CN103031617B - A kind of carbon nano-tube/poly ammonia ester/polyacrylonitrile composite conductive fibre and preparation method thereof - Google Patents
A kind of carbon nano-tube/poly ammonia ester/polyacrylonitrile composite conductive fibre and preparation method thereof Download PDFInfo
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- CN103031617B CN103031617B CN201210564807.9A CN201210564807A CN103031617B CN 103031617 B CN103031617 B CN 103031617B CN 201210564807 A CN201210564807 A CN 201210564807A CN 103031617 B CN103031617 B CN 103031617B
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- polyacrylonitrile
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
- D01F6/54—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polymers of unsaturated nitriles
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/06—Wet spinning methods
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/09—Addition of substances to the spinning solution or to the melt for making electroconductive or anti-static filaments
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
- D01F6/94—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of other polycondensation products
Abstract
The invention discloses a kind of carbon nano-tube/poly ammonia ester/polyacrylonitrile composite conductive fibre, described composite conducting fiber is made up of CNT, polyurethane, polyacrylonitrile, the mass percent of CNT is 1% ~ 10%, and polyurethane is 9% ~ 40%, and polyacrylonitrile is 50% ~ 90%.This patent adopts the method for wet spinning, uses CNT and polyurethane jointly to carry out modification to polyacrylonitrile, prepares carbon nano-tube/poly ammonia ester/polyacrylonitrile composite conductive fibre.Utilize configuration control method in blend polymer spinning process, make polyurethane become fento at spinning process situ, carboxyl and the polyurethane of the acidified process rear surface of CNT form hydrogen bond, and therefore CNT is selectively distributed in in-situ micro-fibril.Make carbon nano-tube/poly ammonia ester fento in polyacrylonitrile matrix, form continuous net chain fento conductive channel like this, obtain composite conducting fiber.
Description
Technical field
The technology of the present invention belongs to conductive nano composite material field, particularly a kind of preparation method of carbon nano-tube/poly ammonia ester/polyacrylonitrile composite conductive fibre.
Background technology
Synthetic fiber achieve consequence with their excellent performances on fiber market, but these fibers are easy to produce electrostatic, easily tarnish; And their ratio resistance is higher, and static behaviour is stronger, be used in interference in taking just clearly, such as can cause that chemical fiber garment is wound around mutually, dust suction, impact dress; Electrostatic accumulation to a certain extent, will discharge as occasion serves, and static discharge can set off an explosion again and fire in specific occasion, also can cause electric shock disaster.Therefore this point just becomes the large defect in synthetic fiber and natural fabric keen competition.
Polyacrylonitrile fibre (acrylic fibers) is a kind of widely used synthetic fiber, and quality is fluffy, soft, density is little, and warmth retention property is good, and resilience is high, have excellent light resistance, weatherability and good dyeability, having the title of artificial wool, is the best substitute of wool.At present its output is only second to polyester fiber and polyamide fiber in synthetic fiber again, is positioned at the 3rd.But due to its hydrophobicity and insulating properties, its electrostatic phenomenon is especially serious.In addition, the ABRASION RESISTANCE of acrylic fibers is the poorest in various synthetic fiber.Therefore skilled addressee has carried out large quantifier elimination to the antistatic method of acrylic fibers.
In the preparation method of polyacrylonitrile conductive fiber, solution blending spining technology receives the concern of numerous researcher.Utilize the method, conductive fill powder (carbon black, metal or metal oxide etc.) is dispersed in polyacrylonitrile solution by solution blended process, prepared conductive fiber has good conductive fiber, but in blend direct fabrics, in order to reach lower volume resistivity, usually add the conductive powder body that content is higher, this not only can make spinnability be deteriorated, but also fibre strength can be caused obviously to decline.
CNT (CNT) is since 1991 are found, with the accurate one dimension tracheary element structure of its distinctive mechanics, electricity and chemical property and uniqueness and the many potential using value that has in following high-tech area, become rapidly the study hotspot of chemistry, physics and material science.The C-C covalent bond segmented structure of CNT is similar to macromolecular chain segment structure, carries out compound by coordinate bond effect and macromolecular material.CNT can be improved intensity and the toughness of macromolecular material as reinforcing material, because CNT is quasi-one-dimensional nanometer material, namely be nano-scale on bidimensional yardstick, draw ratio is very large, a kind of fibrous material, so the polymer after its enhancing is used for spinning fibre suitable advantage.Join using CNTs as filler in polymer and prepare the focus that polymer/CNT composite becomes current research.Patent CN101250770A utilizes wet spinning technology, uses CNT to carry out quick modification to the acrylic as-spun fibre being still in gel state, obtains antistatic acrylic fiber.Patent CN101864015A by carbon nanotube dispersed in ionic liquid, then monomer, initator are added wherein polymerization and obtain polyacrylonitrile/carbon nano tube compound material stoste, adopt wet spinning or dry-jet wet spinning process to prepare polyacrylonitrile/carbon nano tube composite fibre.CNT (CNT) and polyacrylonitrile (PAN) disperse and are dissolved in solvent by patent CN101250770 respectively, and obtain PAN/CNT spinning solution by solution blending, this solution obtains PAN/CNT fiber through wet spinning.
Polyurethane (PU) fiber is obtained obtaining through spinning after the mutually embedding polymer of soft or hard section through polymerisation by dihydroxylic alcohols and vulcabond.A kind of synthetic fiber of high added value are become, in fields such as weaving, clothes, bio-medical materials due to the elasticity of its excellence and rebound performance.The good reputation of spandex also have " class monosodium glutamate type " fiber, as long as add a little spandex in fabric, is just enough to improve fabric property, the class of fabric is greatly improved.
Preparing conductive polymeric composite trend is at present use multi-phase polymer co-mixing system to reduce the content of conductive filler in conduction high polymer, superpolymer blend be separated and inorganic conductive material be optionally distributed to a certain mutually in, the composite of high conductivity can be obtained when conductive agent consumption is lower, reasonable processing characteristics can be provided on the other hand, and effectively reduce the impact of the mechanical performance decline caused because filer content increases.This patent adopts the method for solution-polymerized SBR, uses CNT and polyurethane jointly to carry out modification to polyacrylonitrile, prepares carbon nano-tube/poly ammonia ester/polyacrylonitrile composite conductive fibre.Read the report that documents and materials yet there are no polyurethane and the common modified acrylic fibre of CNT.
Summary of the invention
The object of this invention is to provide a kind of preparation method with the polyacrylonitrile conductive fiber of controlled conductivity and desirable physical mechanical performance.
Carbon nano-tube/poly ammonia ester/polyacrylonitrile fibre provided by the invention is be made up of CNT, polyurethane and polyacrylonitrile.The mass percent that CNT accounts for composite fibre is 1% ~ 10%, and polyurethane accounts for 9% ~ 40%, and polyacrylonitrile accounts for 50% ~ 90%.
CNT used in the present invention can be a kind of or their mixture of single armed CNT, multi-arm carbon nano-tube.
Described polyacrylonitrile is acrylonitrile homopolymer or copolymer.
Described polyurethane is the section of fibre-grade polyurethane.
The preparation method of carbon nano-tube/poly ammonia ester/polyacrylonitrile composite conductive fibre of the present invention comprises the following steps:
(1) CNT is taken out after concentration is reflux 0.5 ~ 4 hour in 70% ~ 98% strong acid solution, dilute with deionized water, filter, and repeatedly rinse with deionized water, gained black solid is placed in vacuum drying oven and is dried to constant weight, obtain carboxylated CNT;
(2) carboxylated CNT, polyurethane and polyacrylonitrile are placed in spin solvent to stir, polyurethane and polyacrylonitrile dissolve and obtain blend solution, then filtration under diminished pressure, vacuum defoamation, obtained co-blended spinning stoste;
(3) on wet process equipment, co-blended spinning solution is filtered, measures, the coagulating bath be made up of spin solvent and water is clamp-oned by spinneret orifice, wherein in coagulating bath, the mass fraction of spin solvent is 20 ~ 60%, carboxylic carbon nano-tube, polyurethane and the polyacrylonitrile concentration in spin solvent is 12 ~ 35%, adopts circulation bath to keep coagulating bath concentration stabilize; Stretch and carry out in aqueous, draw ratio is 3 ~ 8, obtains carbon nano-tube/poly ammonia ester/polyacrylonitrile composite conductive fibre.
Described spin solvent is dimethyl sulfoxide (DMSO) or dimethyl formamide.
Spinnerets hole count used in the present invention from 1 to 1200 holes not etc., the tow fineness of antistatic fibre from 50dtex to 6000dtex not etc.Antistatic fibre prepared by the present invention has good intensity, generally at 2.5CN/dtex ~ 6.4 CN/dtex, can meet the instructions for use in weaving and other field.Electrical conductivity is different because of the content of conductive agent in fiber and the difference of proportioning, can be controlled in 10
-14~ 10
-2(S/cm) in scope.
The invention has the beneficial effects as follows: this patent adopts the method for wet spinning, use CNT and polyurethane jointly to carry out modification to polyacrylonitrile, prepare carbon nano-tube/poly ammonia ester/polyacrylonitrile composite conductive fibre.Utilize configuration control method in blend polymer spinning process, make polyurethane become fento at spinning process situ, carboxyl and the polyurethane of the acidified process rear surface of CNT form hydrogen bond, and therefore CNT is selectively distributed in in-situ micro-fibril.Make carbon nano-tube/poly ammonia ester fento in polyacrylonitrile matrix, form continuous net chain fento conductive channel like this, obtain composite conducting fiber.
This fiber not only have conduction or antistatic behaviour, and due in spinning process polymer flow know from experience make polyurethane fento along fiber axial orientation, thus play fento strengthen effect, greatly can improve the strength and modulus of polyacrylonitrile fibre.The method is without the need to changing production line and the equipment of original acrylic fibers, and technical process is easy, produces flexibly.The fiber produced not only has higher electrical conductivity, and has the features such as intensity is high, good hand touch, can meet the requirement of the later process such as weaving completely.With the anti-static polyacrylonitrile fibre that above-mentioned material and preparation method obtain, there is good electric conductivity, except can be used as semiconductor devices, electromagnetic shielding material and antistatic material, radar, infrared ray, ultraviolet etc. can also be absorbed, be applied to many special dimensions.
Detailed description of the invention
Embodiment 1
A preparation method for carbon nano-tube/poly ammonia ester/polyacrylonitrile composite conductive fibre, step is as follows:
(1) multi-walled carbon nano-tubes puts into single port flask, the red fuming nitric acid (RFNA) of 70% is added under vigorous stirring, put into 140 DEG C of constant temperature oil bath backflows to take out after 1 hour, dilute with deionized water, filter, and repeatedly rinse with deionized water, finally gained black solid is placed in vacuum drying oven and is dried to constant weight in 50 DEG C, obtain carboxylated multi-walled carbon nano-tubes;
(2) 10 grams of carboxylic carbon nano-tubes, 50 grams of polyurethane are placed in 800 grams of dimethyl sulfoxide (DMSO)s and fully stir together with 140 grams of polyacrylonitrile, polyurethane and polyacrylonitrile are dissolved and obtains blend solution.By filtration under diminished pressure, vacuum defoamation, obtained co-blended spinning stoste;
(3) adopt wet spinning technology path, utilize conventional wet lay former, above spinning slurry after filtration, after measuring pump, clamp-on in coagulating bath by spinneret orifice, coagulating bath is the aqueous solution of dimethyl sulfoxide (DMSO), coagulation bath temperature 20 DEG C, and the concentration of dimethyl sulfoxide (DMSO) is 50%.After high polymer solidifies, by deflector roll, stretch in water, draw ratio is 6 times.Silk after stretching enters rinsing machine.Fiber after washing is after oil bath oils, dry in drying machine, reels afterwards.Namely obtain carbon nano-tube/poly ammonia ester/anti-static polyacrylonitrile fibre, the carbon nanotube mass mark of this fiber is 5%, and polyurethane mass fraction is 25%, and the mass fraction of polyacrylonitrile is 70%.The electrical conductivity of fiber is 10
-5s/cm, intensity is 4.96 cN/dtex.
Embodiment 2
A preparation method for carbon nano-tube/poly ammonia ester/polyacrylonitrile composite conductive fibre, step is as follows:
(1) single armed wall carbon nano tube puts into single port flask, the concentrated sulfuric acid of 98% is added under vigorous stirring, put into 120 DEG C of constant temperature oil bath backflows to take out after 1.5 hours, dilute with deionized water, filter, and repeatedly rinse with deionized water, in vacuum drying oven, be dried to constant weight, obtain carboxylated single armed CNT;
(2) by 5 grams of carboxylated CNTs, 60 grams be placed in 600 grams of dimethyl sulfoxide (DMSO)s and fully stir together with 135 grams of polyacrylonitrile, polyurethane and polyacrylonitrile are dissolved and obtain blend solution.Through filtration under diminished pressure, vacuum defoamation, obtained co-blended spinning stoste;
(3) above spinning slurry after filtration, after measuring pump, clamp-on in coagulating bath by spinneret orifice, coagulating bath is the aqueous solution of dimethyl sulfoxide (DMSO), coagulation bath temperature 30 DEG C, and the concentration of dimethyl sulfoxide (DMSO) is 45%.After high polymer solidifies, by deflector roll, stretch in water, draw ratio is 6 times.Silk after stretching enters rinsing machine.Fiber after washing is after oil bath oils, dry in drying machine, reels afterwards.Namely obtain carbon nano-tube/poly ammonia ester/polyacrylonitrile composite fiber, the mass fraction of the CNT of this fiber is 2.5%, and polyurethane mass fraction is 30%, and the mass fraction of polyacrylonitrile is 67.5%.The electrical conductivity of fiber is 10
-7s/cm, intensity is 5.23 cN/dtex.
Embodiment 3
A preparation method for carbon nano-tube/poly ammonia ester/polyacrylonitrile composite conductive fibre, step is as follows:
(1) multi-walled carbon nano-tubes puts into single port flask, 110 DEG C of constant temperature oil bath backflow taking-ups after 0.5 hour put into by the mixed liquor (volume ratio is 3: 1) adding the concentrated sulfuric acid of 98% and the red fuming nitric acid (RFNA) of 70% under vigorous stirring, dilute with deionized water, filter, be dried to constant weight, obtain the CNT of purifying;
(2) 16 grams of carboxylated CNTs, 64 grams of polyurethane are placed in 900 grams of dimethyl formamides and fully stir together with 120 grams of polyacrylonitrile, polyurethane and polyacrylonitrile are dissolved and obtains blend solution.Through filtration under diminished pressure, vacuum defoamation, obtained co-blended spinning stoste;
(3) above spinning slurry after filtration, after measuring pump, clamp-on in coagulating bath by spinneret orifice, coagulating bath is the aqueous solution of dimethyl formamide, coagulation bath temperature 40 DEG C, and the concentration of dimethyl formamide is 40%.After high polymer solidifies, by deflector roll, stretch in water, draw ratio is 4 times.Silk after stretching enters rinsing machine.Fiber after washing is after oil bath oils, dry in drying machine, reels afterwards.Namely obtain carbon nano-tube/poly ammonia ester/polyacrylonitrile composite fiber, the mass fraction of the CNT of this fiber is 8%, and polyurethane mass fraction is 32%, and the mass fraction of polyacrylonitrile is 60%.The electrical conductivity of fiber is 10
-3s/cm, intensity is 4.37 cN/dtex.
Embodiment 4
A preparation method for carbon nano-tube/poly ammonia ester/polyacrylonitrile composite conductive fibre, step is as follows:
(1) multi-walled carbon nano-tubes puts into single port flask, the red fuming nitric acid (RFNA) of 70% is added under vigorous stirring, put into 140 DEG C of constant temperature oil bath backflows to take out after 1 hour, dilute with deionized water, filter, and repeatedly rinse with deionized water, finally gained black solid is placed in vacuum drying oven and is dried to constant weight in 50 DEG C, obtain carboxylated multi-walled carbon nano-tubes;
(2) 18 grams of carboxylic carbon nano-tubes, 80 grams of polyurethane are placed in 1100 grams of dimethyl sulfoxide (DMSO)s and fully stir together with 112 grams of polyacrylonitrile, polyacrylonitrile is dissolved and obtains blend solution.By filtration under diminished pressure, vacuum defoamation, obtained co-blended spinning stoste;
(3) adopt wet spinning technology path, utilize conventional wet lay former, above spinning slurry after filtration, after measuring pump, clamp-on in coagulating bath by spinneret orifice, coagulating bath is the aqueous solution of dimethyl sulfoxide (DMSO), coagulation bath temperature 20 DEG C, and the concentration of dimethyl sulfoxide (DMSO) is 50%.After high polymer solidifies, by deflector roll, stretch in water, draw ratio is 6 times.Silk after stretching enters rinsing machine.Fiber after washing is after oil bath oils, dry in drying machine, reels afterwards.Namely obtain carbon nano-tube/poly ammonia ester/anti-static polyacrylonitrile fibre, the carbon nanotube mass mark of this fiber is 9%, and polyurethane mass fraction is 40%, and the mass fraction of polyacrylonitrile is 51%.The electrical conductivity of fiber is 10
-3s/cm, intensity is 3.93 cN/dtex.
Embodiment 5
A preparation method for carbon nano-tube/poly ammonia ester/polyacrylonitrile composite conductive fibre, step is as follows:
(1) multi-walled carbon nano-tubes puts into single port flask, 110 DEG C of constant temperature oil bath backflow taking-ups after 0.5 hour put into by the mixed liquor (volume ratio is 3: 1) adding the concentrated sulfuric acid of 98% and the red fuming nitric acid (RFNA) of 70% under vigorous stirring, dilute with deionized water, filter, be dried to constant weight, obtain carboxylated CNT;
(2) 20 grams of carboxylated CNTs, 80 grams of polyurethane are placed in 800 grams of dimethyl formamides and fully stir together with 120 grams of polyacrylonitrile, polyurethane and polyacrylonitrile are dissolved and obtains blend solution.Through filtration under diminished pressure, vacuum defoamation, obtained co-blended spinning stoste;
(3) above spinning slurry after filtration, after measuring pump, clamp-on in coagulating bath by spinneret orifice, coagulating bath is the aqueous solution of dimethyl formamide, coagulation bath temperature 40 DEG C, and the concentration of dimethyl formamide is 40%.After high polymer solidifies, by deflector roll, stretch in water, draw ratio is 4 times.Silk after stretching enters rinsing machine.Fiber after washing is after oil bath oils, dry in drying machine, reels afterwards.Namely obtain carbon nano-tube/poly ammonia ester/polyacrylonitrile composite fiber, the mass fraction of the CNT of this fiber is 10%, and polyurethane mass fraction is 40%, and the mass fraction of polyacrylonitrile is 50%.The electrical conductivity of fiber is 10
-2s/cm, intensity is 4.37 cN/dtex.
Embodiment 6
A preparation method for carbon nano-tube/poly ammonia ester/polyacrylonitrile composite conductive fibre, step is as follows:
(1) multi-walled carbon nano-tubes puts into single port flask, 110 DEG C of constant temperature oil bath backflow taking-ups after 1 hour put into by the mixed liquor (volume ratio is 3: 1) adding the concentrated sulfuric acid of 98% and the red fuming nitric acid (RFNA) of 70% under vigorous stirring, dilute with deionized water, filter, be dried to constant weight, obtain the CNT of purifying;
(2) 4 grams of carboxylated CNTs, 56 grams of polyurethane are placed in 1000 grams of dimethyl formamides and fully stir together with 140 grams of polyacrylonitrile, polyurethane and polyacrylonitrile are dissolved and obtains blend solution.Through filtration under diminished pressure, vacuum defoamation, obtained co-blended spinning stoste;
(3) above spinning slurry after filtration, after measuring pump, clamp-on in coagulating bath by spinneret orifice, coagulating bath is the aqueous solution of dimethyl formamide, coagulation bath temperature 40 DEG C, and the concentration of dimethyl formamide is 40%.After high polymer solidifies, by deflector roll, stretch in water, draw ratio is 4 times.Silk after stretching enters rinsing machine.Fiber after washing is after oil bath oils, dry in drying machine, reels afterwards.Namely obtain carbon nano-tube/poly ammonia ester/polyacrylonitrile composite fiber, the mass fraction of the CNT of this fiber is 2%, and polyurethane mass fraction is 28%, and the mass fraction of polyacrylonitrile is 70%, and the electrical conductivity of fiber is 10
-8s/cm, intensity is 4.96 cN/dtex.
Claims (3)
1. carbon nano-tube/poly ammonia ester/polyacrylonitrile composite conductive fibre preparation method, is characterized in that its step is as follows:
(1) CNT is taken out after concentration is reflux 0.5 ~ 4 hour in 70% ~ 98% strong acid solution, dilute with deionized water, filter, and repeatedly rinse with deionized water, gained black solid is placed in vacuum drying oven and is dried to constant weight, obtain carboxylated CNT;
(2) carboxylated CNT, polyurethane and polyacrylonitrile are placed in spin solvent to stir, polyurethane and polyacrylonitrile dissolve and obtain blend solution, then filtration under diminished pressure, vacuum defoamation, obtained co-blended spinning stoste;
(3) on wet process equipment, co-blended spinning solution is filtered, measures, the coagulating bath be made up of spin solvent and water is clamp-oned by spinneret orifice, wherein in coagulating bath, the mass fraction of spin solvent is 20 ~ 60%, carboxylic carbon nano-tube, polyurethane and the polyacrylonitrile concentration in spin solvent is 12 ~ 35%, adopts circulation bath to keep coagulating bath concentration stabilize; Stretch and carry out in aqueous, draw ratio is 3 ~ 8, obtains carbon nano-tube/poly ammonia ester/polyacrylonitrile composite conductive fibre.
2. carbon nano-tube/poly ammonia ester/polyacrylonitrile composite conductive fibre preparation method according to claim 1, is characterized in that: described strong acid is at least one in nitric acid, sulfuric acid.
3. carbon nano-tube/poly ammonia ester/polyacrylonitrile composite conductive fibre preparation method according to claim 1, is characterized in that: described spin solvent is dimethyl sulfoxide (DMSO) or dimethyl formamide.
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| CN103726127B (en) * | 2013-12-26 | 2015-08-12 | 浙江华峰氨纶股份有限公司 | A kind of black polyurethane urea elastomer adding CNT and preparation method thereof |
| CN105155003B (en) * | 2015-08-06 | 2017-10-20 | 武汉纺织大学 | A kind of preparation method of high-strength and high-modulus highly-elastic urethane fiber |
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| CN108708076A (en) * | 2018-04-09 | 2018-10-26 | 南京捷纳思新材料有限公司 | The method that wet spinning prepares core/shell polyurethane-carbon nanotube conducting non-woven fabrics |
| CN109056105B (en) * | 2018-08-02 | 2021-06-04 | 九力绳缆有限公司 | Dye-adsorbing fiber and preparation method of rope thereof |
| CN109355730B (en) * | 2018-10-22 | 2021-04-13 | 华峰化学股份有限公司 | Preparation method of high-modulus high-elasticity polyurethane fiber |
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| CN113235182B (en) * | 2021-04-09 | 2022-04-15 | 大连理工大学 | Preparation method of high-flexibility carbon nanotube fiber |
| CN114507914B (en) * | 2022-01-27 | 2023-12-05 | 闽都创新实验室 | Method for preparing special electrical sensing fiber through wet spinning |
| CN114921882B (en) * | 2022-05-19 | 2023-04-28 | 武汉纺织大学 | Elastic electromagnetic shielding fiber and preparation method and application thereof |
| CN115233320B (en) * | 2022-08-04 | 2024-01-09 | 青岛大学 | Preparation method of high-conductivity special-shaped composite fiber |
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| CN102409422A (en) * | 2011-12-20 | 2012-04-11 | 中原工学院 | Method for preparing antistatic polyacrylonitrile fibers from double-component nano electroconductive agent |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1746343A (en) * | 2005-09-14 | 2006-03-15 | 东华大学 | Carbon nanometer tube composite fibre with high orientation and production thereof |
| CN102409422A (en) * | 2011-12-20 | 2012-04-11 | 中原工学院 | Method for preparing antistatic polyacrylonitrile fibers from double-component nano electroconductive agent |
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