CN102899742B - 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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- CN102899742B CN102899742B CN201210442761.3A CN201210442761A CN102899742B CN 102899742 B CN102899742 B CN 102899742B CN 201210442761 A CN201210442761 A CN 201210442761A CN 102899742 B CN102899742 B CN 102899742B
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- 239000000835 fiber Substances 0.000 title claims abstract description 110
- 239000002131 composite material Substances 0.000 title claims abstract description 65
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 45
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 229920000642 polymer Polymers 0.000 claims abstract description 67
- 239000002270 dispersing agent Substances 0.000 claims abstract description 30
- 239000011159 matrix material Substances 0.000 claims abstract description 30
- 238000009987 spinning Methods 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 23
- 238000009998 heat setting Methods 0.000 claims abstract description 17
- 238000001816 cooling Methods 0.000 claims abstract description 10
- 238000001914 filtration Methods 0.000 claims abstract description 10
- 238000002844 melting Methods 0.000 claims abstract description 10
- 230000008018 melting Effects 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims description 19
- 239000002048 multi walled nanotube Substances 0.000 claims description 17
- 239000002109 single walled nanotube Substances 0.000 claims description 17
- -1 poly (arylene ether nitrile Chemical class 0.000 claims description 15
- 229920002285 poly(styrene-co-acrylonitrile) Polymers 0.000 claims description 15
- 239000004743 Polypropylene Substances 0.000 claims description 13
- 229920001155 polypropylene Polymers 0.000 claims description 11
- 239000004952 Polyamide Substances 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 229920000747 poly(lactic acid) Polymers 0.000 claims description 9
- 229920002647 polyamide Polymers 0.000 claims description 9
- 239000004626 polylactic acid Substances 0.000 claims description 9
- 229920006324 polyoxymethylene Polymers 0.000 claims description 9
- 239000004698 Polyethylene Substances 0.000 claims description 8
- 229920000573 polyethylene Polymers 0.000 claims description 8
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 claims description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 5
- 239000011347 resin Substances 0.000 claims description 2
- 229920005989 resin Polymers 0.000 claims description 2
- 229920006149 polyester-amide block copolymer Polymers 0.000 claims 2
- 238000002156 mixing Methods 0.000 abstract description 3
- 239000006185 dispersion Substances 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 238000009740 moulding (composite fabrication) Methods 0.000 abstract 1
- 239000002952 polymeric resin Substances 0.000 abstract 1
- 238000003756 stirring Methods 0.000 abstract 1
- 229920003002 synthetic resin Polymers 0.000 abstract 1
- 230000005611 electricity Effects 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 7
- 229920000728 polyester Polymers 0.000 description 7
- 229920000433 Lyocell Polymers 0.000 description 5
- 238000002074 melt spinning Methods 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 239000004594 Masterbatch (MB) Substances 0.000 description 4
- 238000010041 electrostatic spinning Methods 0.000 description 4
- 239000000155 melt Substances 0.000 description 4
- 229920002292 Nylon 6 Polymers 0.000 description 3
- 229920002302 Nylon 6,6 Polymers 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 230000003068 static effect Effects 0.000 description 3
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- 238000007306 functionalization reaction Methods 0.000 description 2
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- 239000004094 surface-active agent Substances 0.000 description 2
- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical compound OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-UHFFFAOYSA-N 0.000 description 1
- LFTLOKWAGJYHHR-UHFFFAOYSA-N N-methylmorpholine N-oxide Chemical compound CN1(=O)CCOCC1 LFTLOKWAGJYHHR-UHFFFAOYSA-N 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 229920005601 base polymer Polymers 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000002322 conducting polymer Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
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- 230000003993 interaction Effects 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000005325 percolation Methods 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 125000005259 triarylamine group Chemical group 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
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- Artificial Filaments (AREA)
- Multicomponent Fibers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
本发明涉及一种含碳纳米管的导电复合纤维及其制备方法。本发明的一种含碳纳米管的导电复合纤维，其组分包括：碳纳米管、分散剂聚合物和基体聚合物。该制备方法包括：按比例将碳纳米管、分散剂聚合物树脂切片和基体聚合物切片混合搅拌，然后用双螺杆挤出机将其熔融、过滤、纺丝、冷却成型，并经过拉伸和热定型制备得到导电复合纤维。该方法制备得到的导电复合纤维具有碳纳米管含量高、分散性好、电导率高、制造工艺简单和成本低等优点。The invention relates to a conductive composite fiber containing carbon nanotubes and a preparation method thereof. The conductive composite fiber containing carbon nanotubes of the present invention comprises: carbon nanotubes, dispersant polymers and matrix polymers. The preparation method comprises: mixing and stirring carbon nanotubes, dispersant polymer resin slices and matrix polymer slices in proportion, then melting, filtering, spinning, cooling and forming them with a twin-screw extruder, and stretching and Conductive composite fibers were prepared by heat setting. The conductive composite fiber prepared by the method has the advantages of high carbon nanotube content, good dispersion, high electrical conductivity, simple manufacturing process, low 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 time as dispersant, CNT to be scattered in 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), has the performances such as unique mechanics, electricity due to it, just becomes at once a study hotspot of chemistry, physics and material science.
But the structure of CNT, when giving its excellent properties, has also determined its limitation in application process.CNTs surface has large π key, and few surface defects lacks active group, makes neither hydrophilic also oleophylic not of its surface, is difficult in various solvents, disperse and dissolve (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, makes it easily reunite or be wound around, and destroys the excellent properties of single CNTs.Therefore, CNTs is carried out to modification and become a key in its research and application to improve its dispersiveness.
Common carbon nano-tube modification method has two kinds.A kind of is covalent modified, normally utilizes the defect generation chemical reaction on CNTs surface or 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, 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.Material for non-covalent modification mainly comprises: surfactant, as (Chinese patent application publication numbers: CN 102275899A such as DTABs; Chinese patent ZL 200810159180.2); Aromatic ring base polymer, 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 dielectric category, its resistance is very large, and electrical conductivity is very little, is therefore easy to gather static.The static gathering not only makes textile processing be difficult to carry out smoothly, and brings inconvenience to people's life.In order to eliminate the static of fiber and fabric thereof, prevent the generation of harm, the mankind just start to develop antistatic, conductive fiber from the sixties in 20th century.Because CNTs has superior electric property, 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 by CNTs pickling purifying, with surfactant, it is carried out to functionalization again, then utilizing ultrasonic wave that the CNTs of functionalization is dispersed in to moisture is in N-methylmorpholine-N-oxide water solution of 20 ~ 30%, adopt conventional Lyocell technique dry-wet spinning, preparing CNTs content is the CNTs/Lyocell composite fibre of 0.1 ~ 10wt.%.The method has realized dispersed in Lyocell fiber of CNTs, has significantly improved mechanical property and the electrical conductivity of Lyocell fiber.Chinese patent ZL200510029612.4 is made into co-blended spinning solution by surface-functionalized CNTs and polymer, through method of electrostatic spinning, makes composite fibre.
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 to co-blended spinning, prepare electrically conductive composite fibre.When MWCNT content is 1.5wt%, the electrical conductivity of fiber reaches 10
-5s/cm, illustrates that its percolation threshold is lower than 1.5wt%; When MWCNT content is 7.5wt%, the electrical conductivity of fiber is 10
-3s/cm, but now the diameter thickness of fiber is uneven, widely different; When MWCNT content is further increased to 15wt%, although the electrical conductivity of fiber can reach 2.8S/cm, the non-constant of fibre property, during spinning, frequent fracture of wire, causes difficulty in 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 to co-blended spinning and 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 obtaining after 3 times of drawing-offs, though the mechanical property of fiber be improved, but electrical conductivity is only 10
-6s/cm.
More than prepare in the polymer composite fibrous method of CNTs/, adopt solution spinning and method of electrostatic spinning to exist and need carry out to CNTs the shortcomings 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 the master batch containing CNTs need first be prepared or buy to existing method, and has the shortcomings such as CNTs content is low, bad dispersibility, and the electric conductivity of the composite fibre preparing is also poor.Therefore adopt a polymer that contains aromatic ring and itrile group roughly the same time as dispersant, by non-covalent modification, can significantly improve the dispersive property of CNTs in fibrous matrix polymer, be very significant thereby prepare the composite fibre that CNTs content is high, electric conductivity is excellent.
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 time as dispersant to improve the dispersiveness of CNTs in fibrous matrix polymer, thereby prepare that CNTs content is high, the composite fibre of good dispersion, good conductivity.
The electrically conductive composite fibre of a kind of carbon nanotubes of the present invention, in described electrically conductive composite fibre, comprise CNT (CNTs), polymer dispersant and matrix polymer, described CNTs is embedded in polymer dispersant and 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);
The polymer of described polymer dispersant for contain phenyl ring and itrile group is simultaneously styrene-acrylonitrile copolymer (SAN), Acrylnitrile-Butadiene-Styrene (ABS) or poly (arylene ether nitrile) (PEN);
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 a kind of carbon nanotubes as above, 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.
The electrically conductive composite fibre of a kind of carbon nanotubes as above, described CNTs diameter and length are respectively 0.75 ~ 30nm and 0.1 ~ 50 μ m;
The electrically conductive composite fibre of a kind of carbon nanotubes as above, the melt index of described polymer dispersant is 2.0 ~ 10.0g/10min.
The electrically conductive composite fibre of a kind of carbon nanotubes as above, the melt index of described matrix polymer is 3.0 ~ 80.0g/10min.
The present invention also provides a kind of preparation method of electrically conductive composite fibre of carbon nanotubes, by 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 to 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, twin-screw Zhong Yi district, the region 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 a kind of carbon nanotubes as above, described CNTs is 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 a kind of carbon nanotubes as above, the polymer of described polymer dispersant for contain phenyl ring and itrile group is simultaneously styrene-acrylonitrile copolymer (SAN), Acrylnitrile-Butadiene-Styrene (ABS) or poly (arylene ether nitrile) (PEN); The melt index of described polymer dispersant is 2.0～10.0g/10min; .
The preparation method of the electrically conductive composite fibre of a kind of carbon nanotubes as above, 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) as the phenyl ring in the polymer of dispersant and itrile group, by π-π is stacking, act synergistically with CNTs, can significantly improve the dispersiveness of CNTs, thereby improve the content of CNTs in composite fibre.
(2) covalent modified without CNTs is carried out, can not destroy the structure of CNTs, and without adding the auxiliary agents such as coupling agent, only need can reach the object of improving CNTs dispersive property in fibrous matrix polymer by the method for non-covalent modification.
(3) without preparing master batch, only CNTs, polymer dispersant and matrix polymer melt blending, spinning can need be prepared to 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 are only not used in and limit the scope of the invention for the present invention is described.In addition should be understood that those skilled in the art can make various changes or modifications the present invention after having read the content of the present invention's instruction, these equivalent form of values fall within the application's appended claims limited range equally.
Embodiment 1
Adopt diameter and length is respectively the Single Walled Carbon Nanotube (SWCNT) of 0.75nm and 0.1 μ m, the styrene-acrylonitrile copolymer (SAN) of MFI=5.0g/10min is prepared 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: by SWCNTs, SAN section and the PP 3:3:94 mix and blend in mass ratio 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
2; Twin-screw Zhong Yi district, the region 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 to 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.
In the electrically conductive composite fibre preparing, content of carbon nanotubes is 3.0wt%, and electrical conductivity is 2.1 * 10
-4s/cm, fiber linear density is 8.6dtex, and fracture strength is 2.70cN/dtex, and elongation at break is 18.5%.
Embodiment 2
Adopt diameter and length is respectively the multi-walled carbon nano-tubes (MWCNT) of 30nm and 50 μ m, the styrene-acrylonitrile copolymer (SAN) of MFI=3.5g/10min is prepared 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: by MWCNTs, SAN section and the PE 8:8:84 mix and blend in mass ratio 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
2; Twin-screw Zhong Yi district, the region 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 to 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.
In the electrically conductive composite fibre preparing, content of carbon nanotubes is 8.0wt%, and electrical conductivity is 6.3 * 10
-2s/cm, fiber linear density is 2.40dtex, and fracture strength is 2.20cN/dtex, and elongation at break is 13.0%.
Embodiment 3
Adopt diameter and length is respectively the Single Walled Carbon Nanotube (SWCNT) of 12nm and 3 μ m, the styrene-acrylonitrile copolymer (SAN) of MFI=5g/10min is prepared 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: by SWCNTs, SAN section and the PLA 4:8:88 mix and blend in mass ratio 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
2; Twin-screw Zhong Yi district, the region 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 to 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.
In the electrically conductive composite fibre preparing, content of carbon nanotubes is 4.0wt%, and electrical conductivity is 6.1 * 10
-4s/cm, fiber linear density is 4.9dtex, and fracture strength is 5.10cN/dtex, and elongation at break is 12.7%.
Embodiment 4
Adopt diameter and length is respectively the multi-walled carbon nano-tubes (MWCNT) of 5nm and 3 μ m, the Acrylnitrile-Butadiene-Styrene (ABS) of MFI=8g/10min is prepared 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: by MWCNTs, ABS section and the POM 5:15:80 mix and blend in mass ratio 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
2; Twin-screw Zhong Yi district, the region 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 to 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.
In the electrically conductive composite fibre preparing, content of carbon nanotubes is 5.0wt%, and electrical conductivity is 3.7 * 10
-3s/cm, fiber linear density is 16.0dtex, and fracture strength is 5.60cN/dtex, and elongation at break is 10.0%.
Embodiment 5
Adopt diameter and length is respectively the Single Walled Carbon Nanotube (SWCNT) of 9.5nm and 1.5 μ m, the poly (arylene ether nitrile) (PEN) of MFI=2.0g/10min is prepared 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: by SWCNTs, PEN section and the PET 8:40:52 mix and blend in mass ratio 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
2; Twin-screw Zhong Yi district, the region 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 to 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.
In the electrically conductive composite fibre preparing, content of carbon nanotubes is 8.0wt%, and electrical conductivity is 8.0 * 10
-2s/cm, fiber linear density is 5.30dtex, and fracture strength is 4.40cN/dtex, and elongation at break is 12.0%.
Embodiment 6
Adopt diameter and length is respectively the multi-walled carbon nano-tubes (MWCNT) of 1.5nm and 1 μ m, styrene-butadiene-acrylonitrile (ABS) of MFI=10.0g/10min as the nylon 6(PA6 of polymer dispersant and MFI=80g/min) as matrix polymer, prepare electrically conductive composite fibre.Preparation process is as follows:
(1) preparation of as-spun fibre: by MWCNTs, ABS section and the PA6 6:30:64 mix and blend in mass ratio 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
2; Twin-screw Zhong Yi district, the region 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 to 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.
In the electrically conductive composite fibre preparing, content of carbon nanotubes is 6.0wt%, and electrical conductivity is 8.6 * 10
-3s/cm, fiber linear density is 3.50dtex, and fracture strength is 6.20cN/dtex, and elongation at break is 15.0%.
Embodiment 7
Adopt diameter and length is respectively the Single Walled Carbon Nanotube (SWCNT) of 21nm and 35 μ m, the Acrylnitrile-Butadiene-Styrene (ABS) of MFI=2.7g/10min as the nylon 66(PA66 of polymer dispersant and MFI=65g/min) as matrix polymer, prepare electrically conductive composite fibre.Preparation process is as follows:
(1) preparation of as-spun fibre: by SWCNTs, ABS section and the PA66 7:28:65 mix and blend in mass ratio 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
2; Twin-screw Zhong Yi district, the region 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 to 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.
In the electrically conductive composite fibre preparing, content of carbon nanotubes is 7.0wt%, and electrical conductivity is 3.3 * 10
-2s/cm, fiber linear density is 4.10dtex, and fracture strength is 5.60cN/dtex, and elongation at break is 16.7%.
Claims (7)
1. the electrically conductive composite fibre of a carbon nanotubes, it is characterized in that: in described electrically conductive composite fibre, comprise CNT, polymer dispersant and matrix polymer, be embedded in polymer dispersant and matrix polymer to described even carbon nanotube, 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;
The polymer of described polymer dispersant for contain phenyl ring and itrile group is simultaneously styrene-acrylonitrile copolymer, Acrylnitrile-Butadiene-Styrene or poly (arylene ether nitrile);
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 preparation method of the electrically conductive composite fibre of a kind of carbon nanotubes according to claim 1, it is characterized in that: by CNT, polymer dispersant resin slicer and matrix polymer section mix and blend, with double screw extruder, its melting, filtration, spinning, cooling forming, stretching and HEAT SETTING are prepared to 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, twin-screw Zhong Yi district, the region 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.
5. the preparation method of the electrically conductive composite fibre of a kind of carbon nanotubes as claimed in claim 4, 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.
6. the preparation method of the electrically conductive composite fibre of a kind of carbon nanotubes as claimed in claim 4, it is characterized in that, the polymer of described polymer dispersant for contain phenyl ring and itrile group is simultaneously styrene-acrylonitrile copolymer, Acrylnitrile-Butadiene-Styrene or poly (arylene ether nitrile).
7. the preparation method of the electrically conductive composite fibre of a kind of carbon nanotubes as claimed in claim 4, is characterized in that, described matrix polymer is polyethylene, polypropylene, PLA, polyformaldehyde, polyester or polyamide.
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