CN1304656C - Carbon nanometer tube composite fibre with high orientation and production thereof - Google Patents
Carbon nanometer tube composite fibre with high orientation and production thereof Download PDFInfo
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- CN1304656C CN1304656C CNB2005100296124A CN200510029612A CN1304656C CN 1304656 C CN1304656 C CN 1304656C CN B2005100296124 A CNB2005100296124 A CN B2005100296124A CN 200510029612 A CN200510029612 A CN 200510029612A CN 1304656 C CN1304656 C CN 1304656C
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Abstract
The present invention discloses carbon nanometer tube composite fiber with high orientation, which comprises carbon nanotubes of which the surfaces are functionalized and polymer. The quality ratio of the carbon nanotubes and the polymer is 1/2 to 1000. The present invention also discloses a manufacturing method of the carbon nanometer tube composite fiber with high orientation, which comprises the following steps: dispersing the carbon nanotubes in strong acid in an ultrasonic way for 0.5 to 10 hours; reacting the carbon nanotubes of which the surfaces contain carboxyl and thionyl chloride or diisocyanate in 60 to 75 DEG C for 4 to 24 hours; respectively reacting small molecules and large molecules which can react with COCL and NCO in 50 to 250 DEG C for 4 to 24 hours, and allocating blended spinning solution with the polymer; obtaining the carbon nanometer tube composite fiber with high orientation by high voltage electrostatic spinning. The space of two electrodes of the high voltage electrostatic spinning is 1mm to 100mm. The present invention realizes that the carbon nanotubes are evenly dispersed in nanometer fiber, realizes the effective orientation of the carbon nanotubes in the nanometer fiber, and realizes the high orientation arrangement of the nanometer fiber.
Description
Technical field
The present invention relates to a kind of nano-composite fiber and preparation method thereof, particularly relate to a kind of based on carbon nanotube composite fibre and preparation method thereof.
Background technology
CNT (CNT) has caused the extensive interest of scientists since finding the nineties, be the focus of Recent study, and research has related to fields such as chemistry, physics, biology, microelectronics, photoelectron, materialogy.CNT is divided into multi-walled carbon nano-tubes (MWNTs) and Single Walled Carbon Nanotube (SWNTs), is the seamless nanoscale pipe that single or multiple lift graphite curls and forms by certain helical angle around the center, and every layer of nanotube is one and passes through sp by carbon atom
2The face of cylinder that the hexagon plane that is constituted behind hydridization and 3 the complete bondings of carbon atom is on every side formed.But, wherein also there is sub-fraction carbon to belong to sp owing to there is certain curvature
3Hydridization.CNT has excellent mechanical property, and tensile strength reaches 50GPa～200GPa, is 100 times of steel, and density but has only 1/6 of steel.CNT has good pliability and resilience in addition, CNT is curled by the graphite face and forms, 4 valency electricity in 3 form covalent bonds, electronics of each carbon contribution form metalline delocalized bond, therefore, the cylindrical carbon nanotube axially has good electrical conductivity.CNT and polymer form composite can obviously must improve its mechanical property and electric property.Its research has significance to material science, photoelectron science, bioengineering.Electrostatic spinning has been acknowledged as the technology that a kind of advantages of simplicity and high efficiency prepares nanofiber, but prepare nanometer fiber net or nanofiber mats mostly, it as application number a kind of method and apparatus that adopts high-frequency electric field to prepare nanofiber of Chinese patent of 200410017609.6, this method can be crossed sol-gal process, in the alcosol of metalline, add polyvinylpyrrolidone PVP, method by electrostatic spinning makes nanofiber mats, has excellent electrochemical properties, because nanofiber is a random arrangement, therefore be unfavorable for bringing into play performances such as its mechanics.
Summary of the invention
Technical problem to be solved by this invention provides a kind of carbon nanotube composite fibre and preparation method thereof, to remedy the deficiencies in the prior art and defective, satisfies the needs of producing with some field development.
In order to solve the problems of the technologies described above, one of the technical solution used in the present invention is: a kind of carbon nanotube composite fibre, its component are surface-functionalized CNT and polymer, and the mass ratio of the two is 1: 2～1000.
As optimized technical scheme: described CNT is one or more in Single Walled Carbon Nanotube, multi-walled carbon nano-tubes or the carbon nano-fiber.
Described polymer is one or more of polyacrylonitrile, polyurethane, polyvinyl alcohol, nylon, polyester, cellulose, Sang Sizhong.
In order to solve the problems of the technologies described above, two of the technical solution used in the present invention is: a kind of manufacture method of carbon nanotube composite fibre as claimed in claim 1 comprises the steps:
1. with CNT ultrasonic dispersion 0.5～10 hour in strong acid, through washing, filter the CNT that obtains containing carboxyl.
2. the CNT and the thionyl chloride that the surface are contained carboxyl reacted 4～24 hours at 60～75 ℃, obtained chloride CNT (CNT-COCl).
3. chloride CNT (CNT-COCl) with can with the micromolecule and the macromolecular reaction of COCl radical reaction, preferably, one or more reactions in triton x-100 (Triton X-100), polyoxyethylene, ethylenediamine, hexamethylene diamine, PTMEG, caprolactam, the adipic acid obtain functionalized carbon nanotube through washing, filtration.
4. functionalized carbon nanotube that 3. step is made and polymer are made into co-blended spinning solution, make described composite fibre through high-voltage electrostatic spinning, employed receiving system is double or multi-electrode, electrode material is gold, silver, copper, iron, aluminium, conductive silicon or graphite conductor, and two electrode spacings are 1mm～100mm.As optimized technical scheme: described strong acid refers to the mixed liquor of the red fuming nitric acid (RFNA) or the concentrated sulfuric acid and red fuming nitric acid (RFNA) 3: 1 by volume and 4: 1 proportionings.
Described high-pressure electrostatic is controlled at 5～50KV.
The used solvent of spinning solution is dimethyl formamide, dimethylacetylamide, water, formamide, formic acid, carrene, chloroform, acetone, methyl alcohol, (this kind reagent is Cu (OH) to Schweizer reagent
2Be dissolved in and become dark blue solution in the excessive ammonia) in one or more.
The mass ratio of polymer and solvent is 1: 4～1000 in the electrostatic spinning solution.
The principle of the invention is by carbon nano tube surface grafting micromolecule or polymer, make CNT be dissolved in the organic solvent or the aqueous solution, polymer is dissolved in this organic solvent or the aqueous solution too simultaneously, make CNT form the solution that homogeneous disperses with polymer, solution droplets stretches, splits into the fine fiber of many diameters in the high-voltage electrostatic field high speed, and CNT can be orientated in polymer nanofiber.The principle that realizes high oriented nanofibers is because the nanofiber of high-pressure electrostatic ejection has positive charge, two electrode band negative electrical charges, nanofiber is subjected to the attraction of two electrodes simultaneously, particularly near two electrodes, this power is very strong, be straightened between two electrodes at nanofiber under the effect of electrostatic force, thereby obtain the nanofiber of high orientations.
The invention has the beneficial effects as follows: realized that CNT has even dispersion in nanofiber, realized the effective orientation of CNT in nanofiber, realized the high orientations of nanofiber.
Description of drawings
Fig. 1 is a high-orientation carbon nanotube polyacrylonitrile-radical nano-composite fiber sem photograph.
The specific embodiment
Below in conjunction with accompanying drawing the present invention is further elaborated, with reference to accompanying drawing 1.
Embodiment 1:
1. CNT is put into volume ratio and is 3: 1 the concentrated sulfuric acid and the ultrasonic dispersion of red fuming nitric acid (RFNA) mixed solution 5 hours, through washing, filter and obtain surperficial carboxylic CNT.
2. the CNT and the thionyl chloride that the surface are contained carboxyl reacted 24 hours at 60 ℃.Obtain CNT-COCl.
3. CNT-COCl and Triton X-100 obtained functionalized carbon nanotube in 24 hours 120 ℃ of reactions.
4. the CNT and the polyacrylonitrile that the surface are connected to Triton X-100 are dissolved in the dimethyl formamide jointly, and ultrasonic dispersion made co-blended spinning solution in 2 hours.
5. electrostatic spinning under the high pressure of 30kv is that the double earth electrode of 1mm is collected high orientation nano composite fibre with spacing, makes the carbon nanotube composite fibre.
Measure according to GB, gained CNT (5wt%) nano-composite fiber stretch modulus improves 68%.
Embodiment 2:
1. CNT is put into volume ratio and is 3: 1 concentrated sulfuric acids and the ultrasonic dispersion of red fuming nitric acid (RFNA) mixed solution 10 hours, through washing, filter and obtain surperficial carboxylic CNT.
2. the CNT and the thionyl chloride that the surface are contained carboxyl reacted 24 hours at 60 ℃.Obtain CNT-COCl.
3. CNT-COCl and caprolactam obtain functionalized carbon nanotube 250 ℃ of reactions 12 hours through washing, filtration.
4. the CNT and the nylon 6 that the surface are connected to nylon 6 are dissolved in the formic acid jointly, and ultrasonic dispersion made co-blended spinning solution in 1 hour.
5. electrostatic spinning under the high pressure of 30kv is that the double earth electrode of 1mm is collected high orientation nano composite fibre with spacing, makes the carbon nanotube composite fibre.
Measure according to GB, gained CNT (2wt%) nano-composite fiber stretch modulus improves 48%.
Embodiment 3:
1. CNT was put into volume ratio and is 3: 1 the concentrated sulfuric acid and red fuming nitric acid (RFNA) mixed solution ultrasonic 5 hours, through washing, filter and obtain surperficial carboxylic CNT.
2. the CNT and the thionyl chloride that the surface are contained carboxyl reacted 24 hours at 70 ℃.Obtain CNT-COCl.
3. CNT-COCl and hexamethylene diamine, adipic acid obtained functionalized carbon nanotube in 12 hours 200 ℃ of reactions.
4. the surface being connect skill has the CNT of hexamethylene diamine and adipic acid and nylon 66 to be dissolved in jointly in the formic acid, and decentralized system got co-blended spinning solution in ultrasonic 1 hour.
5. electrostatic spinning under the high pressure of 25kv is that four row's earth electrodes of 20mm are collected high orientation nano composite fibre with spacing, makes the carbon nanotube composite fibre.
Measure according to GB, gained CNT (5wt%) nano-composite fiber stretch modulus improves 69%.
Embodiment 4:
1. CNT was put into volume ratio and is 4: 1 the concentrated sulfuric acid and red fuming nitric acid (RFNA) mixed solution ultrasonic 5 hours, through washing, filter and obtain surperficial carboxylic CNT.
2. the CNT and the thionyl chloride that the surface are contained carboxyl reacted 24 hours at 65 ℃.Obtain CNT-COCl.
3. CNT-COCl and PVA obtained functionalized carbon nanotube in 12 hours 60 ℃ of reactions.
4. the surface being connect skill has the CNT of PVA and cellulose to be dissolved in jointly in the Schweizer reagent, and ultrasonic dispersion made co-blended spinning solution in 3 hours.
5. electrostatic spinning under the high pressure of 20kv is that the double earth electrode of 80mm is collected high orientation nano composite fibre with spacing, makes the carbon nanotube composite fibre.
Measure according to GB, gained CNT (20wt%) nano-composite fiber stretch modulus improves 106%.
Claims (9)
1. carbon nanometer tube composite fibre with high orientation, it is characterized in that: its component is surface-functionalized CNT and polymer, and the mass ratio of the two is 1: 2～1000.
2. composite fibre according to claim 1 is characterized in that: described CNT is one or more in Single Walled Carbon Nanotube, multi-walled carbon nano-tubes or the carbon nano-fiber.
3. composite fibre according to claim 1 is characterized in that: described polymer is one or more of polyacrylonitrile, polyvinyl alcohol, nylon, polyester, cellulose, Sang Sizhong.
4. the manufacture method of a composite fibre as claimed in claim 1 is characterized in that: comprise the steps:
1. with CNT ultrasonic dispersion 0.5～10 hour in strong acid, through washing, filter the CNT that obtains containing carboxyl.
2. will show and contain the CNT of carboxyl and thionyl chloride, obtain the chloride CNT 60～75 ℃ of reactions 4～24 hours.
3. the chloride CNT with can with the micromolecule of COCl radical reaction and big molecule 50～250 ℃ of reactions 4～24 hours down, after reacting completely, through washing, filter and obtain functionalized carbon nanotube.
4. functionalized carbon nanotube that 3. step is made and polymer are made into co-blended spinning solution, make described composite fibre through high-voltage electrostatic spinning, employed receiving system is double or multi-electrode, electrode material is gold, silver, copper, iron, aluminium, conductive silicon or graphite conductor, and two electrode spacings are 1mm～100mm.
5. the manufacture method of composite fibre according to claim 4, it is characterized in that: described strong acid refers to the mixed liquor of the red fuming nitric acid (RFNA) or the concentrated sulfuric acid and red fuming nitric acid (RFNA) 3: 1 by volume and 4: 1 proportionings.
6. the manufacture method of composite fibre according to claim 4, it is characterized in that: described high-pressure electrostatic is controlled at 5～50KV.
7. the manufacture method of composite fibre according to claim 4, it is characterized in that: the used solvent of spinning solution is one or more in dimethyl formamide, dimethylacetylamide, water, formamide, formic acid, carrene, chloroform, acetone, methyl alcohol, the Schweizer reagent.
8. the manufacture method of composite fibre according to claim 4, it is characterized in that: the mass ratio of polymer and solvent is 1: 4～1000 in the electrostatic spinning solution.
9. the manufacture method of composite fibre according to claim 4 is characterized in that: can be in triton x-100 (Triton X-100), polyoxyethylene, ethylenediamine, hexamethylene diamine, PTMEG, caprolactam, the adipic acid one or more with the micromolecule of COCl, NCO radical reaction and big molecule.
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| CN101069755B (en) * | 2007-06-19 | 2010-05-19 | 东南大学 | Bone-imitation tissue engineering stent material based on electric-woven super-fine fiber |
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| CN103779110B (en) * | 2014-01-27 | 2016-07-27 | 华南理工大学 | The preparation method of the full carbon supercapacitor electrode of a kind of linear flexible and application |
| CN106435797B (en) * | 2016-09-21 | 2018-11-23 | 东华大学 | A kind of preparation method of cellulose/carbon nano composite fibre |
| CN106854779A (en) * | 2016-12-15 | 2017-06-16 | 华南理工大学 | A kind of carbon nano-tube oriented enhanced carbon fibre composite and preparation method thereof |
| CN107523891A (en) * | 2017-07-26 | 2017-12-29 | 华南理工大学 | A kind of nanometer PVA fibrous composites of carbon nano-tube oriented enhancing and preparation method thereof |
| CN108532014A (en) * | 2018-04-10 | 2018-09-14 | 天津工业大学 | A kind of nanofiber electroactive polymer material and preparation method thereof |
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| CN110257944B (en) * | 2019-04-29 | 2022-05-13 | 东莞理工学院 | Preparation method and application of functionalized nano composite membrane |
| CN114921860B (en) * | 2022-06-27 | 2023-04-28 | 浙江鼎艺新材料科技有限公司 | Fine denier chinlon 6DTY and production method thereof |
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Patent Citations (3)
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| JPH0812310A (en) * | 1994-07-05 | 1996-01-16 | Nec Corp | Purifying-opening method of carbon-nanotube in liquid phase and introducing method of functional group |
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