperature are 200 ℃; Spinning speed is 3000m/min.
(2) stretching of as-spun fibre and HEAT SETTING: as-spun fibre drawn and HEAT SETTING are prepared electrically conductive composite fibre, and wherein temperature of heat plate is 60 ℃, and hot plate temperature is 115 ℃; Stretching ratio is 1.7 times, and drafting rate is 150m/min.
Content of carbon nanotubes is 8.0wt% in the electrically conductive composite fibre for preparing, and electrical conductivity is 6.3 * 10
-2S/cm, fiber linear density are 2.40dtex, and fracture strength is 2.20cN/dtex, and elongation at break is 13.0%.
Embodiment 3
The styrene-acrylonitrile copolymer (SAN) that adopts diameter and length to be respectively Single Walled Carbon Nanotube (SWCNT), the MFI=5g/10min of 12nm and 3 μ m prepares electrically conductive composite fibre as the PLA (PLA) of polymer dispersant and MFI=3.0g/min as matrix polymer.Preparation process is as follows:
(1) preparation of as-spun fibre: with SWCNTs, SAN section and the PLA in mass ratio 4:8:88 mix and blend of cutting into slices, then with double screw extruder its melting, filtration, spinning, cooling forming are obtained conducting electricity compound as-spun fibre.Wherein the rotating speed of double screw extruder is 180rpm; Pressure is 165kg/cm
2The twin-screw regional Zhong Yi district temperature of heating is 200 ℃, and two district's temperature are 200 ℃, and three district's temperature are 205 ℃, and four district's temperature are 215 ℃; Spinning speed is 1600m/min.
(2) stretching of as-spun fibre and HEAT SETTING: as-spun fibre drawn and HEAT SETTING are prepared electrically conductive composite fibre, and wherein temperature of heat plate is 95 ℃, and hot plate is 135 ℃; Stretching ratio is 5.0 times, and drafting rate is 100m/min.
Content of carbon nanotubes is 4.0wt% in the electrically conductive composite fibre for preparing, and electrical conductivity is 6.1 * 10
-4S/cm, fiber linear density are 4.9dtex, and fracture strength is 5.10cN/dtex, and elongation at break is 12.7%.
Embodiment 4
The Acrylnitrile-Butadiene-Styrene (ABS) that adopts diameter and length to be respectively multi-walled carbon nano-tubes (MWCNT), the MFI=8g/10min of 5nm and 3 μ m prepares electrically conductive composite fibre as the polyformaldehyde (POM) of polymer dispersant and MFI=15.0g/min as matrix polymer.Preparation process is as follows:
(1) preparation of as-spun fibre: with MWCNTs, ABS section and the POM in mass ratio 5:15:80 mix and blend of cutting into slices, with double screw extruder its melting, filtration, spinning, cooling forming are obtained conducting electricity compound as-spun fibre.Wherein the rotating speed of double screw extruder is 150rpm; Pressure is 110kg/cm
2The twin-screw regional Zhong Yi district temperature of heating is 195 ℃, and two district's temperature are 195 ℃, and three district's temperature are 205 ℃, and four district's temperature are 215 ℃; Spinning speed is 450m/min.
(2) stretching of as-spun fibre and HEAT SETTING: as-spun fibre drawn and HEAT SETTING are prepared electrically conductive composite fibre, and wherein temperature of heat plate is 75 ℃, and hot plate temperature is 120 ℃; Stretching ratio is 6.0 times, and drafting rate is 250m/min.
Content of carbon nanotubes is 5.0wt% in the electrically conductive composite fibre for preparing, and electrical conductivity is 3.7 * 10
-3S/cm, fiber linear density are 16.0dtex, and fracture strength is 5.60cN/dtex, and elongation at break is 10.0%.
Embodiment 5
The poly (arylene ether nitrile) (PEN) that adopts diameter and length to be respectively Single Walled Carbon Nanotube (SWCNT), the MFI=2.0g/10min of 9.5nm and 1.5 μ m prepares electrically conductive composite fibre as the polyester (PET) of polymer dispersant and MFI=60.0g/min as matrix polymer.Preparation process is as follows:
(1) preparation of as-spun fibre: with SWCNTs, PEN section and the PET in mass ratio 8:40:52 mix and blend of cutting into slices, with double screw extruder its melting, filtration, spinning, cooling forming are obtained conducting electricity compound as-spun fibre.Wherein the rotating speed of double screw extruder is 200rpm; Pressure is 180kg/cm
2The twin-screw regional Zhong Yi district temperature of heating is 300 ℃, and two district's temperature are 300 ℃, and three district's temperature are 305 ℃, and four district's temperature are 315 ℃; Spinning speed is 2100m/min.
(2) stretching of as-spun fibre and HEAT SETTING: as-spun fibre drawn and HEAT SETTING are prepared electrically conductive composite fibre, and wherein temperature of heat plate is 110 ℃, and hot plate temperature is 165 ℃; Stretching ratio is 3.0 times, and drafting rate is 150m/min.
Content of carbon nanotubes is 8.0wt% in the electrically conductive composite fibre for preparing, and electrical conductivity is 8.0 * 10
-2S/cm, fiber linear density are 5.30dtex, and fracture strength is 4.40cN/dtex, and elongation at break is 12.0%.
Embodiment 6
Adopt diameter and length to be respectively styrene-butadiene-acrylonitrile (ABS) of multi-walled carbon nano-tubes (MWCNT), MFI=10.0g/10min of 1.5nm and 1 μ m as the nylon 6(PA6 of polymer dispersant and MFI=80g/min) prepare electrically conductive composite fibre as matrix polymer.Preparation process is as follows:
(1) preparation of as-spun fibre: with MWCNTs, ABS section and the PA6 in mass ratio 6:30:64 mix and blend of cutting into slices, with double screw extruder its melting, filtration, spinning, cooling forming are obtained conducting electricity compound as-spun fibre.Wherein the rotating speed of double screw extruder is 100rpm; Pressure is 85kg/cm
2The twin-screw regional Zhong Yi district temperature of heating is 305 ℃, and two district's temperature are 305 ℃, and three district's temperature are 305 ℃, and four district's temperature are 315 ℃; Spinning speed is 2600m/min.
(2) stretching of as-spun fibre and HEAT SETTING: as-spun fibre drawn and HEAT SETTING are prepared electrically conductive composite fibre, and wherein temperature of heat plate is 110 ℃, and hot plate temperature is 135 ℃; Stretching ratio is 2.0 times, and drafting rate is 80m/min.
Content of carbon nanotubes is 6.0wt% in the electrically conductive composite fibre for preparing, and electrical conductivity is 8.6 * 10
-3S/cm, fiber linear density are 3.50dtex, and fracture strength is 6.20cN/dtex, and elongation at break is 15.0%.
Embodiment 7
Adopt diameter and length to be respectively the Acrylnitrile-Butadiene-Styrene (ABS) of Single Walled Carbon Nanotube (SWCNT), MFI=2.7g/10min of 21nm and 35 μ m as the nylon 66(PA66 of polymer dispersant and MFI=65g/min) prepare electrically conductive composite fibre as matrix polymer.Preparation process is as follows:
(1) preparation of as-spun fibre: with SWCNTs, ABS section and the PA66 in mass ratio 7:28:65 mix and blend of cutting into slices, with double screw extruder its melting, filtration, spinning, cooling forming are obtained conducting electricity compound as-spun fibre.Wherein the rotating speed of double screw extruder is 60rpm; Pressure is 40kg/cm
2The twin-screw regional Zhong Yi district temperature of heating is 275 ℃, and two district's temperature are 275 ℃, and three district's temperature are 280 ℃, and four district's temperature are 285 ℃; Spinning speed is 4200m/min.
(2) stretching of as-spun fibre and HEAT SETTING: as-spun fibre drawn and HEAT SETTING are prepared electrically conductive composite fibre, and wherein temperature of heat plate is 110 ℃, and hot plate temperature is 145 ℃; Stretching ratio is 1.5 times, and drafting rate is 80m/min.
Content of carbon nanotubes is 7.0wt% in the electrically conductive composite fibre for preparing, and electrical conductivity is 3.3 * 10
-2S/cm, fiber linear density are 4.10dtex, and fracture strength is 5.60cN/dtex, and elongation at break is 16.7%.
Claims (9)
1. the electrically conductive composite fibre of a carbon nanotubes, it is characterized in that: comprise CNT, polymer dispersant and matrix polymer in the described electrically conductive composite fibre, be embedded in to described even carbon nanotube in polymer dispersant and the matrix polymer, form conductive network; Described content of carbon nanotubes is 3.0 ~ 8.0wt.%; Polymer dispersant content is 3.0 ~ 40.0wt.%; Matrix polymer content is 94.0 ~ 52.0wt.%;
Described CNT is Single Walled Carbon Nanotube or multi-walled carbon nano-tubes;
Described polymer dispersant is styrene-acrylonitrile copolymer, Acrylnitrile-Butadiene-Styrene or poly (arylene ether nitrile) for containing simultaneously the polymer of phenyl ring and itrile group;
Described matrix polymer is polyethylene, polypropylene, PLA, polyformaldehyde, polyester or polyamide.
2. the electrically conductive composite fibre of a kind of carbon nanotubes as claimed in claim 1 is characterized in that, the electrical conductivity of the electrically conductive composite fibre of described carbon nanotubes is 2.1 * 10
-4~ 8.0 * 10
-2S/cm, fracture strength is 2.20 ~ 6.20cN/dtex.
3. the electrically conductive composite fibre of a kind of carbon nanotubes as claimed in claim 1 is characterized in that, described CNT diameter and length are respectively 0.75 ~ 30nm and 0.1 ~ 50 μ m.
4. the electrically conductive composite fibre of a kind of carbon nanotubes as claimed in claim 1 is characterized in that, the melt index of described polymer dispersant is 2.0 ~ 10.0g/10min.
5. the electrically conductive composite fibre of a kind of carbon nanotubes as claimed in claim 1 is characterized in that, the melt index of described matrix polymer is 3.0 ~ 80.0g/10min.
6. the preparation method of the electrically conductive composite fibre of a kind of carbon nanotubes according to claim 1, it is characterized in that: with CNT, polymer dispersant resin slicer and polymer chips mix and blend, with double screw extruder its melting, filtration, spinning, cooling forming, stretching and HEAT SETTING are prepared electrically conductive composite fibre in proportion;
Described content of carbon nanotubes is 3.0 ~ 8.0wt.%; Polymer dispersant content is 3.0 ~ 40.0wt.%; Matrix polymer content is 52.0 ~ 94.0wt.%;
The rotating speed of described double screw extruder is 35 ~ 200rpm, and pressure is 25 ~ 180kg/cm
2, the twin-screw regional Zhong Yi district temperature of heating is 190 ~ 305 ℃, and two district's temperature are 190 ~ 305 ℃, and three district's temperature are 190 ~ 305 ℃, and four district's temperature are 200 ~ 315 ℃;
Described spinning speed is 450 ~ 4200m/min.
Described drawing process is: temperature of heat plate is 60 ~ 110 ℃, and hot plate temperature is 115 ~ 165 ℃; Stretching ratio is 1.5 ~ 6.0 times, and drafting rate is 80 ~ 250m/min.
7. the preparation method of the electrically conductive composite fibre of a kind of carbon nanotubes as claimed in claim 6 is characterized in that, described CNT is Single Walled Carbon Nanotube or multi-walled carbon nano-tubes; Described CNT diameter and length are respectively 0.75 ~ 30nm and 0.1 ~ 50 μ m.
8. the preparation method of the electrically conductive composite fibre of a kind of carbon nanotubes as claimed in claim 6, it is characterized in that, described polymer dispersant is styrene-acrylonitrile copolymer, Acrylnitrile-Butadiene-Styrene or poly (arylene ether nitrile) for containing simultaneously the polymer of phenyl ring and itrile group; The melt index of described polymer dispersant is 2.0 ~ 10.0g/10min.
9. the preparation method of the electrically conductive composite fibre of a kind of carbon nanotubes as claimed in claim 6, it is characterized in that, described matrix polymer is polyethylene, polypropylene, PLA, polyformaldehyde, polyester or polyamide, and the melt index of described matrix polymer is 3.0 ~ 80.0g/10min.
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