CN104532384A - Polyacrylonitrile/carbon nano-tube fiber and preparation method thereof - Google Patents

Abstract

The invention discloses a polyacrylonitrile/carbon nano-tube fiber. An as-formed fiber of the polyacrylonitrile/carbon nanotube fiber is a PAN (polyacrylonitrile)/IL (ionic liquid)/CNTs (carbon nano-tubes) system containing PAN, IL and CNTs, wherein an 'atom-pi' interaction is formed between the carbon nano-tubes and the ionic liquid, and a 'pi-pi' interaction is formed between CNTs and PAN; the carbon nano-tubes are uniformly dispersed in polyacrylonitrile and do not form agglomeration, and the breaking strength is 4.9-6.0cN/dtex; and the as-formed fiber is extracted by using an extracting agent, and then is dried to obtain the polyacrylonitrile/carbon nano-tube fiber, wherein the carbon nano-tubes are uniformly dispersed in polyacrylonitrile and do not form agglomeration, and the breaking strength of the fiber is 7.0-9.0cN/dtex. The invention also discloses a method for preparing the polyacrylonitrile/carbon nano-tube fiber.

Description

A kind of polyacrylonitrile/carbon nano-tube fibre and preparation method thereof

Technical field

The invention belongs to polymeric material field, polyacrylonitrile/carbon nano-tube fibre relating to a kind of high strength and preparation method thereof, more particularly, relate to a kind of polyacrylonitrile/carbon nano-tube fibre prepared by plasticising spinning technique.

Background technology

Polyacrylonitrile/carbon nano tube compound material is one of emerging in recent years composite.Due to adding of CNT (being called for short CNTs), the mechanical property of polyacrylonitrile/carbon nano tube compound material, electric property, hot property aspect comparatively polyacrylonitrile have and improve significantly, and this composite is all had wide practical use in fields such as space flight, weaving, automobiles.Intensity and the CNT dispersing uniformity in the fibre of polyacrylonitrile/carbon nano-tube fibre (referred to as PAN/CNTs fiber) are closely related, disperse more even, the possibility of the Contact of polyacrylonitrile (referred to as PAN) strand and carbon nano tube surface is larger, therefore polyacrylonitrile strand needs the resistance that overcomes larger when Tensile, causes fracture strength higher.And, the intensity of polyacrylonitrile/carbon nano-tube fibre (referred to as PAN/CNTs fiber) also with the molecular weight of polyacrylonitrile (PAN) and the concentration (i.e. the solid content of polyacrylonitrile) of spinning system closely related, polyacrylonitrile molecular weight is larger, interaction force between fiber molecule chain is stronger, the resistance that during fibrous fracture, needs overcome is larger, and therefore fracture strength is larger; The concentration of spinning system is higher, the strand increasing number in the fiber unit volume spun, and strand is more less likely to occur slippage fracture, and therefore intensity is higher.The method that the usual PAN/CNTs of preparation fiber adopts is solution spinning (being called for short solution to spin), and wherein viscosity average molecular weigh wider range of polyacrylonitrile is 1 × 10 ⁴g/mol ~ 5 × 10 ⁴g/mol, and solid content is only 20wt.% ~ 30wt.%.This is because solution spins, used solution is dimethyl formamide (DMAC), dimethylacetylamide (DMF), dimethyl sulfoxide (DMSO) (DMSO), the polarity of these solvents is still strong not, causes PAN powder dissolubility in the solution limited.Solution spins and distinctively causes the intensity of prepared PAN/CNTs fiber lower compared with low-solid content, and the scope of common intensity is 4-6cN/dtex, cannot meet high strength requirement.

In addition, employ macro-corrosion chemical solvent because solution spins in process, these solvents easily cause health and environmental pollution etc. problem.Reduce environmental pollution just to need to increase organic solvent recovery unit, need to consume a large amount of manpowers and financial resources.Meanwhile, when using conventional solvent to prepare polyacrylonitrile fibre, spinning speed is lower, and production efficiency is low, very uneconomical.

Summary of the invention

Above-mentioned defect in polyacrylonitrile/carbon nano-tube fibre technology of preparing is spun in order to overcome solution, inventor furthers investigate for the preparation method of polyacrylonitrile/carbon nano-tube fibre, develop a kind of plasticising spinning (being called for short plasticising to spin) technique, it uses hypotoxic ionic liquid as plasticizer, effectively can not only improve spinning speed, enhance productivity, and decrease the pollution to environment and the potential injury to human body, the technique reclaimed is simple, reduces production cost.This technique is applicable to high molecular weight polypropylene nitrile (the viscosity average molecular weigh scope 1 × 10 of high polymerization degree ⁵g/mol ~ 9 × 10 ⁵g/mol), can be used for the spinning system of high PAN concentration.Inventor is also surprised to find that, ionic liquid is used to improve the inner molecular structure of polyacrylonitrile/carbon nano-tube fibre as the plasticising spinning process of plasticizer, in obtained polyacrylonitrile/carbon nano-tube fibre, the dispersing uniformity of CNT improves greatly, overcome the agglomeration of CNT, make the intensity of fiber far above the polyacrylonitrile/carbon nano-tube fibre of prior art.

Therefore, an object of the present invention is the polyacrylonitrile/carbon nano-tube fibre providing a kind of high strength.

Another object of the present invention is to provide a kind of method preparing polyacrylonitrile/carbon nano-tube fibre.

For achieving the above object, the present invention adopts following technical scheme:

A kind of polyacrylonitrile/ionic liquid/carbon nano-tube fibre, it is the as-spun fibre of polyacrylonitrile/carbon nano-tube fibre, the PAN/IL/CNTs system comprising polyacrylonitrile (PAN), ionic liquid (IL) and CNT (CNTs), wherein polyacrylonitrile: ionic liquid: the mass ratio of CNT is 47-83: 9-50: 0.1-8; Wherein form " atom-π " between CNT and ionic liquid to interact, form " π-π " between CNTs and PAN and interact; Wherein even carbon nanotube to be scattered in polyacrylonitrile and not to form reunion, and the fracture strength of as-spun fibre is 4.9-6.0cN/dtex.

A kind of polyacrylonitrile/carbon nano-tube fibre, be by use extractant to extract above-mentioned as-spun fibre and dry after, wherein even carbon nanotube to be scattered in polyacrylonitrile and not to form reunion, and the fracture strength of fiber is 7.0-9.0cN/dtex.

Preferably, polyacrylonitrile in above-mentioned two kinds of fibers is homopolymers, bipolymer or multiple copolymer, the monomer of wherein said homopolymers is acrylonitrile, the monomer of bipolymer or multiple copolymer is acrylonitrile and the monomer containing unsaturated group, and the wherein said monomer containing unsaturated group is selected from methyl acrylate, methyl methacrylate, itaconic acid, acrylamide, methacrylic acid, Sodium styrene sulfonate or their two or more mixtures; Viscosity average molecular weigh (the M of polyacrylonitrile _η) be 1 × 10 ⁵~ 9 × 10 ⁵g/mol, more preferably 2 × 10 ⁵~ 9 × 10 ⁵g/mol; Optimization polypropylene nitrile is Powdered.

Preferably, the purity of the CNT in above-mentioned two kinds of fibers is not less than 90%, and described CNT is Single Walled Carbon Nanotube and/or multi-walled carbon nano-tubes; The diameter of wherein said Single Walled Carbon Nanotube is 0.7nm ~ 3.0nm, and length is 0.5 ~ 5 μm; The diameter of described multi-walled carbon nano-tubes is 15nm ~ 30nm, and length is 0.3 ~ 5 μm.

Preferably, CNT in above-mentioned two kinds of fibers can be Single Walled Carbon Nanotube or the multi-walled carbon nano-tubes of modification, is such as hydroxyl modified multi-walled carbon nano-tubes, carboxyl modified multi-walled carbon nano-tubes, hydroxyl modified Single Walled Carbon Nanotube, carboxyl modified Single Walled Carbon Nanotube.

Preferably, the CATION of the ionic liquid in above-mentioned two kinds of fibers is selected from alkyl-quaternaryammonium cations, Wan Ji quaternary phosphine CATION, N, N-dialkylimidazolium cation and N-alkylpyridiniium cation; Anion is selected from halide ion (Cl ^-, Br ^-, I ^-), acetate ion (CH ₃cO ₂ ^-), nitrate ion (NO ₃ ^-), tetrafluoro boric acid salt ion (BF ₄ ^-) and trifluoracetic acid salt ion (CF ₃cO ₂ ^-).

Preferably, the ionic liquid in above-mentioned two kinds of fibers can be a kind of ionic liquid, also can be the mixture of two or more ionic liquid.

Prepare a method for above-mentioned polyacrylonitrile/ionic liquid/carbon nano-tube fibre, comprise the steps:

The first step: prepare ionic liquid/carbon nanotube systems by in-situ synthesized or blending method, wherein ionic liquid: CNT: the mass ratio of surfactant is 9-50: 0.1-8: 0.01-0.8, wherein in-situ synthesized be by the raw material needed for synthesis ionic liquid, CNT, surfactant is first admixed together reacts, the ionic liquid/carbon nanotube systems needed for generation; Blending method be by CNT, surfactant and in advance at 80 DEG C-150 DEG C the ionic liquid of melting mix, then at 80 DEG C-150 DEG C, mix 12-24h, until mix;

Second step: prepared by spinning system: fully mixed by the ionic liquid/carbon nanotube systems of polyacrylonitrile and first step gained, obtain uniformly as the mixture of spinning system, wherein polyacrylonitrile: ionic liquid: CNT: the mass ratio of surfactant is 47-83: 9-50: 0.1-8: 0.01-0.8;

3rd step: use extruder to carry out spinning in the mixture of second step gained, obtain as-spun fibre.

Prepare a method for above-mentioned polyacrylonitrile/carbon nano-tube fibre, comprise the steps:

The first step: prepare ionic liquid/carbon nanotube systems by in-situ synthesized or blending method, wherein ionic liquid: CNT: the mass ratio of surfactant is 9-50: 0.1-8: 0.01-0.8, wherein in-situ synthesized be by the raw material needed for synthesis ionic liquid, CNT, surfactant is first admixed together reacts, the ionic liquid/carbon nanotube systems needed for generation; Blending method be by CNT, surfactant and in advance at 80 DEG C-150 DEG C the ionic liquid of melting mix, then at 80 DEG C-150 DEG C, mix 12-24h, until mix;

Second step: prepared by spinning system: fully mixed by the ionic liquid/carbon nanotube systems of polyacrylonitrile and first step gained, obtain uniformly as the mixture of spinning system, wherein polyacrylonitrile: ionic liquid: CNT: the mass ratio of surfactant is 47-83: 9-50: 0.1-8: 0.01-0.8;

3rd step: use extruder to carry out spinning in the mixture of second step gained, obtain as-spun fibre;

4th step: the as-spun fibre extractant of the 3rd step gained is extracted, air dry or oven dry, obtain polyacrylonitrile/carbon nano-tube fibre.

Preferably, the described surfactant in above-mentioned two kinds of methods is at least one in soap class surfactant, hydrosulphate, azochlorosulfonate acid compound, cationic surfactant and amphoteric ionic surfactant.Such as, surfactant can be alkali metal soap such as soda soap or potash soap, alkaling earth metal base class such as calcium soap or barium soap, lauryl sodium sulfate, organic amine soap such as textile soap, triethanolamine soap such as trihydroxy ethylamine oleate soap, sulfated castor oil, neopelex, sodium glycocholate, fatty glyceride such as glycerol tristearate, palmitin or glycerol trioleate.

Preferably, depend on kind and/or the specification of ionic liquid starting material, CNT, surfactant, the reaction temperature of the first step situ method of formation in above-mentioned two kinds of methods is 50-150 DEG C, and the reaction time is 8-84h.

Preferably, depend on content and/or the specification of the physico-chemical property of spinning system, polyacrylonitrile and ionic liquid/carbon nanotube systems, in the 3rd step in above-mentioned two kinds of methods, spinning temperature is 80-350 DEG C, and the linear velocity of up-coiler is 100m/min ~ 1500m/min.

Preferably, depend on the physico-chemical property of as-spun fibre, ionic liquid and extractant kind, the extraction temperature in the 4th step is 5-200 DEG C.

Preferably, the extractant in the 4th step is can dissolved ions liquid but do not destroy the C of polyacrylonitrile fibre ₁-C ₁₈polyalcohol, ester, acid, one or more mixture in water and other solvent.

Preferably, the extractant in the 4th step is one or more the mixture in methyl alcohol, ethanol, propyl alcohol, butanols, octanol, ethylene glycol, butanediol, glycerol, n-hexane, acetone, ethyl acetate, isoamyl acetate, phosphate, carboxylic acid, sulfuric acid, sulfonic acid and water.

The present invention adopts plasticising spin processes to prepare PAN/CNTs fiber, effectively prevent the use of a large amount of toxic chemical, achieves Green synthesis, protect ecological environment, also greatly reduce production cost; And by disperseing CNTs with ionic liquid, effectively overcoming the agglomeration of CNTs, substantially increasing the intensity of PAN/CNTs fiber.

Accompanying drawing explanation

Fig. 1 is that in embodiment 1, PAN/IL/CNTs as-spun fibre and PAN/IL as-spun fibre contrast the infrared spectrum comparison diagram of sample at 160 DEG C.

Fig. 2 is the SEM photo of gained PAN/CNTs fiber longitudinal direction in embodiment 1.

Fig. 3 is the SEM photo of gained PAN/CNTs fiber cross section in embodiment 1.

Detailed description of the invention

Below in conjunction with specific embodiment and accompanying drawing, the invention will be further described.Should be understood that these embodiments are only not used in for illustration of the present invention to limit the scope of the invention.

Relate to the addition of many kinds of substance, content and concentration herein, wherein said " part ", unless otherwise indicated, all refers to " weight portion "; Described percentage composition, unless otherwise indicated, all refers to mass percentage.

Herein, the fiber that term " as-spun fibre " obtains after referring to and spinning system extruder being carried out spinning, extracts without extractant.Polyacrylonitrile in as-spun fibre of the present invention: ionic liquid: the mass ratio of CNT is 47-83: 9-50: 0.1-8.It can comprise surfactant, now polyacrylonitrile: ionic liquid: CNT: the mass ratio of surfactant is 47-83: 9-50: 0.1-8: 0.01-0.8.

The as-spun fibre of polyacrylonitrile/carbon nano-tube fibre of the present invention is the PAN/IL/CNTs system comprising polyacrylonitrile (PAN), ionic liquid (IL) and CNT (CNTs), wherein form " atom-π " between CNT and ionic liquid to interact, form " π-π " between CNTs and PAN and interact; Wherein even carbon nanotube to be scattered in polyacrylonitrile and not to form reunion, and fracture strength is 4.9-6.0cN/dtex; As-spun fibre extractant carries out extracting and obtains polyacrylonitrile/carbon nano-tube fibre after drying, and wherein even carbon nanotube to be scattered in polyacrylonitrile and not to form reunion, and the fracture strength of fiber is 7.0-9.0cN/dtex.

In the present invention, optimization polypropylene nitrile is bipolymer or multiple copolymer, monomer whose is acrylonitrile and the monomer containing unsaturated group, and the wherein said monomer containing unsaturated group is selected from methyl acrylate, methyl methacrylate, itaconic acid, acrylamide, methacrylic acid, Sodium styrene sulfonate or their two or more mixtures.Compare acrylonitrile homopolymer, bipolymer or multiple copolymer seem more easily and ionic liquid forms intermolecular hydrogen bond, and its mechanism waits further research.

In the present invention, the CATION in ionic liquid is selected from 4 kinds of CATION with following structural formula:

In fuse salt state under ionic liquid room temperature, there is very wide liquid temperature range, have without characteristics such as obvious volatility, heat endurance, hypotoxicity, strong polarity.CNT has obvious draw ratio, and radial dimension is nanometer scale, and axial dimension is micron dimension.There is between CNT " π-π " interaction force, be aggregating state under causing its normality, obvious agglomeration is there is when being dissolved in organic solvent as enhancing additive, although the method solved employs ultrasonic disperse technology and adds dispersant etc., reunite and remain a very formidable natural phenomena.For the organic solvent of routine, ionic liquid demonstrates stronger polarity effect, particularly there is very strong Hyarogen-bonding between anions and canons.

Ionic liquid is used as the plasticizer of polymer at present, such as polyvinyl alcohol, polyvinyl chloride, polymethyl methacrylate etc., and ionic liquid effectively reduces the fusing point, glass transition temperature etc. of polymer; Also improve the viscoplasticity of polymer simultaneously.And ionic liquid rarely has report for plasticized polypropylene nitrile.

Inventor surprisingly finds, spin in process in plasticising, above-mentioned ionic liquid not only can and CNT between form very strong " atom-π " interaction force, and can and polyacrylonitrile between form very strong hydrogen bond, good Accessory Effect is served to the dispersion of CNT in polyacrylonitrile strand.

Another surprisingly finds, spin in process in plasticising, " atom-π " of above-mentioned polyacrylonitrile and above-mentioned ionic liquid/formed between carbon nanotube systems intermediate ion liquid and CNT interacts, formed between ionic liquid and polyacrylonitrile " π-π " interacts all clearly, and it is all very strong, this phenomenon was not seen in report, and its mechanism waits further research.

Research also finds, traditional CNT of comparing, and modified carbon nano-tube that is hydroxyl or carboxyl can also form " π-π " and interacts with ionic liquid, the dispersion of more favourable CNT; Modified carbon nano-tube can produce stronger interaction force with the itrile group of polyacrylonitrile, plasticising better simultaneously, is conducive to the intensity improving polyacrylonitrile/carbon nano-tube fibre.

In the present invention, the method for preparing polyacrylonitrile/carbon nano-tube fibre compares many 4th step--the as-spun fibre extraction step of the method preparing polyacrylonitrile/ionic liquid/carbon nano-tube fibre.In this step, extractant extracts ionic liquid constituents in as-spun fibre and surface active agent composition, but remains the homogeneously dispersed state that CNT do not reunite.

The advantage of method of the present invention is the high-load spinning system being applicable to prepare high molecular weight polypropylene nitrile, and improves the blended uniformity of system.

In the present invention, the viscosity average molecular weigh (M of polyacrylonitrile _η) scope be 1 × 10 ⁵~ 9 × 10 ⁵g/mol, its lower limit is 1 × 10 ⁵g/mol, is preferably 1.3 × 10 ⁵, 1.5 × 10 ⁵, 1.8 × 10 ⁵, 2.0 × 10 ⁵, 2.3 × 10 ⁵, 2.5 × 10 ⁵, 2.8 × 10 ⁵, 3.0 × 10 ⁵, 3.3 × 10 ⁵, 3.5 × 10 ⁵, 3.8 × 10 ⁵, 4.0 × 10 ⁵g/mol.Its upper limit is 9 × 10 ⁵g/mol, is preferably 8.8 × 10 ⁵, 8.5 × 10 ⁵, 8.3 × 10 ⁵, 8.0 × 10 ⁵, 7.8 × 10 ⁵, 7.5 × 10 ⁵, 7.3 × 10 ⁵, 7.0 × 10 ⁵, 6.8 × 10 ⁵, 6.5 × 10 ⁵, 6.3 × 10 ⁵, 6.0 × 10 ⁵, 5.8 × 10 ⁵, 5.5 × 10 ⁵, 5.3 × 10 ⁵, 5.0 × 10 ⁵g/mol.If the viscosity average molecular weigh of polyacrylonitrile is lower than 1 × 10 ⁵g/mol, the fracture strength of the polyacrylonitrile/carbon nano-tube fibre obtained and polyacrylonitrile/ionic liquid/carbon nano-tube fibre is tending towards declining, and can not meet high strength requirement.If the viscosity average molecular weigh of polyacrylonitrile is higher than 9 × 10 ⁵g/mol, in spinning process, spinning system viscosity is excessive, causes difficulty in spinning.

Preferably, the purity of the CNT in polyacrylonitrile/carbon nano-tube fibre and polyacrylonitrile/ionic liquid/carbon nano-tube fibre is preferably not less than 90%, more preferably be not less than 91%, be more preferably not less than 92%, be more preferably not less than 93%, more preferably 94% is not less than, more preferably be not less than 95%, be more preferably not less than 96%, be more preferably not less than 97%, more preferably be not less than 98%, be more preferably not less than 99%.If the purity of CNT is lower than 90%, can have a negative impact to the mechanical property of polyacrylonitrile/carbon nano-tube fibre and polyacrylonitrile/ionic liquid/carbon nano-tube fibre, cause fracture strength decline or uncontrollable.

The diameter of Single Walled Carbon Nanotube is 0.7nm ~ 3.0nm, and such as mean value can be 1.0,1.3,1.5,1.8,2.0,2.3,2.5 or 2.8nm.If the diameter of Single Walled Carbon Nanotube is less than 0.7nm, then the high cost of Single Walled Carbon Nanotube, causes the economy of final products to decline; If the diameter of Single Walled Carbon Nanotube is greater than 3.0nm, then the dispersing uniformity of Single Walled Carbon Nanotube in polyacrylonitrile declines, and has a negative impact to the mechanical property of fiber.

The length of Single Walled Carbon Nanotube is 0.5 ~ 5 μm, and such as mean value can be 1.0,1.5,2.0,2.5,3.0,3.5,4.0 or 4.5 μm.If the length of Single Walled Carbon Nanotube is less than 0.5 μm, then the high cost of Single Walled Carbon Nanotube, causes the economy of final products to decline; If the length of Single Walled Carbon Nanotube is greater than 5 μm, then the dispersing uniformity of Single Walled Carbon Nanotube in polyacrylonitrile declines, and has a negative impact to the mechanical property of fiber.

The diameter of multi-walled carbon nano-tubes is 15nm ~ 30nm, and such as mean value can be 18,20,23,25 or 28nm.If the diameter of multi-walled carbon nano-tubes is less than 15nm, then the high cost of multi-walled carbon nano-tubes, causes the economy of final products to decline; If the diameter of multi-walled carbon nano-tubes is greater than 30nm, then the dispersing uniformity of multi-walled carbon nano-tubes in polyacrylonitrile declines, and has a negative impact to the mechanical property of fiber.

The length of multi-walled carbon nano-tubes is 0.3 ~ 5 μm, and such as mean value can be 0.5,1.0,1.5,2.0,2.5,3.0,3.5,4.0 or 4.5 μm.If the length of multi-walled carbon nano-tubes is less than 0.5 μm, then the high cost of multi-walled carbon nano-tubes, causes the economy of final products to decline; If the length of multi-walled carbon nano-tubes is greater than 5 μm, then the dispersing uniformity of multi-walled carbon nano-tubes in polyacrylonitrile declines, and has a negative impact to the mechanical property of fiber.

Plasticising spinning process of the present invention improves the inner molecular structure of polyacrylonitrile/carbon nano-tube fibre, and in obtained polyacrylonitrile/carbon nano-tube fibre, the dispersing uniformity of CNT improves greatly, substantially increases the intensity of fiber.

Embodiment

Below in conjunction with embodiment and accompanying drawing, technical scheme of the present invention is further described, but described embodiment is not only construed as limiting the invention for illustration of the present invention.

One, method of testing and standard:

Polyacrylonitrile/the carbon nano-tube fibre obtain following each embodiment and polyacrylonitrile/ionic liquid/carbon nano-tube fibre carry out the testing evaluation of following technical indicator.

Fracture strength: the intensity using fibre strength instrument test fiber, the clamp distance of fiber is 20mm, and draw speed is 20mm/min.

Fiber microscopic pattern: fiber is quenched after disconnected and surperficial metal spraying through freeze drying, liquid nitrogen, with Japanese JSM-5600LV type scanning electron microscope test.

Experiment material:

Viscosity average molecular weigh (M _η) be respectively 1.3 × 10 ⁵g/mol, 1.5 × 10 ⁵g/mol, 1.8 × 10 ⁵g/mol, 2 × 10 ⁵the polyacrylonitrile available from Sigma of g/mol.

Viscosity average molecular weigh (M _η) be respectively 2.3 × 10 ⁵g/mol, 2.5 × 10 ⁵g/mol, 3 × 10 ⁵g/mol, 3.5 × 10 ⁵the polyacrylonitrile available from Sigma of g/mol.

Viscosity average molecular weigh (M _η) be respectively 5.0 × 10 ⁵g/mol, 5.3 × 10 ⁵g/mol, 6.0 × 10 ⁵g/mol, 6.8 × 10 ⁵g/mol, 7.0 × 10 ⁵the polyacrylonitrile purchased from American Amoco company of g/mol.

Viscosity average molecular weigh (M _η) be respectively 9 × 10 ⁵g/mol, 8.5 × 10 ⁵g/mol, 8 × 10 ⁵g/mol, 7.5 × 10 ⁵the polyacrylonitrile purchased from American Zoltek company of g/mol.

Single Walled Carbon Nanotube (specification is TNS, TNSH and TNSC) and multi-walled carbon nano-tubes (specification is TNGM2, TNGMH2 and TNGMC2) are purchased from Chengdu Organical Chemical Co., Ltd., Chinese Academy of Sciences;

Single Walled Carbon Nanotube (specification is SWNT-12), multi-walled carbon nano-tubes (specification is MWNT-10) are purchased from nanometer port, Shenzhen Co., Ltd;

Hydroxyl modified Single Walled Carbon Nanotube (CNT200, CNT201)) purchased from Beijing Deco Dao Jin Science and Technology Ltd.;

Carboxyl modified Single Walled Carbon Nanotube (specification is HQNANO-CNTs-002C) is purchased from Suzhou permanent ball science and technology sales department;

Hydroxyl modified multi-walled carbon nano-tubes (CNT202, CNT204 and CNT206) and carboxyl modified multi-walled carbon nano-tubes (specification is CNT302, CNT304 and CNT306) are purchased from Beijing Deco Dao Jin Science and Technology Ltd..

It is pure that other reagent are all analysis, purchased from China Medicine (Group) Shanghai Chemical Reagent Co..

Extruder: DSM Xplore type extruder, Beijing Ying Gehaide analytical technology Co., Ltd.

Embodiment 1

Prepare ionic liquid/carbon nanotube systems by in-situ synthesized: 17.35g mono-chlorobutane, 13.9gN methylimidazole, 0.1g carboxyl modified Single Walled Carbon Nanotube (CNT200), 0.392g lauryl sodium sulfate are mixed in there-necked flask, react 48 hours at 80 DEG C; Add the sodium hexafluoro phosphate of 28.49g again, with the acetone of 100ml for solvent, synthesis 1-butyl-3-methyl hexafluorophosphate/carbon nanotube mixture stratification removes sodium chloride further.Use the ethyl acetate of 30ml to carry out washing three times to blend, obtain ionic liquid/carbon nanotube systems; Or

Ionic liquid/carbon nanotube systems is prepared: in single port flask, add 0.1g CNT (CNT200), 0.392g lauryl sodium sulfate by blend method, add 48.16g 1-butyl-3-methyl hexafluorophosphate again, at 90 DEG C, fully mixing 48h makes it even; Use the ethyl acetate of 30ml to carry out washing three times to blend, obtain ionic liquid/carbon nanotube systems.

By polyacrylonitrile powder, (viscosity average molecular weigh is 2 × 10 ⁵g/mol, acrylonitrile: methyl methacrylate: itaconic acid=91.5mol%: 6.5mol%: 2mol%) and above-mentioned ionic liquid/carbon nanotube systems in liquid nitrogen, fully mix 10min, obtain spinning system.Wherein polyacrylonitrile powder: ionic liquid: CNT: the mass percent of lauryl sodium sulfate is 51.35%: 48.16%: 0.1%: 0.392%.

Use extruder to carry out spinning the spinning system of gained, the temperature of setting spinning is 230 DEG C, and the linear velocity of up-coiler is 1000m/min; Obtain as-spun fibre PAN/CNTs/ [Bmim] PF ₆.The intensity of as-spun fibre is 5.24cN/dtex.

As-spun fibre is carried out high-temperature infrared sign, and prepares PAN/ [Bmim] PF formed by polyacrylonitrile and above-mentioned ionic liquid ₆fiber (not carbon nanotubes) is contrast sample.As shown in Figure 1, can find out, at 160 DEG C of temperature, PAN/ [Bmim] PF ₆on the imidazole ring of fiber intermediate ion liquid, the position at C-H peak is 3137.17cm ^-1, and in PAN, the position at itrile group peak is 2240.16cm ^-1.PAN/CNTs/ [Bmim] PF ₆the position at fiber imidazoles peak is by 3137.17cm ^-1red shift is to 3145.73cm ^-1, illustrate after adding CNT CNTs, " atom-π " interaction force can be formed between CNT and ionic liquid, and this strong interaction force be conducive to CNTs at ionic liquid IL ([Bmim] PF ₆) in dispersion.This " atom-π " interactional formation can weaken original polyacrylonitrile (PAN) and [Bmim] PF ₆between hydrogen bond action, cause the red shift at itrile group peak.Meanwhile, it should be noted that can form again " π-π " interaction force between CNTs and PAN, this interaction force can cause the blue shift at itrile group peak when after introducing CNTs.The displacement basic neutralisation that two kinds of interaction forces cause, so as can be seen from infrared spectrum, PAN/CNTs/ [Bmim] PF ₆the position of the itrile group of fiber is at 2240.5cm ^-1, that is there is no and be subjected to displacement.Therefore, as can be seen from infrared spectrum, between CNTs and PAN, there is strong interaction, be conducive to the intensity improving final PAN/CNTs fiber like this.

Be extract the as-spun fibre prepared during the 10wt.% glycerol of 100 DEG C and the aqueous solution of 10wt.% acetone are bathed in temperature, air dry, obtains PAN/CNTs fiber.As shown in Figure 2, the diameter of fiber is 14-15 μm, fracture strength be 7.1cN/dtex, CNTs dispersiveness in the pan as shown in Figure 3, display CNTs be uniformly dispersed, do not form reunion, therefore use a small amount of CNTs just to obtain very high fibre strength.

Embodiment 2

Ionic liquid/carbon nanotube systems is prepared: the pyridine of 4.22g, 5.45g mono-chlorobutane, 7.65g Single Walled Carbon Nanotube (TNS), 0.51g textile soap are mixed in there-necked flask by in-situ synthesized, react 72 hours at 60 DEG C, generate N-butyl-pyridinium villaumite/carbon nanotube mixture.Use the ethyl acetate of 30ml to carry out washing three times to blend, obtain ionic liquid/carbon nanotube systems; Or

Prepare ionic liquid/carbon nanotube systems by blend method: in single port flask, add 7.65g CNT (TNS), 0.51g textile soap, then add 9.18gN-butyl-pyridinium villaumite, at 80 DEG C, mix 36h.Use the ethyl acetate of 30ml to carry out washing three times to blend, obtain ionic liquid/carbon nanotube systems.

By polyacrylonitrile powder, (viscosity average molecular weigh is 3 × 10 ⁵g/mol, acrylonitrile: methyl methacrylate: itaconic acid=97.5mol%: 1.5mol%: 1mol%) and above-mentioned ionic liquid/carbon nanotube systems at 40 DEG C, fully mix 20min, obtain spinning system.Wherein polyacrylonitrile powder: ionic liquid: CNT: the mass percent of textile soap is 82.66%: 9.18%: 7.65%: 0.51%.

Use extruder to carry out spinning the spinning system of gained, the temperature of setting spinning is 220 DEG C, and the linear velocity of up-coiler is 700m/min; The intensity of the as-spun fibre of preparation is 5.14cN/dtex.Infrared spectrogram shows to form " π-π " interaction force in as-spun fibre between CNTs and PAN, form " atom-π " interaction force (not shown) between CNTs and ionic liquid.Be extract in the 15wt.% glycerin solution of 200 DEG C in temperature by the as-spun fibre prepared, air dry, obtains PAN/CNTs fiber.The diameter of fiber is 15-16 μm, and intensity is 7.7cN/dtex.CNTs is uniformly dispersed in the pan, does not form reunion (not shown).

Embodiment 3

Ionic liquid/carbon nanotube systems is prepared: 19.8g bromic ether and 13.4gN methylimidazole, 4.48g hydroxyl modified Single Walled Carbon Nanotube (CNT200), 0.32g trihydroxy ethylamine oleate soap are mixed in there-necked flask by in-situ synthesized, agitating heating 12 hours under 70 DEG C of conditions, generates 1-ethyl-3-methylimidazole bromine salt/carbon nanotube mixture.Use the ethyl acetate of 30ml to carry out washing three times to blend, obtain ionic liquid/carbon nanotube systems; Or

Prepare ionic liquid/carbon nanotube systems by blend method: in single port flask, add 4.48g CNT (CNT200), 0.32g triethanolamine soap, then add 31.2g 1-ethyl-3-methylimidazole bromine salt.24h is mixed at 80 DEG C.Use the ethyl acetate of 30ml to carry out washing three times to blend, obtain ionic liquid/carbon nanotube systems.

By polyacrylonitrile powder, (viscosity average molecular weigh is 5 × 10 ⁵g/mol, acrylonitrile: methyl acrylate: itaconic acid=85mol%: 7.5mol%: 7.5mol%) and above-mentioned ionic liquid/carbon nanotube systems at room temperature fully mix 30min, obtain spinning system.Wherein polyacrylonitrile powder: ionic liquid: CNT: the mass percent of trihydroxy ethylamine oleate soap is 64%: 31.2%: 4.48%: 0.32%.

Use extruder to carry out spinning the spinning system of gained, the temperature of setting spinning is 230 DEG C, and the linear velocity of up-coiler is 800m/min; The intensity of the as-spun fibre of preparation is 4.97cN/dtex.Infrared spectrogram shows to form " π-π " interaction force in as-spun fibre between CNTs and PAN, form " atom-π " interaction force (not shown) between CNTs and ionic liquid.Be extract the as-spun fibre prepared during the 0.1wt.% tributyl phosphate of 130 DEG C and the aqueous solution of 0.1wt.% dioctyl octyl phosphate are bathed in temperature, air dry, obtains PAN/CNTs fiber.The diameter of fiber is 14.7-15.8 μm, and intensity is 7.15cN/dtex.CNTs is uniformly dispersed in the pan, does not form reunion (not shown).

Embodiment 4

Ionic liquid/carbon nanotube systems is prepared: a chlorobutane of 29.37g and 23.69g N methylimidazole, 0.167g hydroxyl modified multi-walled carbon nano-tubes (CNT202), 0.0167g calcium soap are mixed in there-necked flask by in-situ synthesized, react 48 hours at 150 DEG C, add 23.66g sodium acetate again, with the acetone of 110ml for solvent, synthesis 1-ethyl-3-methylimidazole acetate/carbon nanotube mixture, stratification removes sodium chloride.Use the ethyl acetate of 30ml to carry out washing three times to blend, obtain ionic liquid/carbon nanotube systems; Or

Prepare ionic liquid/carbon nanotube systems by blend method: in single port flask, add 0.167g CNT (CNT202), 0.0167g calcium soap, then add 49.12g 1-ethyl-3-methylimidazole acetate.24h is mixed at 60 DEG C.Use the ethyl acetate of 30ml to carry out washing three times to blend, obtain ionic liquid/carbon nanotube systems.

By polyacrylonitrile powder, (viscosity average molecular weigh is 5 × 10 ⁵g/mol, acrylonitrile: methyl acrylate: itaconic acid=87mol%: 10.5mol%: 2.5mol%) and above-mentioned ionic liquid/carbon nanotube systems in ice-water bath, fully mix 40min, obtain spinning system.Wherein polyacrylonitrile powder: ionic liquid: CNT: the mass percent of calcium soap is 50.7%: 49.12%: 0.167%: 0.0167%.

Use extruder to carry out spinning the spinning system of gained, the temperature of setting spinning is 130 DEG C, and the linear velocity of up-coiler is 150m/min; The intensity of the as-spun fibre of preparation is 5.57cN/dtex.Infrared spectrogram shows to form " π-π " interaction force in as-spun fibre between CNTs and PAN, form " atom-π " interaction force (not shown) between CNTs and ionic liquid.Be extract the as-spun fibre prepared during the 15wt.% ethanol of 5 DEG C and the aqueous solution of 5wt.% methyl alcohol are bathed in temperature, dry, obtain PAN/CNTs fiber.The diameter of fiber is 15-16 μm, and intensity is 8.1cN/dtex.CNTs is uniformly dispersed in the pan, does not form reunion (not shown).

Embodiment 5

Prepare ionic liquid/carbon nanotube systems by in-situ synthesized: a chlorobutane of 17.48g and 14.1g N methylimidazole, 0.19g carboxyl modified Single Walled Carbon Nanotube (HQNANO-CNTs-002C), 0.02g lauryl sodium sulfate are mixed in there-necked flask, react 12 hours at 110 DEG C; Add the sodium hexafluoro phosphate of 28.84g again, with the acetone of 110ml for solvent, synthesis 1-butyl-3-methyl hexafluorophosphate/carbon nanotube mixture further, stratification removes sodium chloride; Use the ethyl acetate of 30ml to carry out washing three times to blend, obtain ionic liquid/carbon nanotube systems; Or

Ionic liquid/carbon nanotube systems is prepared: in single port flask, add 0.19g CNT (HQNANO-CNTs-002C), 0.02g lauryl sodium sulfate by blend method, add 48.49g 1-butyl-3-methyl hexafluorophosphate again, at 90 DEG C, mix 48h make it even; Use the ethyl acetate of 30ml to carry out washing three times to blend, obtain ionic liquid/carbon nanotube systems.

By polyacrylonitrile powder, (viscosity average molecular weigh is 7 × 10 ⁵g/mol, acrylonitrile: methyl methacrylate: acrylamide=95mol%: 2.5mol%: 2.5mol%) and above-mentioned ionic liquid/carbon nanotube systems fully mix 1h at 150 DEG C, obtain spinning system.Wherein polyacrylonitrile powder: ionic liquid: CNT: the mass percent of lauryl sodium sulfate is 51%: 48.79%: 0.19%: 0.02%.

Use extruder to carry out spinning the spinning system of gained, the temperature of setting spinning is 150 DEG C, and the linear velocity of up-coiler is 300m/min; The intensity of the as-spun fibre of preparation is 5.56cN/dtex.Infrared spectrogram shows to form " π-π " interaction force in as-spun fibre between CNTs and PAN, form " atom-π " interaction force (not shown) between CNTs and ionic liquid.Be extract the as-spun fibre prepared during the 19wt.% ethanol of 10 DEG C and the aqueous solution of 8wt.% methyl alcohol are bathed in temperature, dry, obtain PAN/CNTs fiber.The diameter of fiber is 14.3-15.4 μm, and intensity is 8.7cN/dtex.CNTs is uniformly dispersed in the pan, does not form reunion (not shown).

Embodiment 6

Ionic liquid/carbon nanotube systems is prepared: a chlorobutane of 23.68g and 19.1g N methylimidazole, 0.235g carboxyl modified multi-walled carbon nano-tubes CNT302,0.059g sulfated castor oil are mixed in there-necked flask by in-situ synthesized, react 24 hours at 80 DEG C, add 31.63g sodium trifluoroacetate again, with the acetone of 100ml for solvent, synthesis 1-butyl-3-methyl trifluoro acetate/carbon nanotube mixture, stratification removes sodium chloride; Use the ethyl acetate of 30ml to carry out washing three times to blend, obtain ionic liquid/carbon nanotube systems; Or

Ionic liquid/carbon nanotube systems is prepared: in single port flask, add 0.235g CNT (CNT302), 0.059g sulfated castor oil by blend method, add 47.71g 1-butyl-3-methyl trifluoro acetate again, at 90 DEG C, mix 12h make it even; Use the ethyl acetate of 30ml to carry out washing three times to blend, obtain ionic liquid/carbon nanotube systems.

By polyacrylonitrile powder, (viscosity average molecular weigh is 9 × 10 ⁵g/mol, acrylonitrile: methyl acrylate: acrylamide=95mol%: 2.5mol%: 2.5mol%) and above-mentioned ionic liquid/carbon nanotube systems in ice-water bath, fully mix 2h, obtain spinning system.Wherein polyacrylonitrile powder: ionic liquid: CNT: the mass percent of sulfated castor oil is 52%: 47.71%: 0.235%: 0.059%.

Use extruder to carry out spinning the spinning system of gained, the temperature of setting spinning is 180 DEG C, and the linear velocity of up-coiler is 500m/min; The intensity of the as-spun fibre of preparation is 5.42cN/dtex.Infrared spectrogram shows to form " π-π " interaction force in as-spun fibre between CNTs and PAN, form " atom-π " interaction force (not shown) between CNTs and ionic liquid.Be extract the as-spun fibre prepared during the 19wt.% ethanol of 5 DEG C and the aqueous solution of 8wt.% methyl alcohol are bathed in temperature, dry, obtain PAN/CNTs fiber.The diameter of fiber is 15.1-16.4 μm, and intensity is 7.8cN/dtex.CNTs is uniformly dispersed in the pan, does not form reunion (not shown).

Embodiment 7

Ionic liquid/carbon nanotube systems is prepared: the pyridine of 12.23g, 15.74g mono-chlorobutane, 2.3g Single Walled Carbon Nanotube (SWNT-12), 0.23g neopelex are mixed in there-necked flask by in-situ synthesized, react 72 hours under 120 DEG C of conditions, add 16.97g sodium tetrafluoroborate again, with the acetone of 100ml for solvent, synthesis N-butyl-pyridinium tetrafluoroborate/carbon nanotube mixture, stratification removes sodium chloride; Use the ethyl acetate of 30ml to carry out washing three times to blend, obtain ionic liquid/carbon nanotube systems; Or

Ionic liquid/carbon nanotube systems is prepared: in single port flask, add 2.3g CNT (SWNT-12), 0.23g neopelex by blend method, add 34.47gN-butyl-pyridinium tetrafluoroborate again, at 120 DEG C, mix 24h make it even; Use the ethyl acetate of 30ml to carry out washing three times to blend, obtain ionic liquid/carbon nanotube systems.

By polyacrylonitrile powder, (viscosity average molecular weigh is 3 × 10 ⁵g/mol, acrylonitrile homopolymer) and above-mentioned ionic liquid/carbon nanotube systems in ice-water bath, fully mix 3h, obtain spinning system.Wherein polyacrylonitrile powder: ionic liquid: CNT: the mass percent of lauryl sodium sulfate is 63%: 34.47%: 2.3%: 0.23%.

Use extruder to carry out spinning the spinning system of gained, the temperature of setting spinning is 250 DEG C, and the linear velocity of up-coiler is 1200m/min; The intensity of the as-spun fibre of preparation is 4.92cN/dtex.Infrared spectrogram shows to form " π-π " interaction force in as-spun fibre between CNTs and PAN, form " atom-π " interaction force (not shown) between CNTs and ionic liquid.Be extract the as-spun fibre prepared during the 19wt.% ethanol of 40 DEG C and the aqueous solution of 8wt.% methyl alcohol are bathed in temperature, dry, obtain PAN/CNTs fiber.The diameter of final fiber is 15.8-16.7 μm, and intensity is 8.14cN/dtex.CNTs is uniformly dispersed in the pan, does not form reunion (not shown).

Embodiment 8

Ionic liquid/carbon nanotube systems is prepared: the pyridine of 12.38g, 15.94g mono-chlorobutane, 1.76g multi-walled carbon nano-tubes (TNGMH2), 0.22g sodium glycocholate are mixed in there-necked flask by in-situ synthesized, react 72 hours at 130 DEG C, add 26.3g sodium hexafluoro phosphate again, with the acetone of 101ml for solvent, synthesis N-butyl-pyridinium hexafluorophosphate/carbon nanotube mixture, stratification removes sodium chloride; Use the ethyl acetate of 30ml to carry out washing three times to blend, obtain ionic liquid/carbon nanotube systems; Or

Ionic liquid/carbon nanotube systems is prepared: in single port flask, add 1.76g CNT (TNGMH2), 0.22g sodium glycocholate by blend method, add 44.02gN-butyl-pyridinium hexafluorophosphate again, at 110 DEG C, mix 12h make it even; Use the ethyl acetate of 30ml to carry out washing three times to blend, obtain ionic liquid/carbon nanotube systems.

By polyacrylonitrile powder, (viscosity average molecular weigh is 9 × 10 ⁵g/mol, acrylonitrile: methyl acrylate: acrylamide=87mol%: 10mol%: 3mol%) and above-mentioned ionic liquid/carbon nanotube systems in liquid nitrogen, fully mix 4h, obtain spinning system.Wherein polyacrylonitrile powder: ionic liquid: CNT: the mass percent of sodium glycocholate is 54%: 44.02%: 1.76%: 0.22%.

Use extruder to carry out spinning the spinning system of gained, the temperature of setting spinning is 240 DEG C, and the linear velocity of up-coiler is 1500m/min; The intensity of the as-spun fibre of preparation is 5.12cN/dtex.Infrared spectrogram shows to form " π-π " interaction force in as-spun fibre between CNTs and PAN, form " atom-π " interaction force (not shown) between CNTs and ionic liquid.Be the 2wt.%C of 30 DEG C in temperature by the polyacrylonitrile fibre prepared ₁₄extract in alcohol solution, air dry, obtain PAN/CNTs fiber.The diameter of final fiber is 15.1-16.1 μm, and intensity is 7.38cN/dtex.CNTs is uniformly dispersed in the pan, does not form reunion (not shown).

Embodiment 9

Ionic liquid/carbon nanotube systems is prepared: the 1-allyl chloride of the N methylimidazole of 12.52g, 12.83g, 3.12g hydroxyl modified Single Walled Carbon Nanotube (model: HQNANO-CNTs-002C), 0.36g palmitin are mixed in there-necked flask by in-situ synthesized, react 12 hours at 70 DEG C, add 25.61g sodium hexafluoro phosphate again, with the acetone of 120ml for solvent, synthesis 1-allyl-3-methylimidazole hexafluorophosphate/carbon nanotube mixture, stratification removes sodium chloride; Use the ethyl acetate of 30ml to carry out washing three times to blend, obtain ionic liquid/carbon nanotube systems; Or

Ionic liquid/carbon nanotube systems is prepared: in single port flask, add 3.12g CNT (HQNANO-CNTs-002C), 0.36g palmitin by blend method, add 44.52g 1-allyl imidazole hexafluorophosphate again, at 130 DEG C, mix 12h make it even; Use the ethyl acetate of 30ml to carry out washing three times to blend, obtain ionic liquid/carbon nanotube systems.

By polyacrylonitrile powder, (viscosity average molecular weigh is 2.3 × 10 ⁵g/mol, acrylonitrile: methyl acrylate=92mol%: 8mol%) and above-mentioned ionic liquid/carbon nanotube systems at room temperature fully mix 5h, obtain spinning system.Wherein polyacrylonitrile powder: ionic liquid: CNT: the mass percent of palmitin is 52%: 44.52%: 3.12%: 0.36%.

Use extruder to carry out spinning the spinning system of gained, the temperature of setting spinning is 165 DEG C, and the linear velocity of up-coiler is 1100m/min; The intensity of the as-spun fibre of preparation is 5.15cN/dtex.Infrared spectrogram shows to form " π-π " interaction force in as-spun fibre between CNTs and PAN, form " atom-π " interaction force (not shown) between CNTs and ionic liquid.Be extract in the β-cinnamic acid aqueous solution of the 15wt.% of 200 DEG C in temperature by the as-spun fibre prepared, air dry, obtains PAN/CNTs fiber.The diameter of final fiber is 14.8-16.1 μm, and intensity is 7.71cN/dtex.CNTs is uniformly dispersed in the pan, does not form reunion (not shown).

Embodiment 10

1-butyl-3-methyl hexafluorophosphate/carboxyl modified Single Walled Carbon Nanotube mixture and N-butyl-pyridinium villaumite/Single Walled Carbon Nanotube mixture is synthesized by embodiment 1 and the method for embodiment 2; Two kinds of mixtures are fully mixed 5 hours at 100 DEG C, and the mass ratio of two kinds of mixtures is 50wt.%: 50wt.%.

By polyacrylonitrile powder, (viscosity average molecular weigh is 5.3 × 10 ⁵g/mol, acrylonitrile: Sodium styrene sulfonate=92mol%: 8mol%) and above-mentioned ionic liquid/carbon nanotube systems in liquid nitrogen, fully mix 10h, obtain spinning system.Wherein polyacrylonitrile powder: ionic liquid: CNT: the mass percent 72%: 24%: 3.5%: 0.5% of surfactant.

Use extruder to carry out spinning the spinning system of gained, the temperature of setting spinning is 180 DEG C, and the linear velocity of up-coiler is 800m/min; The intensity of the as-spun fibre of preparation is 5.15cN/dtex.Infrared spectrogram shows to form " π-π " interaction force in as-spun fibre between CNTs and PAN, form " atom-π " interaction force (not shown) between CNTs and ionic liquid.Be extract in the 15wt.% β-cinnamic acid aqueous solution of 5 DEG C in temperature by the as-spun fibre prepared, air dry, obtains PAN/CNTs fiber.The diameter of final fiber is 14.1-16.3 μm, and intensity is 7.75cN/dtex.CNTs is uniformly dispersed in the pan, does not form reunion (not shown).

Embodiment 11

1-ethyl-3-methylimidazole bromine salt/hydroxyl modified Single Walled Carbon Nanotube mixture and 1-ethyl-3-methylimidazole acetate/hydroxyl modified multi-walled carbon nano-tubes mixture is synthesized by the method for embodiment 3 and embodiment 4; Two kinds of mixtures are fully mixed 5 hours at 100 DEG C, and the mass ratio of two kinds of mixtures is 30wt.%: 70wt.%.

By polyacrylonitrile powder, (viscosity average molecular weigh is 2.3 × 10 ⁵g/mol, acrylonitrile: methyl methacrylate=98mol%: 2mol%) and above-mentioned ionic liquid/carbon nanotube systems in ice-water bath, fully mix 7h, obtain spinning system.Wherein polyacrylonitrile powder: ionic liquid: CNT: the mass percent 66%: 30%: 3.5%: 0.5% of surfactant.

Use extruder to carry out spinning the spinning system of gained, the temperature of setting spinning is 250 DEG C, and the linear velocity of up-coiler is 600m/min; The intensity of the as-spun fibre of preparation is 5.45cN/dtex.Infrared spectrogram shows to form " π-π " interaction force in as-spun fibre between CNTs and PAN, form " atom-π " interaction force (not shown) between CNTs and ionic liquid.Be extract in the 18wt.% DBSA aqueous solution of 160 DEG C in temperature by the polyacrylonitrile fibre prepared, air dry, obtains PAN/CNTs fiber.The diameter of final fiber is 15.1-15.9 μm, and intensity is 7.18cN/dtex.CNTs is uniformly dispersed in the pan, does not form reunion (not shown).

Embodiment 12

1-butyl-3-methyl hexafluorophosphate/carboxyl modified Single Walled Carbon Nanotube mixture, 1-butyl-3-methyl trifluoro acetate/carboxyl modified multi-walled carbon nano-tubes mixture and N-butyl-pyridinium tetrafluoroborate/Single Walled Carbon Nanotube mixture is synthesized by the method for embodiment 5, embodiment 6, embodiment 7; Three kinds of mixtures are fully mixed 5 hours at 110 DEG C, and the mass ratio of two kinds of mixtures is 30wt.%: 30wt.%: 40wt.%.

By polyacrylonitrile powder, (viscosity average molecular weigh is 1.5 × 10 ⁵g/mol, acrylonitrile homopolymer) and above-mentioned ionic liquid/carbon nanotube systems in ice-water bath, fully mix 10h, obtain spinning system.Wherein polyacrylonitrile powder: ionic liquid: CNT: the mass percent of surfactant is 56%: 37.84%: 5.6%: 0.56%;

Use extruder to carry out spinning the spinning system of gained, the temperature of setting spinning is 260 DEG C, and the linear velocity of up-coiler is 1300m/min; The intensity of the as-spun fibre of preparation is 5.46cN/dtex.Infrared spectrogram shows to form " π-π " interaction force in as-spun fibre between CNTs and PAN, form " atom-π " interaction force (not shown) between CNTs and ionic liquid.Be extract the polyacrylonitrile fibre prepared during the 9wt.% DBSA of 160 DEG C and the aqueous solution of 5.5wt.% tri-nonyl naphthalene sulfonic acids are bathed in temperature, air dry, obtains PAN/CNTs fiber.The diameter of final fiber is 15.1-17.2 μm, and intensity is 7.48cN/dtex.CNTs is uniformly dispersed in the pan, does not form reunion (not shown).

Embodiment 13

1-ethyl-3-methylimidazole acetate/hydroxyl modified multi-walled carbon nano-tubes mixture, N-butyl-pyridinium hexafluorophosphate/multi-walled carbon nano-tubes mixture and 1-allyl imidazole hexafluorophosphate/hydroxyl modified Single Walled Carbon Nanotube mixture is synthesized by the method for embodiment 4, embodiment 8, embodiment 9; Three kinds of mixtures are fully mixed 5 hours at 110 DEG C, and the mass ratio of two kinds of mixtures is 20wt.%: 35wt.%: 35wt.%.

By polyacrylonitrile powder, (viscosity average molecular weigh is 3.5 × 10 ⁵g/mol, acrylonitrile: methyl methacrylate=90mol%: 10mol%) and above-mentioned ionic liquid/carbon nanotube systems at room temperature fully mix 2h, obtain spinning system.Wherein polyacrylonitrile powder: ionic liquid: CNT: the mass percent of surfactant is 68%: 25.84%: 5.6%: 0.56%.

Use extruder to carry out spinning the spinning system of gained, the temperature of setting spinning is 210 DEG C, and the linear velocity of up-coiler is 600m/min; The intensity of the as-spun fibre of preparation is 5.07cN/dtex.Infrared spectrogram shows to form " π-π " interaction force in as-spun fibre between CNTs and PAN, form " atom-π " interaction force (not shown) between CNTs and ionic liquid.By the polyacrylonitrile fibre prepared temperature be the 7.5wt.% ethanol of 60 DEG C, the aqueous solution of 5wt.% methyl alcohol and 4.5wt.% octanol extracts in bathing, air dry, obtains PAN/CNTs fiber.The diameter obtaining final fiber is 15.6-17.9 μm, and intensity is 7.55cN/dtex.CNTs is uniformly dispersed in the pan, does not form reunion (not shown).

Embodiment 14

1-ethyl-3-methylimidazole bromine salt/hydroxyl modified Single Walled Carbon Nanotube mixture, 1-butyl-3-methyl hexafluorophosphate/carboxyl modified Single Walled Carbon Nanotube mixture and 1-allyl imidazole hexafluorophosphate/hydroxyl modified Single Walled Carbon Nanotube mixture is synthesized by the method for embodiment 3, embodiment 5, embodiment 9; Three kinds of mixtures are fully mixed 5 hours at 110 DEG C, and the mass ratio of two kinds of mixtures is 45wt.%: 25wt.%: 30wt.%.

By polyacrylonitrile powder, (viscosity average molecular weigh is 6 × 10 ⁵g/mol, acrylonitrile: methyl methacrylate=85mol%: 15mol%) and above-mentioned ionic liquid/carbon nanotube systems in liquid nitrogen, fully mix 2h, obtain spinning system.Wherein polyacrylonitrile powder: ionic liquid: CNT: the mass percent of surfactant is 78%: 18.75%: 3.2%: 0.05%.

Use extruder to carry out spinning the spinning system of gained, the temperature of setting spinning is 220 DEG C, and the linear velocity of up-coiler is 700m/min; The intensity of the as-spun fibre of preparation is 5.28cN/dtex.Infrared spectrogram shows to form " π-π " interaction force in as-spun fibre between CNTs and PAN, form " atom-π " interaction force (not shown) between CNTs and ionic liquid.By the polyacrylonitrile fibre prepared temperature be the 7.5wt.% ethanol of 60 DEG C, the aqueous solution of 5wt.% methyl alcohol and 4.5wt.% octanol extracts in bathing, air dry, obtains PAN/CNTs fiber.The diameter obtaining final fiber is 14.6-17.4 μm, and intensity is 7.14cN/dtex.CNTs is uniformly dispersed in the pan, does not form reunion (not shown).

Embodiment 15

1-butyl-3-methyl hexafluorophosphate/carboxyl modified Single Walled Carbon Nanotube mixture, N-butyl-pyridinium tetrafluoroborate/Single Walled Carbon Nanotube mixture and N-butyl-pyridinium hexafluorophosphate/multi-walled carbon nano-tubes mixture is synthesized by the in-situ polymerization of embodiment 1, embodiment 7, embodiment 8; Three kinds of mixtures are fully mixed 5 hours at 110 DEG C, and the mass ratio of two kinds of mixtures is 40wt.%: 30wt.%: 30wt.%.

By polyacrylonitrile powder, (viscosity average molecular weigh is 3.5 × 10 ⁵g/mol, acrylonitrile: methyl methacrylate: acrylamide=87mol%: 10mol%: 3mol%) and above-mentioned ionic liquid/carbon nanotube systems at room temperature fully mix 30min, obtain spinning system.Wherein polyacrylonitrile powder: ionic liquid: CNT: the mass percent of surfactant is 66%: 27.84%: 5.6%: 0.56%;

Use extruder to carry out spinning the spinning system of gained, the temperature of setting spinning is 190 DEG C, and the linear velocity of up-coiler is 800m/min; The intensity of the as-spun fibre of preparation is 5.09cN/dtex.Infrared spectrogram shows to form " π-π " interaction force in as-spun fibre between CNTs and PAN, form " atom-π " interaction force (not shown) between CNTs and ionic liquid.Be extract in the 18wt.% DBSA aqueous solution of 160 DEG C in temperature by the polyacrylonitrile fibre prepared, air dry, obtains PAN/CNTs fiber.The diameter of final fiber is 15.6-17.1 μm, and intensity is 7.24cN/dtex.CNTs is uniformly dispersed in the pan, does not form reunion (not shown).

Embodiment 16

Ionic liquid/carbon nanotube systems is prepared: in single port flask, add 3.3g CNT (CNT206), 0.7g neopelex by blend method, add 40g trimethyl quaternary ammonium villaumite again, mixture is fully mixed 5 hours at 100 DEG C.Use the ethyl acetate of 30ml to carry out washing three times to blend, obtain ionic liquid/carbon nanotube systems.

By polyacrylonitrile powder, (viscosity average molecular weigh is 3.5 × 10 ⁵g/mol, acrylonitrile: methyl methacrylate: acrylamide=87mol%: 10mol%: 3mol%) and above-mentioned ionic liquid/carbon nanotube systems at 10 DEG C, fully mix 3h, obtain spinning system.Wherein polyacrylonitrile powder: ionic liquid: CNT: the mass percent of neopelex is 56%: 40%: 3.3%: 0.7%.

Use extruder to carry out spinning the spinning system of gained, the temperature of setting spinning is 205 DEG C, and the linear velocity of up-coiler is 900m/min; The intensity of the as-spun fibre of preparation is 5.58cN/dtex.Infrared spectrogram shows to form " π-π " interaction force in as-spun fibre between CNTs and PAN, form " atom-π " interaction force (not shown) between CNTs and ionic liquid.Be extract in the 18wt.% DBSA aqueous solution of 200 DEG C in temperature by the as-spun fibre of preparation, air dry, obtains PAN/CNTs fiber.The diameter obtaining final fiber is 15.1-17.8 μm, and intensity is 7.67cN/dtex.CNTs is uniformly dispersed in the pan, does not form reunion (not shown).

Embodiment 17

Ionic liquid/carbon nanotube systems is prepared: in single port flask, add 3.3g CNT (CNT306), 0.7g sodium glycocholate by blend method, add 32g trimethyl quaternary phosphine nitrate again, mixture is fully mixed 8 hours at 120 DEG C.Use the ethyl acetate of 30ml to carry out washing three times to blend, obtain ionic liquid/carbon nanotube systems.

By polyacrylonitrile powder, (viscosity average molecular weigh is 7 × 10 ⁵g/mol, acrylonitrile: methyl methacrylate: itaconic acid=95mol%: 4.5mol%: 0.5mol%) and above-mentioned ionic liquid/carbon nanotube systems in liquid nitrogen, fully mix 3h, obtain spinning system.Wherein polyacrylonitrile powder: ionic liquid: CNT: the mass percent of sodium glycocholate is 64%: 32%: 3.3%: 0.7%.

Use extruder to carry out spinning the spinning system of gained, the temperature of setting spinning is 240 DEG C, and the linear velocity of up-coiler is 700m/min; The intensity of the as-spun fibre of preparation is 5.38cN/dtex.Infrared spectrogram shows to form " π-π " interaction force in as-spun fibre between CNTs and PAN, form " atom-π " interaction force (not shown) between CNTs and ionic liquid.Be extract the as-spun fibre prepared during the 7.2wt.% DBSA of 150 DEG C and the aqueous solution of 8.5wt.% tri-nonyl naphthalene sulfonic acids are bathed in temperature, air dry, obtains PAN/CNTs fiber.The diameter of final fiber is 15.6-17.1 μm, and intensity is 7.24cN/dtex.CNTs is uniformly dispersed in the pan, does not form reunion (not shown).

Embodiment 18

Prepare ionic liquid/carbon nanotube systems by blend method: in single port flask, add 0.235g CNT (CNT304), 0.059g sodium glycocholate, then add 49g cetyl trimethyl quaternary ammonium nitrate, 1-butyl-3-methylimidazole salt compounded of iodine.Mixture is fully mixed 7 hours at 110 DEG C, and wherein the mass percent of cetyl trimethyl quaternary ammonium nitrate and 1-butyl-3-methylimidazole salt compounded of iodine is 20%: 80%.Use the ethyl acetate of 30ml to carry out washing three times to blend, obtain ionic liquid/carbon nanotube systems.

By polyacrylonitrile powder, (viscosity average molecular weigh is 5.3 × 10 ⁵g/mol, acrylonitrile: methyl acrylate: acrylamide=85mol%-10mol%: 5mol%) and above-mentioned ionic liquid/carbon nanotube systems in ice-water bath, fully mix 5h, obtain spinning system.Wherein polyacrylonitrile powder: ionic liquid: CNT: the mass percent of sodium glycocholate is 50.71%: 49%: 0.235%: 0.059%.

Use extruder to carry out spinning the spinning system of gained, the temperature of setting spinning is 220 DEG C, and the linear velocity of up-coiler is 700m/min; The intensity of the as-spun fibre of preparation is 5.19cN/dtex.Infrared spectrogram shows to form " π-π " interaction force in as-spun fibre between CNTs and PAN, form " atom-π " interaction force (not shown) between CNTs and ionic liquid.Be extract the as-spun fibre prepared during the 9wt.% DBSA of 160 DEG C and the aqueous solution of 5.5wt.% tri-nonyl naphthalene sulfonic acids are bathed in temperature, air dry, obtains PAN/CNTs fiber.The diameter obtaining final fiber is 14.6-17.4 μm, and intensity is 7.74cN/dtex.CNTs is uniformly dispersed in the pan, does not form reunion (not shown).

Embodiment 19

Prepare ionic liquid/carbon nanotube systems by blend method: in single port flask, add 0.167g CNT (CNT204), 0.0167g sulfated castor oil, then add 21.7g trimethyl quaternary phosphine villaumite, cetyl trimethyl quaternary ammonium villaumite, 1-ethyl-3-methylimidazole villaumite.Mixture is fully mixed 8 hours at 120 DEG C, wherein trimethyl quaternary phosphine villaumite: cetyl trimethyl quaternary ammonium villaumite: the mass percent of 1-ethyl-3-methylimidazole villaumite is 20%: 50%: 30%.Use the ethyl acetate of 30ml to carry out washing three times to blend, obtain ionic liquid/carbon nanotube systems.

By polyacrylonitrile powder, (viscosity average molecular weigh is 5 × 10 ⁵g/mol, acrylonitrile: methyl methacrylate: itaconic acid=85mol%: 10mol%: 5mol%) and above-mentioned ionic liquid/carbon nanotube systems at room temperature fully mix 5h, obtain spinning system.Wherein polyacrylonitrile powder: ionic liquid: CNT: the mass percent of sulfated castor oil is 78.11%: 21.7%: 0.167%: 0.0167%.

Use extruder to carry out spinning the spinning system of gained, the temperature of setting spinning is 262 DEG C, and the linear velocity of up-coiler is 900m/min; The intensity of the as-spun fibre of preparation is 5.48cN/dtex.Infrared spectrogram shows to form " π-π " interaction force in as-spun fibre between CNTs and PAN, form " atom-π " interaction force (not shown) between CNTs and ionic liquid.Be extract in the 15wt.% DBSA aqueous solution of 80 DEG C in temperature by the as-spun fibre prepared, air dry obtains PAN/CNTs fiber.The diameter obtaining final fiber is 15.2-16.8 μm, and intensity is 7.34cN/dtex.CNTs is uniformly dispersed in the pan, does not form reunion (not shown).

Embodiment 20

Prepare ionic liquid/carbon nanotube systems by blend method: in single port flask, add 0.167g CNT (CNT202), 0.0167g sulfated castor oil, then add 34.11g trimethyl quaternary ammonium acetate, trimethyl quaternary phosphine acetate, trimethyl quaternary ammonium nitrate mixture.Mixture is fully mixed 6 hours at 130 DEG C, wherein trimethyl quaternary ammonium acetate: trimethyl quaternary phosphine acetate: the mass percent of trimethyl quaternary ammonium nitrate is 30%: 40%: 30%.Use the ethyl acetate of 30ml to carry out washing three times to blend, obtain ionic liquid/carbon nanotube systems.

By polyacrylonitrile powder, (viscosity average molecular weigh is 6 × 10 ⁵g/mol, acrylonitrile: methyl methacrylate=97.5mol%: 2.5mol%) and above-mentioned ionic liquid/carbon nanotube systems in liquid nitrogen, fully mix 10min, obtain spinning system.Wherein polyacrylonitrile powder: ionic liquid: CNT: the mass percent of sulfated castor oil is 65.7%: 34.11%: 0.167%: 0.0167%.

Use extruder to carry out spinning the spinning system of gained, the temperature of setting spinning is 270 DEG C, and the linear velocity of up-coiler is 900m/min; The intensity of the as-spun fibre of preparation is 5.48cN/dtex.Infrared spectrogram shows to form " π-π " interaction force in as-spun fibre between CNTs and PAN, form " atom-π " interaction force (not shown) between CNTs and ionic liquid.Be extract in the 15wt.% DBSA aqueous solution of 80 DEG C in temperature by the as-spun fibre prepared, air dry obtains PAN/CNTs fiber.The diameter obtaining final fiber is 14.5-17.8 μm, and intensity is 7.45cN/dtex.CNTs is uniformly dispersed in the pan, does not form reunion (not shown).

Embodiment 21

Ionic liquid/carbon nanotube systems is prepared: in single port flask, add 2.5g CNT (CNT200), 0.5g potash soap by blend method, add 37.5g trimethyl quaternary ammonium tetrafluoroborate again, mixture is fully mixed 5 hours at 110 DEG C.Use the ethyl acetate of 30ml to carry out washing three times to blend, obtain ionic liquid/carbon nanotube systems.

By polyacrylonitrile powder, (viscosity average molecular weigh is 6 × 10 ⁵g/mol, acrylonitrile: methacrylonitrile methyl esters=97.5mol%: 2.5mol%) and above-mentioned ionic liquid/carbon nanotube systems in liquid nitrogen, fully mix 30min, obtain spinning system.Wherein polyacrylonitrile powder: ionic liquid: CNT: the mass percent of potash soap is 59.5%: 37.5%: 2.5%: 0.5%.

Use extruder to carry out spinning the spinning system of gained, the temperature of setting spinning is 210 DEG C, and the linear velocity of up-coiler is 600m/min; The intensity of the as-spun fibre of preparation is 5.28cN/dtex.Infrared spectrogram shows to form " π-π " interaction force in as-spun fibre between CNTs and PAN, form " atom-π " interaction force (not shown) between CNTs and ionic liquid.Be extract in the 17wt.% DBSA aqueous solution of 160 DEG C in temperature by the as-spun fibre prepared, air dry obtains PAN/CNTs fiber.The diameter obtaining final fiber is 15.3-17.1 μm, and intensity is 7.73cN/dtex.CNTs is uniformly dispersed in the pan, does not form reunion (not shown).

Embodiment 22

Prepare ionic liquid/carbon nanotube systems by blend method: in single port flask, add 3.8g CNT (being SWNT-12), 0.2g soda soap, then add 48g 1-ethyl-3-methylimidazole tetrafluoroborate, trimethyl quaternary phosphine tetrafluoroborate, N-butyl-pyridinium trifluoroacetate add carry out blended.Mixture is fully mixed 6 hours at 110 DEG C, wherein 1-ethyl-3-methylimidazole tetrafluoroborate: trimethyl quaternary phosphine tetrafluoroborate: the mass percent of N-butyl-pyridinium trifluoroacetate is 35%: 30%: 35%.Use the ethyl acetate of 30ml to carry out washing three times to blend, obtain ionic liquid/carbon nanotube systems.

By polyacrylonitrile powder, (viscosity average molecular weigh is 2.5 × 10 ⁵g/mol, acrylonitrile: acrylamide=97.5mol%: 2.5mol%) and above-mentioned ionic liquid/carbon nanotube systems at room temperature fully mix 4h, obtain spinning system.Wherein polyacrylonitrile powder: ionic liquid: CNT: the mass percent of alkali metal soap (particular compound is soda soap) is 48%: 48%: 3.8%: 0.2%.

Use extruder to carry out spinning the spinning system of gained, the temperature of setting spinning is 235 DEG C, and the linear velocity of up-coiler is 700m/min; The intensity of the as-spun fibre of preparation is 5.18cN/dtex.Infrared spectrogram shows to form " π-π " interaction force in as-spun fibre between CNTs and PAN, form " atom-π " interaction force (not shown) between CNTs and ionic liquid.Be extract in the 17wt.% aqueous acetone solution of 30 DEG C in temperature by the as-spun fibre prepared, air dry obtains PAN/CNTs fiber.The diameter obtaining final fiber is 15.6-17.1 μm, and intensity is 7.75cN/dtex.CNTs is uniformly dispersed in the pan, does not form reunion (not shown).

Embodiment 23

Prepare ionic liquid/carbon nanotube systems by blend method: in single port flask, add 3.4g CNT (TNSH), 0.6g barium soap, then add 38g 1-ethyl-3-methylimidazole tetrafluoroborate, N-hexyl pyridinium iodide, dodecyl trifluoroacetate.Mixture is fully mixed 5 hours at 130 DEG C, wherein 1-ethyl-3-methylimidazole tetrafluoroborate: N-hexyl pyridinium iodide: the mass percent of dodecyl trifluoroacetate is 20%: 40%: 40%.Use the ethyl acetate of 30ml to carry out washing three times to blend, obtain ionic liquid/carbon nanotube systems.

By polyacrylonitrile powder, (viscosity average molecular weigh is 6 × 10 ⁵g/mol, acrylonitrile: acrylonitrile methyl esters=95mol%: 5mol%) and above-mentioned ionic liquid/carbon nanotube systems at 40 DEG C, fully mix 5h, obtain spinning system.Wherein polyacrylonitrile powder: ionic liquid: CNT: the mass percent of barium soap is 58%: 38%: 3.4%: 0.6%.

Use extruder to carry out spinning the spinning system of gained, the temperature of setting spinning is 230 DEG C, and the linear velocity of up-coiler is 500m/min; The intensity of the as-spun fibre of preparation is 5.18cN/dtex.Infrared spectrogram shows to form " π-π " interaction force in as-spun fibre between CNTs and PAN, form " atom-π " interaction force (not shown) between CNTs and ionic liquid.Be extract in the 0.2wt.% tributyl phosphate aqueous solution of 70 DEG C in temperature by the as-spun fibre prepared, air dry obtains PAN/CNTs fiber.The diameter obtaining final fiber is 15.3-17.5 μm, and intensity is 7.57cN/dtex.CNTs is uniformly dispersed in the pan, does not form reunion (not shown).

Embodiment 24

Prepare ionic liquid/carbon nanotube systems by blend method: in single port flask, add 3.8g CNT (MWNT-10), 0.2g trihydroxy ethylamine oleate soap, then add 48g 1-butyl-3-methyl imidazolium tetrafluoroborate, cetyl trimethyl quaternary ammonium iodide salt.Mixture is fully mixed 6 hours at 120 DEG C, wherein 1-butyl-3-methyl imidazolium tetrafluoroborate: the mass percent of cetyl trimethyl quaternary ammonium iodide salt is 40%: 60%.Use the ethyl acetate of 30ml to carry out washing three times to blend, obtain ionic liquid/carbon nanotube systems.

By polyacrylonitrile powder, (viscosity average molecular weigh is 3 × 10 ⁵g/mol, acrylonitrile homopolymer) and above-mentioned ionic liquid/carbon nanotube systems in ice-water bath, fully mix 7h, obtain spinning system.Wherein polyacrylonitrile powder: ionic liquid _:cNT: the mass percent of trihydroxy ethylamine oleate soap is 48%: 48%: 3.8%: 0.2%.

Use extruder to carry out spinning the spinning system of gained, the temperature of setting spinning is 243 DEG C, and the linear velocity of up-coiler is 900m/min; The intensity of the as-spun fibre of preparation is 5.68cN/dtex.Infrared spectrogram shows to form " π-π " interaction force in as-spun fibre between CNTs and PAN, form " atom-π " interaction force (not shown) between CNTs and ionic liquid.Be extract in the β-cinnamic acid aqueous solution of the 15wt.% of 230 DEG C in temperature by the as-spun fibre prepared, air dry obtains PAN/CNTs fiber.The diameter obtaining final fiber is 15.1-16.5 μm, and intensity is 7.88cN/dtex.CNTs is uniformly dispersed in the pan, does not form reunion (not shown).

Embodiment 25

Prepare ionic liquid/carbon nanotube systems by blend method: in single port flask, add 3.8g CNT (CNT302), 0.2g soda soap, then add 44g trimethyl quaternary ammonium bromine salt, N-picoline salt compounded of iodine, 1-ethyl-3-methylimidazole salt compounded of iodine.Mixture is fully mixed 7 hours at 110 DEG C, wherein trimethyl quaternary ammonium bromine salt: N-picoline salt compounded of iodine: the mass percent of 1-ethyl-3-methylimidazole salt compounded of iodine is 15%: 35%: 50%.Use the ethyl acetate of 30ml to carry out washing three times to blend, obtain ionic liquid/carbon nanotube systems.

By polyacrylonitrile powder, (viscosity average molecular weigh is 2.5 × 10 ⁵g/mol, acrylonitrile: acrylonitrile methyl esters: itaconic acid=95mol%: 4mol%: 1mol%) and above-mentioned ionic liquid/carbon nanotube systems in liquid nitrogen, fully mix 5h, obtain spinning system.Wherein polyacrylonitrile powder: ionic liquid: CNT: the mass percent of soda soap is 52%: 44%: 3.8%: 0.2%.

Use extruder to carry out spinning the spinning system of gained, the temperature of setting spinning is 251 DEG C, and the linear velocity of up-coiler is 1000m/min; The intensity of the as-spun fibre of preparation is 5.48cN/dtex.Infrared spectrogram shows to form " π-π " interaction force in as-spun fibre between CNTs and PAN, form " atom-π " interaction force (not shown) between CNTs and ionic liquid.Be extract in the 12wt.% dodecoic acid aqueous solution of 200 DEG C in temperature by the as-spun fibre prepared, air dry obtains PAN/CNTs fiber.The diameter obtaining final fiber is 14.6-17.3 μm, and intensity is 7.70cN/dtex.CNTs is uniformly dispersed in the pan, does not form reunion (not shown).

Should be understood that those skilled in the art can make various changes or modifications the present invention, and these equivalent form of values fall within the application's appended claims limited range equally after having read the content that the present invention tells about.

Claims (10)

1. polyacrylonitrile/ionic liquid/carbon nano-tube fibre, it is as-spun fibre, is that to comprise viscosity average molecular weigh be 1 × 10 ⁵~ 9 × 10 ⁵the polyacrylonitrile (PAN) of g/mol, the PAN/IL/CNTs system of ionic liquid IL and CNT CNTs, wherein polyacrylonitrile: ionic liquid: the mass ratio of CNT is 47-83: 9-50: 0.1-8; Wherein form " atom-π " between CNT and ionic liquid to interact, form " π-π " between CNTs and PAN and interact; Wherein even carbon nanotube to be scattered in polyacrylonitrile and not to form reunion, and fracture strength is 4.9-6.0cN/dtex.

2. polyacrylonitrile/carbon nano-tube fibre, be by using extractant to extract polyacrylonitrile/ionic liquid/carbon nano-tube fibre according to claim 1, dry after, wherein even carbon nanotube to be scattered in polyacrylonitrile and not to form reunion, and the fracture strength of fiber is 7.0-9.0cN/dtex.

3. polyacrylonitrile/ionic liquid/carbon nano-tube fibre according to claim 1 or polyacrylonitrile/carbon nano-tube fibre according to claim 2, it is characterized in that, described CNT is Single Walled Carbon Nanotube, multi-walled carbon nano-tubes, hydroxyl modified multi-walled carbon nano-tubes, carboxyl modified multi-walled carbon nano-tubes, hydroxyl modified Single Walled Carbon Nanotube or carboxyl modified Single Walled Carbon Nanotube.

4. polyacrylonitrile/ionic liquid/carbon nano-tube fibre according to claim 1 or polyacrylonitrile/carbon nano-tube fibre according to claim 2, it is characterized in that, the CATION of ionic liquid is selected from alkyl-quaternaryammonium cations, Wan Ji quaternary phosphine CATION, N, N-dialkylimidazolium cation and N-alkylpyridiniium cation; Anion is selected from halide ion, acetate ion, nitrate ion, tetrafluoro boric acid salt ion and trifluoracetic acid salt ion.

5. polyacrylonitrile/ionic liquid/carbon nano-tube fibre according to claim 1 or polyacrylonitrile/carbon nano-tube fibre according to claim 2, it is characterized in that, ionic liquid is the mixture of a kind of ionic liquid or two or more ionic liquid.

6. prepare a method for polyacrylonitrile/ionic liquid/carbon nano-tube fibre according to any one of claim 1 to 5, it comprises the steps:

The first step: prepare ionic liquid/carbon nanotube systems by in-situ synthesized or blending method, wherein ionic liquid: CNT: the mass ratio of surfactant is 9-50: 0.1-8: 0.01-0.8, wherein in-situ synthesized be by the raw material needed for synthesis ionic liquid, CNT, surfactant is first admixed together reacts, the ionic liquid/carbon nanotube systems needed for generation; Blending method be by CNT, surfactant and in advance at 80 DEG C-150 DEG C the ionic liquid of melting mix, then at 80 DEG C-150 DEG C, mix 12-24h, until mix;

Second step: prepared by spinning system: by the ionic liquid/carbon nanotube systems mixing 10min ~ 10h of polyacrylonitrile and first step gained, obtain the mixture as spinning system, wherein polyacrylonitrile: ionic liquid: CNT: the mass ratio of surfactant is 47-83: 9-50: 0.1-8: 0.01-0.8;

3rd step: use extruder to carry out spinning in the mixture of second step gained, obtain as-spun fibre.

7. method according to claim 6, is characterized in that, the reaction temperature of first step situ method of formation is 50-150 DEG C, and the reaction time is 8-84h.

8. method according to claim 6, it is characterized in that, described surfactant is selected from alkali metal soap, alkaling earth metal base, lauryl sodium sulfate, organic amine soap, triethanolamine soap, sulfated castor oil, neopelex, sodium glycocholate, fatty glyceride.

9. prepare a method for polyacrylonitrile/carbon nano-tube fibre according to any one of claim 2 to 5, it, except comprising the first step, second step and the 3rd step in method described in claim 6 or 7, also comprises the steps:

4th step: the as-spun fibre extractant of the 3rd step gained is extracted, air dry or oven dry, obtain polyacrylonitrile/carbon nano-tube fibre.

10. method according to claim 9, it is characterized in that, described extractant is one or more the mixture in methyl alcohol, ethanol, propyl alcohol, butanols, octanol, ethylene glycol, butanediol, glycerol, n-hexane, acetone, ethyl acetate, isoamyl acetate, phosphate, carboxylic acid, sulfuric acid, sulfonic acid and water.