CN105463613A - Polyamide6-graphene quantum dot/carbon nanotube anti-static fiber and preparation - Google Patents
Polyamide6-graphene quantum dot/carbon nanotube anti-static fiber and preparation Download PDFInfo
- Publication number
- CN105463613A CN105463613A CN201510953236.1A CN201510953236A CN105463613A CN 105463613 A CN105463613 A CN 105463613A CN 201510953236 A CN201510953236 A CN 201510953236A CN 105463613 A CN105463613 A CN 105463613A
- Authority
- CN
- China
- Prior art keywords
- cnt
- gqd
- graphene quantum
- quantum dot
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
- D01F6/90—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 polyamides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/08—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino-carboxylic acids
- C08G69/14—Lactams
- C08G69/16—Preparatory processes
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Textile Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Artificial Filaments (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides polyamide6-graphene quantum dot/carbon nanotube anti-static fiber and preparation. According to the method, the molecular template effect of graphene quantum dots is utilized for being compounded with a carbon nanotube to form a self-assembled three-dimensional network structure first and then combined with a PA6 knitting state structure to form a dislocation effect to construct a conductive path, conductivity is improved on the condition of not losing a mechanical property of PA6 fiber, and meanwhile conductivity and the mechanical property of the PA fiber are promoted. Moreover, by means of compounding of the graphene quantum dots and the carbon nano tube and the self-assembled three-dimensional network structure, electronic transmission efficiency in the carbon nano tube is improved, a small quantity of GQD/CNT is added, conductivity of the fiber can be improved, and transparency is improved at the same time, which is beneficial for treatment technologies like dyeing in the fiber preparing process. By means of the traditional mature PA6 melt spinning technology, the high-strength and high-conductivity PA6-GQD/CNT composite fiber with tensile strength being 0.52-0.81 GPa and line resistance being magnitude 106 is prepared and can be applied to anti-static clothes, needle-punched carpet, filter felt, industrial non-woven fabric, medical supplies and the like.
Description
Technical field
The invention belongs to composite fibre technology field, relate to a kind of polyamide 6-graphene quantum dot/CNT antistatic fiber and preparation.
Background technology
Be separated again after the object contact of any two unlike materials, can electrostatic be produced.Static electric charge is not fearful, and the electrostatic on the person can run up to several ten thousand volts sometimes, the release that fearful is electrostatic is uneven and violent, very easily detonator circuit puncture, fire, the malignant event such as information interference, therefore the strick precaution of electrostatic is extremely important.The electrostatic that in life, conventional antistatic textiles removing is harmful, anti-static fabric is mainly knitted with antistatic fiber and is done.Antistatic fiber generally adopts conductive fiber and antistatic fibre.The antistatic effect of antistatic fibre and the humidity of environment closely related, when ambient humidity is very low, its antistatic effect is very weak even to disappear, and quite a few antistatic fibre washability is poor, and persistence is poor.Conductive fiber has and does not rely on environment and stablize outstanding electric conductivity and excellent wear-resisting persistence, so the parent being more and more subject to people looks at.
Conductive fiber can be divided into metal fibre, carbon fiber, conductive polymer fiber, composite conducting fiber etc.; wherein adopt composite spinning method electrically conductive particles to be mixed into composite conducting fiber obtained in fiber stoste and neither affect the original physical property of fiber; make again fiber be provided with electric conductivity, therefore obtain investigation and application more and more widely.Wherein being most widely used of polyamide 6 conductive fiber, the method preparing polyamide 6 conductive fiber at present in the matrix of fiber, adds conductive filler carry out spinning, and the conductive filler of employing mainly comprises the large class of metal system and carbon system two.The electric conductivity of metal system composite conducting fiber is poor, and conductive materials is difficult to dispersed, spinning solution poor fluidity, difficulty in spinning in polymeric matrix, and fibrous mechanical property worsens.Carbon system filler mainly comprises: carbon black, CNT and Graphene.Black grain diameter is comparatively large, be difficult to dispersion, critical content is higher, and the composite conducting fiber obtained in grey black, be not suitable for light textiles, and mechanical performance is poor, therefore its range of application is restricted usually.Road has been widened in the development developing into composite conducting fiber of the new carbon such as CNT, Graphene, makes it likely have good mechanical property and electric conductivity concurrently simultaneously.
1991, Iijima (the S.Iijima of NEC Corporation of Japan, Nature, 1991,354,56), when analyzing with high-resolution-ration transmission electric-lens the cathode deposition that arc discharge produces, found the CNT with nano-scale (CNTs), CNTs had that size is little, draw ratio is large, intensity is high, electrical conductivity is high, good corrosion resistance and the advantage such as density is little.CNTs is made up of C mono-C chain structure, close with polymer chain structure, and researcher found through experiments and CNTs and macromolecular material are carried out compound, the nano composite material that available can be excellent.Since (P.M.Ajayanetal., Science, 1994,265, the 1212) reported first such as Ajayan adopt CNTs to prepare polymer composites as filler, the compound of CNTs and polymer becomes a study hotspot.CNTs is as a kind of novel one-dimensional nano carbon system material, unique texture in size, specific area etc. gives its electrical properties being far superior to carbon black, its arrangement directed or orderly in polymeric matrix, produces impact greatly by the electricity of composite and mechanical property.But because CNTs specific area is large, draw ratio is large, strong van der Waals interaction each other in addition, make them usually become bulk or pencil aggregation, the dispersion in polymeric matrix is more difficult, constrains its commercial application in polymer composites.
Since Graphene was found by Geim and Novoselov etc. from 2004 (K.S.Novoselov, A.K.Geim, etal., Science, 2004,306,666), be subject to the favor of researcher always.Because it has very excellent mechanical performance, such as: high Young's modulus and fracture strength, outstanding thermal conductivity and specific area, splendid electrical property, Graphene is the ideal filler of the high tough conductive polymers based composite of preparation.Graphene is as the member of newfound carbon-based material, and combine the advantage of other carbon system filler, have conductivity percolation threshold values low, the advantages such as relative inexpensiveness, the modification for polymer provides new chance.In recent years, the research of polymer/graphene composite material obtains development at full speed, has had a large amount of reports (A.K.Geim, Science, 2009,19,1530 both at home and abroad; Tension force, Wu Juntao, Jiang Lei, chemical progress, 2014,26,560).But because specific area and surface free energy are large, the sheet interlayer of Graphene has very strong electrostatic force and Van der Waals force, usually there are (S.Stankovich, etal., Carbon, 2007,45,1558) with reunion form.The aggregate of Graphene is unfavorable for the excellent properties playing itself, easily causes polymer composites to produce defect, is unfavorable for the improvement of material property.Therefore, the fine dispersion of Graphene in polymeric matrix is realized and peeling effect is the important prerequisite manufacturing desirable nano composite material.
In order to improve Graphene and the dispersion effect of CNT in polymeric matrix, in conjunction with both advantage, Graphene and CNT are used for composite (M.A.Worsley, etal., J.Am.Chem.Soc.2010,132,14067 by people jointly; W.H.Guo, etal., J.Mater.Chem.2012,22,903), build CNT-graphene composite structure.Carbon nanometer tube-graphene composite material forms tridimensional network (as shown in Figure 1) by wire-board junction, increases the effective contact between electrical-conductive nanometer material, forms bridging structure.By the cooperative effect between them, the two collaborative dispersion, CNT can be used as the intercalation material of Graphene, contribute to the dispersion of the two, avoid the formation of microaggregate, make it show the isotropic conductivity (V.C.Tung more excellent than any one homogenous material, etal., NanoLett.2009,9,1949).But ordinary graphite alkene due to its radial dimension large, easy formation fold, the localized micro structure such as stacking, cause effective binding site of CNT and its generation very few, microscopic contact resistance is large, and the conduction advantage of graphene-carbon nano tube tridimensional network is difficult to play.
Summary of the invention
The object of the present invention is to provide a kind of polyamide 6-graphene quantum dot/CNT antistatic fiber and preparation, solve carbon nanomaterial dispersed and imperfect problem of fibrous transparent degree in composite fibre, this fiber has lightweight, good conductivity, transparency advantages of higher.
Graphene quantum dot (Graphenequantumdot, be abbreviated as GQD) be the nano material (two dimensional surface size <100nm) of accurate zero dimension, the motion of its internal electron in all directions is more active, so quantum effect is remarkable especially, there is the character of many uniquenesses, show more significant nanoscale effect.Find through our group study, face-the electric conductivity of line compound self assembled three-dimensional network structure to daiamid-6 fiber that graphene quantum dot and CNT are formed has and significantly strengthens effect, add a small amount of graphene quantum dot and CNT just can obtain desirable effect, obtained composite fibre also has good mechanical property and transparency simultaneously.
The present invention adopts graphene quantum dot and carbon mano-tube composite as polyamide-6 fiber electrical-conductive nanometer filler, utilize that graphene quantum dot radial dimension is little, marginal texture enriches, be easy to CNT and form the cancellated feature of conducting three-dimensional, solve the easy fold of ordinary graphite alkene and the stacking problem causing its difficulties in dispersion, obtain polyamide-6 composite conducting fiber that transparency is better, electric conductivity is excellent.
The present invention relates to a kind of polyamide 6-graphene quantum dot/CNT antistatic fiber preparation method, the method comprises the following steps:
The first step, the preparation of graphene quantum dot/CNT (GQD/CNT) composite
(1) get graphene quantum dot 0.1 ~ 1 weight portion, dispersant 0.1 ~ 1 weight portion, be dissolved in the deionized water of 48 ~ 49.8 weight portions, through dispersion, obtain homodisperse graphene quantum dot dispersion; The graphite flake layer of described graphene quantum dot is 1 ~ 3 layer, is of a size of 10 ~ 100nm;
(2) in (1), add CNT 0.1 ~ 1 weight portion, dispersant 0.1 ~ 1 weight portion, deionized water 48 ~ 49.8 weight portion, through dispersion, centrifugal, filtration, obtain homodisperse GQD/CNT mixed liquor; Described CNT is single wall and multi-walled carbon nano-tubes, diameter 2 ~ 20nm, and length is 0.1 ~ 2 μm; Described scatter operation is ultrasonic wave or high-pressure homogeneous dispersion, adopts ultrasonic cell disruption instrument, its power 1000 ~ 4000W; Or employing superhigh-voltage homogenizing machine, its power is 2500W;
(3) above-mentioned GQD/CNT mixed liquor is obtained GQD/CNT composite powder after vacuum filtration, vacuumize; The described vacuum filtration time is 0.5-2h, and vacuumize temperature is 60-100 DEG C, and drying time is 0.5-2h;
Second step, the preparation of polyamide 6-graphene quantum dot/CNT (PA6-GQD/CNT) master batch
(1) get caprolactam 79 ~ 97.5 weight portion, above-mentioned GQD/CNT composite powder 2-20 weight portion, add initator 0.5 ~ 1 weight portion, stirring, ultrasonic disperse, be mixed with caprolactam-GQD/CNT mixture; Described initator is the one in 6-aminocaprolc acid, butyric acid, phosphoric acid; Described dispersant is any one situation of statement in (a) ~ (c): (a) polyethenoxy ether class or ester class tween, (b) Sulfonates, Sulfates, phosphate or phosphite anionoid activating agent, the mixture of one or more arbitrary proportions in (c) amino acids, imidazoles, oxidation amine amphoteric surfactant;
(2) by above-mentioned mixed liquor through steps such as prepolymerization, polymerization, granulation, washing, vacuumizes, obtained PA6-GQD/CNT master batch; Described prepolymerization temperature is 150-200 DEG C, and the time is 1-3h; Polymerization temperature is 250-270 DEG C, and the time is 10-30h; Vacuumize temperature is 60-100 DEG C, and drying time is 2-5h;
3rd step, melt spinning
(1) above-mentioned PA6-GQD/CNT master batch 1 ~ 10 weight portion, pure polyamide 6 about 10 ~ 20 weight portion are added in screw extruder extrude after melt blending, make section;
(2) common melt spinning machine is adopted to carry out melt spinning, preparation PA6-GQD/CNT composite fibre; In described melt spinning process, spinning temperature is 220 ~ 280 DEG C; Different according to purposes, PA6-GQD/CNT composite fibre to be oiled, curling and/or cut off.
The invention still further relates to a kind of polyamide 6-graphene quantum dot/CNT antistatic fiber, this antistatic fiber is prepared from by said method.
Said method utilizes the molecular template effect of graphene quantum dot, first be compounded to form self assembled three-dimensional network structure with CNT, form dislocation effect again and between PA6 texture, build conductive path, improving its electric conductivity when not losing PA6 fibrous mechanical property, achieving the lifting of PA6 filamentary conductive energy and mechanical property simultaneously.Due to compound and the self assembled three-dimensional network structure thereof of graphene quantum dot in the present invention and CNT, substantially increase electronics efficiency of transmission wherein, add the electric conductivity that a small amount of GQD/CNT can improve fiber greatly, improve its transparency simultaneously, be conducive to the treatment process such as the dyeing in fiber manufacturing process.Having prepared TENSILE STRENGTH by the PA6 melt spinning process that tradition is ripe is 0.52 ~ 0.81GPa, and line resistance is 10
6the PA6-GQD/CNT composite fibre that the strength high electrical conductivity of magnitude is good, can be used for antistatic clothes, needle punched carpet, filter felt, Industrial Nonwovens, medical supplies etc.
Accompanying drawing explanation
Fig. 1 is graphene quantum dot/CNT face-line complex three-dimensional network structure schematic diagram.
Detailed description of the invention
Below in conjunction with drawings and Examples, the invention will be further described, but should not be construed the above-mentioned subject area of the present invention and be only limitted to following embodiment.Without departing from the idea case in the present invention described above, according to ordinary skill knowledge and customary means, make various replacement and change, all should be included in protection scope of the present invention.
Embodiment 1:
A preparation method for polyamide 6-graphene quantum dot/CNT antistatic fiber, comprises the following steps:
1. the preparation of graphene quantum dot/CNT (GQD/CNT) composite
(1) graphene quantum dot 8g, polyoxyethylene nonylphenol ether (OP-10) 4g is got, be dissolved in the deionized water of 488g, through ultrasonic disperse (using ultrasonic cell disruption instrument, its power 2000W), obtain the homodisperse graphene quantum dot aqueous solution;
(2) in (1), add CNT 4g, polyoxyethylene nonylphenol ether (OP-10) 4g, deionized water 492g, filter after ultrasonic cell disruption instrument (power 2000W) ultrasonic disperse, 1000g centrifugal force, obtain homodisperse GQD/CNT mixed liquor.The graphite flake layer of the graphene quantum dot adopted in this step is 1 ~ 3 layer, is of a size of 10 ~ 100nm, and CNT is Single Walled Carbon Nanotube, diameter 2 ~ 10nm, and length is 0.1 ~ 2 μm;
(3) above-mentioned GQD/CNT mixed liquor is drained to put at vacuum drying chamber 80 DEG C after moisture through vacuum filtration 0.5h after vacuumize 2h, obtain GQD/CNT composite powder.
2. the preparation of polyamide 6-graphene quantum dot/CNT (PA6-GQD/CNT) master batch
(1) get caprolactam 84.28g, above-mentioned GQD/CNT composite powder 14.88g, add 6-aminocaprolc acid 0.84g, be heated to 100 DEG C, mechanical agitation 3h, and coordinate ultrasonic disperse (power 2000W), be mixed with PA6-GQD/CNT mixture;
(2) above-mentioned mixed liquor is obtained prepolymer at 180 DEG C of prepolymerization 3h, be then polymerized 12h at 250 DEG C; The Small molecular or oligomer and initator that are not fully polymerized is washed away respectively, vacuumize 4h at 80 DEG C, obtained PA6-GQD/CNT master batch with deionized water and ethanol.
3. melt spinning
(1) above-mentioned PA6-GQD/CNT master batch 50g, pure polyamide 6 section 200g are added in screw extruder extrude after melt blending, make section;
(2) adopt common melt spinning machine to carry out melt spinning, preparation PA6-GQD/CNT composite fibre, in melt spinning process, spinning temperature is 250 DEG C.
The fracture strength of the present embodiment gained composite fibre is 0.71GPa, and line resistance is 4.3 × 10
6Ω/cm.
Embodiment 2:
A preparation method for polyamide 6-graphene quantum dot/CNT antistatic fiber, comprises the following steps:
1. the preparation of graphene quantum dot/CNT (GQD/CNT) composite
(1) get graphene quantum dot 10g, lauryl sodium sulfate 10g, be dissolved in the deionized water of 480g, through homogenous disperse (using superhigh-voltage homogenizing machine JN-10HC, its power 2500W), obtain the homodisperse graphene quantum dot aqueous solution;
(2) in (1), CNT 2g, lauryl sodium sulfate 4g, deionized water 494g is added, filter after ultrasonic cell disruption instrument (power 1000W) ultrasonic disperse, 1000g centrifugal force, obtain homodisperse GQD/CNT mixed solution.The graphite flake layer of the graphene quantum dot adopted in this step is 1 ~ 3 layer, is of a size of 10 ~ 100nm, and CNT is Single Walled Carbon Nanotube, diameter 2 ~ 10nm, and length is 0.1 ~ 2 μm;
(3) above-mentioned GQD/CNT mixed liquor is drained to put at vacuum drying chamber 60 DEG C after moisture through vacuum filtration 2h after vacuumize 2h, obtain GQD/CNT composite powder.
2. the preparation of polyamide 6-graphene quantum dot/CNT (PA6-GQD/CNT) master batch
(1) get caprolactam 82.32g, above-mentioned GQD/CNT composite powder 16.86g, add butyric acid 0.82g, be heated to 100 DEG C, mechanical agitation 3h, and coordinate ultrasonic disperse (power 2000W), be mixed with PA6-GQD/CNT mixture;
(2) above-mentioned mixed liquor is obtained prepolymer at 150 DEG C of prepolymerization 3h, then polyase 13 0h at 250 DEG C; The Small molecular or oligomer and initator that are not fully polymerized is washed away respectively, vacuumize 5h at 60 DEG C, obtained PA6-GQD/CNT master batch with deionized water and ethanol.
3. melt spinning
(1) above-mentioned PA6-GQD/CNT master batch 30g, pure polyamide 6 section 300g are added in screw extruder extrude after melt blending, make section;
(2) common melt spinning machine is adopted to carry out melt spinning, preparation PA6-GQD/CNT composite fibre.In melt spinning process, spinning temperature is 220 DEG C.
The fracture strength of the present embodiment gained composite fibre is 0.70GPa, and line resistance is 9.0 × 10
6Ω/cm.
Embodiment 3:
A preparation method for polyamide 6-graphene quantum dot/CNT antistatic fiber, comprises the following steps:
1. the preparation of graphene quantum dot/CNT (GQD/CNT) composite
(1) get graphene quantum dot 6g, alkylphenol polyoxyethylene 6g, be dissolved in the deionized water of 488g, through ultrasonic disperse (using ultrasonic cell disruption instrument, its power 4000W), obtain the homodisperse graphene quantum dot aqueous solution;
(2) in (1), CNT 10g, alkylphenol polyoxyethylene 10g, deionized water 480g is added, filter after ultrasonic cell disruption instrument (power 2000W) ultrasonic disperse, 1000g centrifugal force, obtain homodisperse GQD/CNT mixed solution.The graphite flake layer of the graphene quantum dot adopted in this step is 1 ~ 3 layer, is of a size of 10 ~ 100nm, and CNT is Single Walled Carbon Nanotube, diameter 2 ~ 10nm, and length is 0.1 ~ 2 μm;
(3) above-mentioned GQD/CNT mixed liquor is drained to put at vacuum drying chamber 100 DEG C after moisture through vacuum filtration 1h after vacuumize 1h, obtain GQD/CNT composite powder.
2. the preparation of polyamide 6-graphene quantum dot/CNT (PA6-GQD/CNT) master batch
(1) get caprolactam 79.0g, above-mentioned GQD/CNT composite powder 20.0g, add phosphatase 11 .0g, be heated to 100 DEG C, mechanical agitation 3h, and coordinate ultrasonic disperse (power 2000W), be mixed with PA6-GQD/CNT mixture;
(2) above-mentioned mixed liquor is obtained prepolymer at 200 DEG C of prepolymerization 1h, be then polymerized 10h at 270 DEG C; The Small molecular or oligomer and initator that are not fully polymerized is washed away respectively, vacuumize 2h at 100 DEG C, obtained PA6-GQD/CNT master batch with deionized water and ethanol.
3. melt spinning
(1) above-mentioned PA6-GQD/CNT master batch 15g, pure polyamide 6 section 300g are added in screw extruder extrude after melt blending, make section;
(2) common melt spinning machine is adopted to carry out melt spinning, preparation PA6-GQD/CNT composite fibre.In melt spinning process, spinning temperature is 280 DEG C.
The fracture strength of the present embodiment gained composite fibre is 0.68GPa, and line resistance is 9.3 × 10
6Ω/cm.
Embodiment 4:
A preparation method for polyamide 6-graphene quantum dot/CNT antistatic fiber, comprises the following steps:
1. the preparation of graphene quantum dot/CNT (GQD/CNT) composite
(1) get graphene quantum dot 4g, lauryl sodium sulfate 2.4g, be dissolved in the deionized water of 493.6g, through ultrasonic disperse (using ultrasonic cell disruption instrument, its power 2000W), obtain the homodisperse graphene quantum dot aqueous solution;
(2) in (1), CNT 4g, lauryl sodium sulfate 1.6g, deionized water 494.4g is added, through high pressure homogenizer dispersion (superhigh-voltage homogenizing machine JN-10HC, its power 2500W), filter after 1000g centrifugal force, obtain homodisperse GQD/CNT mixed solution.The graphite flake layer of the graphene quantum dot adopted in this step is 1 ~ 3 layer, is of a size of 10 ~ 100nm, and CNT is Single Walled Carbon Nanotube, diameter 2 ~ 10nm, and length is 0.1 ~ 2 μm;
(3) above-mentioned GQD/CNT mixed liquor is drained to put at vacuum drying chamber 80 DEG C after moisture through vacuum filtration 0.5h after vacuumize 2h, obtain GQD/CNT composite powder.
2. the preparation of polyamide 6-graphene quantum dot/CNT (PA6-GQD/CNT) master batch
(1) get caprolactam 91.16g, above-mentioned GQD/CNT composite powder 7.93g, add 6-aminocaprolc acid 0.91g, be heated to 100 DEG C, mechanical agitation 3h, and coordinate ultrasonic disperse (power 2000W), be mixed with PA6-GQD/CNT mixture;
(2) above-mentioned mixed liquor is obtained prepolymer at 180 DEG C of prepolymerization 3h, be then polymerized 12h at 250 DEG C; The Small molecular or oligomer and initator that are not fully polymerized is washed away respectively, vacuumize 4h at 80 DEG C, obtained PA6-GQD/CNT master batch with deionized water and ethanol.
3. melt spinning
(1) above-mentioned PA6-GQD/CNT master batch 50g, pure polyamide 6 section 200g are added in screw extruder extrude after melt blending, make section;
(2) common melt spinning machine is adopted to carry out melt spinning, preparation PA6-GQD/CNT composite fibre.In melt spinning process, spinning temperature is 250 DEG C.
The fracture strength of the present embodiment gained composite fibre is 0.72GPa, and line resistance is 6.5 × 10
6Ω/cm.
Embodiment 5:
A preparation method for polyamide 6-graphene quantum dot/CNT antistatic fiber, comprises the following steps:
1. the preparation of graphene quantum dot/CNT (GQD/CNT) composite
(1) graphene quantum dot 4g, alkyl phenol polyethenoxy ether sodium sulfate 4g is got, be dissolved in the deionized water of 488g, through ultrasonic disperse (using ultrasonic cell disruption instrument, its power 2000W), obtain the homodisperse graphene quantum dot aqueous solution;
(2) in (1), CNT 2g, alkyl phenol polyethenoxy ether sodium sulfate 2g, deionized water 486g is added, through high pressure homogenizer dispersion (superhigh-voltage homogenizing machine JN-10HC, its power 2500W), filter after 1000g centrifugal force, obtain homodisperse GQD/CNT mixed solution.The graphite flake layer of the graphene quantum dot adopted in this step is 1 ~ 3 layer, is of a size of 10 ~ 100nm, and CNT is Single Walled Carbon Nanotube, diameter 2 ~ 10nm, and length is 0.1 ~ 2 μm;
(3) above-mentioned GQD/CNT mixed liquor is drained to put at vacuum drying chamber 80 DEG C after moisture through vacuum filtration 0.5h after vacuumize 2h, obtain GQD/CNT composite powder.
2. the preparation of polyamide 6-graphene quantum dot/CNT (PA6-GQD/CNT) master batch
(1) get caprolactam 89.20g, above-mentioned GQD/CNT composite powder 9.91g, add phosphoric acid 0.89g, be heated to 100 DEG C, mechanical agitation 3h, and coordinate ultrasonic disperse (power 2000W), be mixed with PA6-GQD/CNT mixture;
(2) above-mentioned mixed liquor is obtained prepolymer at 180 DEG C of prepolymerization 3h, be then polymerized 12h at 250 DEG C; The Small molecular or oligomer and initator that are not fully polymerized is washed away respectively, vacuumize 4h at 80 DEG C, obtained PA6-GQD/CNT master batch with deionized water and ethanol.
3. melt spinning
(1) above-mentioned PA6-GQD/CNT master batch 50g, pure polyamide 6 section 200g are added in screw extruder extrude after melt blending, make section;
(2) common melt spinning machine is adopted to carry out melt spinning, preparation PA6-GQD/CNT composite fibre.In melt spinning process, spinning temperature is 250 DEG C.
The fracture strength of the present embodiment gained composite fibre is 0.69GPa, and line resistance is 7.1 × 10
6Ω/cm.
Embodiment 6:
A preparation method for polyamide 6-graphene quantum dot/CNT antistatic fiber, comprises the following steps:
1. the preparation of graphene quantum dot/CNT (GQD/CNT) composite
(1) get graphene quantum dot 2g, lauryl sodium sulfate 1g, be dissolved in the deionized water of 497g, through homogenous disperse (using superhigh-voltage homogenizing machine JN-10HC, its power 2500W), obtain the homodisperse graphene quantum dot aqueous solution;
(2) in (1), CNT 2g, lauryl sodium sulfate 1g, deionized water 497g is added, filter after ultrasonic cell disruption instrument (power 2000W) ultrasonic disperse, 1000g centrifugal force, obtain homodisperse GQD/CNT mixed solution.The graphite flake layer of the graphene quantum dot adopted in this step is 1 ~ 3 layer, is of a size of 10 ~ 100nm, and CNT is Single Walled Carbon Nanotube, diameter 2 ~ 10nm, and length is 0.1 ~ 2 μm;
(3) above-mentioned GQD/CNT mixed liquor is drained to put at vacuum drying chamber 80 DEG C after moisture through vacuum filtration 0.5h after vacuumize 2h, obtain GQD/CNT composite powder;
2. the preparation of polyamide 6-graphene quantum dot/CNT (PA6-GQD/CNT) master batch
(1) get caprolactam 95g, above-mentioned GQD/CNT composite powder 4g, add butyric acid 1g, be heated to 100 DEG C, mechanical agitation 3h, and coordinate ultrasonic disperse (power 2000W), be mixed with PA6-GQD/CNT mixture;
(2) above-mentioned mixed liquor is obtained prepolymer at 180 DEG C of prepolymerization 3h, be then polymerized 12h at 250 DEG C; The Small molecular or oligomer and initator that are not fully polymerized is washed away respectively, vacuumize 4h at 80 DEG C, obtained PA6-GQD/CNT master batch with deionized water and ethanol.
3. melt spinning
(1) above-mentioned PA6-GQD/CNT master batch 50g, pure polyamide 6 section 200g are added in screw extruder extrude after melt blending, make section;
(2) common melt spinning machine is adopted to carry out melt spinning, preparation PA6-GQD/CNT composite fibre.In melt spinning process, spinning temperature is 250 DEG C.
The fracture strength of the present embodiment gained composite fibre is 0.79GPa, and line resistance is 8.3 × 10
6Ω/cm.
Embodiment 7:
A preparation method for polyamide 6-graphene quantum dot/CNT antistatic fiber, comprises the following steps:
1. the preparation of graphene quantum dot/CNT (GQD/CNT) composite
(1) graphene quantum dot 1g, polyoxyethylene nonylphenol ether (OP-10) 1g is got, be dissolved in the deionized water of 497g, through homogenous disperse (using superhigh-voltage homogenizing machine JN-10HC, its power 2500W), obtain the homodisperse graphene quantum dot aqueous solution;
(2) in (1), add CNT 1g, polyoxyethylene nonylphenol ether (OP-10) 1g, deionized water 498g, (superhigh-voltage homogenizing machine JN-10HC is used through homogenous disperse, its power 2500W), filter after 1000g centrifugal force, obtain homodisperse GQD/CNT mixed solution.The graphite flake layer of the graphene quantum dot adopted in this step is 1 ~ 3 layer, is of a size of 10 ~ 100nm, and CNT is Single Walled Carbon Nanotube, diameter 2 ~ 10nm, and length is 0.1 ~ 2 μm;
(3) above-mentioned GQD/CNT mixed liquor is drained to put at vacuum drying chamber 100 DEG C after moisture through vacuum filtration 1h after vacuumize 0.5h, obtain GQD/CNT composite powder.
2. the preparation of polyamide 6-graphene quantum dot/CNT (PA6-GQD/CNT) master batch
(1) get caprolactam 97.5g, above-mentioned GQD/CNT composite powder 2g, add 6-aminocaprolc acid 0.5g, be heated to 100 DEG C, mechanical agitation 3h, and coordinate ultrasonic disperse (power 2000W), be mixed with PA6-GQD/CNT mixture;
(2) above-mentioned mixed liquor is obtained prepolymer at 160 DEG C of prepolymerization 3h, be then polymerized 15h at 260 DEG C; The Small molecular or oligomer and initator that are not fully polymerized is washed away respectively, vacuumize 4h at 60 DEG C, obtained PA6-GQD/CNT master batch with deionized water and ethanol.
3. melt spinning
(1) above-mentioned PA6-GQD/CNT master batch 150g, pure polyamide 6 section 150g are added in screw extruder extrude after melt blending, make section;
(2) common melt spinning machine is adopted to carry out melt spinning, preparation PA6-GQD/CNT composite fibre.In melt spinning process, spinning temperature is 260 DEG C.
The fracture strength of the present embodiment gained composite fibre is 0.81GPa, and line resistance is 8.5 × 10
6Ω/cm.
Embodiment 8:
A preparation method for polyamide 6-graphene quantum dot/CNT antistatic fiber, comprises the following steps:
1. the preparation of graphene quantum dot/CNT (GQD/CNT) composite
(1) get graphene quantum dot 8g, lauryl sodium sulfate 4g, be dissolved in the deionized water of 488g, through homogenous disperse (using superhigh-voltage homogenizing machine JN-10HC, its power 2500W), obtain the homodisperse graphene quantum dot aqueous solution;
(2) in (1), CNT 2g, lauryl sodium sulfate 4g, deionized water 494g is added, filter after ultrasonic cell disruption instrument (power 2000W) ultrasonic disperse, 1000g centrifugal force, obtain homodisperse GQD/CNT mixed solution.The graphite flake layer of the graphene quantum dot adopted in this step is 1 ~ 3 layer, is of a size of 10 ~ 100nm, and CNT is Single Walled Carbon Nanotube, diameter 2 ~ 10nm, and length is 0.1 ~ 2 μm;
(3) above-mentioned GQD/CNT mixed liquor is drained to put at vacuum drying chamber 80 DEG C after moisture through vacuum filtration 1h after vacuumize 2h, obtain GQD/CNT composite powder.
2. the preparation of polyamide 6-graphene quantum dot/CNT (PA6-GQD/CNT) master batch
(1) get caprolactam 80g, above-mentioned GQD/CNT composite powder 19.2g, add 6-aminocaprolc acid 0.8g, be heated to 100 DEG C, mechanical agitation 3h, and coordinate ultrasonic disperse (power 2000W), be mixed with PA6-GQD/CNT mixture;
(2) above-mentioned mixed liquor is obtained prepolymer at 180 DEG C of prepolymerization 3h, be then polymerized 12h at 250 DEG C; The Small molecular or oligomer and initator that are not fully polymerized is washed away respectively, vacuumize 4h at 80 DEG C, obtained PA6-GQD/CNT master batch with deionized water and ethanol.
3. melt spinning
(1) above-mentioned PA6-GQD/CNT master batch 50g, pure polyamide 6 section 200g are added in screw extruder extrude after melt blending, make section;
(2) common melt spinning machine is adopted to carry out melt spinning, preparation PA6-GQD/CNT composite fibre.In melt spinning process, spinning temperature is 250 DEG C.
The fracture strength of the present embodiment gained composite fibre is 0.52GPa, and line resistance is 4.6 × 10
6Ω/cm.
Embodiment 9:
A preparation method for polyamide 6-graphene quantum dot/CNT antistatic fiber, comprises the following steps:
1. the preparation of graphene quantum dot/CNT (GQD/CNT) composite
(1) get graphene quantum dot 6g, lauryl sodium sulfate 3g, be dissolved in the deionized water of 491g, through homogenous disperse (using superhigh-voltage homogenizing machine JN-10HC, its power 2500W), obtain the homodisperse graphene quantum dot aqueous solution;
(2) in (1), CNT 3g, lauryl sodium sulfate 3g, deionized water 494g is added, filter after ultrasonic cell disruption instrument (power 2000W) ultrasonic disperse, 1000g centrifugal force, obtain homodisperse GQD/CNT mixed solution.The graphite flake layer of the graphene quantum dot adopted in this step is 1 ~ 3 layer, is of a size of 10 ~ 100nm, and CNT is Single Walled Carbon Nanotube, diameter 2 ~ 10nm, and length is 0.1 ~ 2 μm;
(3) above-mentioned GQD/CNT mixed liquor is drained to put at vacuum drying chamber 80 DEG C after moisture through vacuum filtration 0.5h after vacuumize 2h, obtain GQD/CNT composite powder.
2. the preparation of polyamide 6-graphene quantum dot/CNT (PA6-GQD/CNT) master batch
(1) get caprolactam 87g, above-mentioned GQD/CNT composite powder 12.1g, add phosphoric acid 0.9g, be heated to 100 DEG C, mechanical agitation 3h, and coordinate ultrasonic disperse (power 2000W), be mixed with PA6-GQD/CNT mixture;
(2) above-mentioned mixed liquor is obtained prepolymer at 180 DEG C of prepolymerization 3h, be then polymerized 12h at 250 DEG C; The Small molecular or oligomer and initator that are not fully polymerized is washed away respectively, vacuumize 4h at 80 DEG C, obtained PA6-GQD/CNT master batch with deionized water and ethanol.
3. melt spinning
(1) above-mentioned PA6-GQD/CNT master batch 50g, pure polyamide 6 section 200g are added in screw extruder extrude after melt blending, make section;
(2) common melt spinning machine is adopted to carry out melt spinning, preparation PA6-GQD/CNT composite fibre.In melt spinning process, spinning temperature is 250 DEG C.
The fracture strength of the present embodiment gained composite fibre is 0.71GPa, and line resistance is 6.3 × 10
6Ω/cm.
Embodiment 10:
A preparation method for polyamide 6-graphene quantum dot/CNT antistatic fiber, comprises the following steps:
1. the preparation of graphene quantum dot/CNT (GQD/CNT) composite
(1) get graphene quantum dot 8g, lauryl sodium sulfate 6g, be dissolved in the deionized water of 486g, through homogenous disperse (using superhigh-voltage homogenizing machine JN-10HC, its power 2500W), obtain the homodisperse graphene quantum dot aqueous solution;
(2) in (1), CNT 1g, lauryl sodium sulfate 2g, deionized water 497g is added, filter after ultrasonic cell disruption instrument (power 2000W) ultrasonic disperse, 1000g centrifugal force, obtain homodisperse GQD/CNT mixed solution.The graphite flake layer of the graphene quantum dot adopted in this step is 1 ~ 3 layer, is of a size of 10 ~ 100nm, and CNT is Single Walled Carbon Nanotube, diameter 2 ~ 10nm, and length is 0.1 ~ 2 μm;
(3) above-mentioned GQD/CNT mixed liquor is drained to put at vacuum drying chamber 80 DEG C after moisture through vacuum filtration 0.5h after vacuumize 2h, obtain GQD/CNT composite powder.
2. the preparation of polyamide 6-graphene quantum dot/CNT (PA6-GQD/CNT) master batch
(1) get caprolactam 85g, above-mentioned GQD/CNT composite powder 14.2g, add butyric acid 0.8g, be heated to 100 DEG C, mechanical agitation 3h, and coordinate ultrasonic disperse (power 2000W), be mixed with PA6-GQD/CNT mixture;
(2) above-mentioned mixed liquor is obtained prepolymer at 180 DEG C of prepolymerization 3h, be then polymerized 12h at 250 DEG C; The Small molecular or oligomer and initator that are not fully polymerized is washed away respectively, vacuumize 4h at 80 DEG C, obtained PA6-GQD/CNT master batch with deionized water and ethanol.
3. melt spinning
(1) above-mentioned PA6-GQD/CNT master batch 50g, pure polyamide 6 section 200g are added in screw extruder extrude after melt blending, make section;
(2) common melt spinning machine is adopted to carry out melt spinning, preparation PA6-GQD/CNT composite fibre.In melt spinning process, spinning temperature is 250 DEG C.
The fracture strength of the present embodiment gained composite fibre is 0.64GPa, and line resistance is 6.2 × 10
6Ω/cm.
Claims (2)
1. polyamide 6-graphene quantum dot/CNT antistatic fiber preparation method, is characterized in that the method comprises the following steps:
The first step, the preparation of graphene quantum dot/CNT (GQD/CNT) composite
(1) get graphene quantum dot 0.1 ~ 1 weight portion, dispersant 0.1 ~ 1 weight portion, be dissolved in the deionized water of 48 ~ 49.8 weight portions, through dispersion, obtain homodisperse graphene quantum dot dispersion; The graphite flake layer of described graphene quantum dot is 1 ~ 3 layer, is of a size of 10 ~ 100nm;
(2) in (1), add CNT 0.1 ~ 1 weight portion, dispersant 0.1 ~ 1 weight portion, deionized water 48 ~ 49.8 weight portion, through dispersion, centrifugal, filtration, obtain homodisperse GQD/CNT mixed liquor; Described CNT is single wall and multi-walled carbon nano-tubes, diameter 2 ~ 20nm, and length is 0.1 ~ 2 μm; Described scatter operation is ultrasonic wave or high-pressure homogeneous dispersion, adopts ultrasonic cell disruption instrument, its power 1000 ~ 4000W; Or employing superhigh-voltage homogenizing machine, its power is 2500W;
(3) above-mentioned GQD/CNT mixed liquor is obtained GQD/CNT composite powder after vacuum filtration, vacuumize; The described vacuum filtration time is 0.5-2h, and vacuumize temperature is 60-100 DEG C, and drying time is 0.5-2h;
Second step, the preparation of polyamide 6-graphene quantum dot/CNT (PA6-GQD/CNT) master batch
(1) get caprolactam 79 ~ 97.5 weight portion, above-mentioned GQD/CNT composite powder 2-20 weight portion, add initator 0.5 ~ 1 weight portion, stirring, ultrasonic disperse, be mixed with caprolactam-GQD/CNT mixture; Described initator is the one in 6-aminocaprolc acid, butyric acid, phosphoric acid; Described dispersant is any one situation of statement in (a) ~ (c): (a) polyethenoxy ether class or ester class tween, (b) Sulfonates, Sulfates, phosphate or phosphite anionoid activating agent, the mixture of one or more arbitrary proportions in (c) amino acids, imidazoles, oxidation amine amphoteric surfactant;
(2) by above-mentioned mixed liquor through steps such as prepolymerization, polymerization, granulation, washing, vacuumizes, obtained PA6-GQD/CNT master batch; Described prepolymerization temperature is 150-200 DEG C, and the time is 1-3h; Polymerization temperature is 250-270 DEG C, and the time is 10-30h; Vacuumize temperature is 60-100 DEG C, and drying time is 2-5h;
3rd step, melt spinning
(1) above-mentioned PA6-GQD/CNT master batch 1 ~ 10 weight portion, pure polyamide 6 about 10 ~ 20 weight portion are added in screw extruder extrude after melt blending, make section;
(2) common melt spinning machine is adopted to carry out melt spinning, preparation PA6-GQD/CNT composite fibre; In described melt spinning process, spinning temperature is 220 ~ 280 DEG C; Different according to purposes, PA6-GQD/CNT composite fibre to be oiled, curling and/or cut off.
2. polyamide 6-graphene quantum dot/CNT antistatic fiber, is characterized in that this antistatic fiber is prepared from by the method for claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510953236.1A CN105463613B (en) | 2015-12-17 | 2015-12-17 | Polyamide 6 graphene quantum dot/CNT antistatic fiber and preparation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510953236.1A CN105463613B (en) | 2015-12-17 | 2015-12-17 | Polyamide 6 graphene quantum dot/CNT antistatic fiber and preparation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105463613A true CN105463613A (en) | 2016-04-06 |
| CN105463613B CN105463613B (en) | 2018-03-09 |
Family
ID=55601754
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510953236.1A Expired - Fee Related CN105463613B (en) | 2015-12-17 | 2015-12-17 | Polyamide 6 graphene quantum dot/CNT antistatic fiber and preparation |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105463613B (en) |
Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106192192A (en) * | 2016-08-24 | 2016-12-07 | 福建省百凯经编实业有限公司 | The preparation method of patterned tricot lace fabric |
| CN106435827A (en) * | 2016-09-21 | 2017-02-22 | 东莞市联洲知识产权运营管理有限公司 | Ceramic/resin/graphene quantum dot composite fibers and preparation method thereof |
| CN106480532A (en) * | 2016-11-10 | 2017-03-08 | 过冬 | A kind of preparation method of Graphene reinforcing fiber |
| CN106675006A (en) * | 2017-01-05 | 2017-05-17 | 上海华峰超纤材料股份有限公司 | Conductive microfiber synthetic leather and production method thereof |
| CN107674385A (en) * | 2017-10-31 | 2018-02-09 | 西南石油大学 | A kind of preparation method of toughness reinforcing drop resistance carbon fibre composite |
| CN108951177A (en) * | 2017-05-18 | 2018-12-07 | 安安(中国)有限公司 | A kind of processing method of the suede superfine fiber synthetic leather with higher scratch resistance wear-resisting property |
| CN109592670A (en) * | 2018-12-20 | 2019-04-09 | 湖北工程学院 | The dispersing method of single-walled carbon nanotube |
| CN109930188A (en) * | 2019-01-31 | 2019-06-25 | 山东金宝电子股份有限公司 | A method of holey copper is prepared based on conductive fiber |
| CN110230110A (en) * | 2019-07-09 | 2019-09-13 | 杭州高烯科技有限公司 | A kind of low cost, the terylene of antistatic and preparation method thereof |
| CN110230109A (en) * | 2019-07-09 | 2019-09-13 | 杭州高烯科技有限公司 | A kind of low cost, the polyamide fibre of antistatic and preparation method thereof |
| CN110306250A (en) * | 2019-07-09 | 2019-10-08 | 杭州高烯科技有限公司 | A kind of compound nylon fabric of long-acting antistatic and preparation method thereof |
| CN110359121A (en) * | 2019-07-09 | 2019-10-22 | 杭州高烯科技有限公司 | A kind of fire-resistant antistatic polyamide fibre and preparation method thereof |
| CN110511375A (en) * | 2018-05-22 | 2019-11-29 | 上海杰事杰新材料(集团)股份有限公司 | A kind of static resistant polyamide composite material and preparation method |
| CN111411519A (en) * | 2020-03-27 | 2020-07-14 | 东华大学 | Early-warning type flame-retardant polylactic acid fabric and preparation method thereof |
| CN112030269A (en) * | 2020-09-04 | 2020-12-04 | 安徽瑜合警用装备有限公司 | Special lasting electric heating self-heating composite functional fiber material for military police and preparation method and application thereof |
| CN112457558A (en) * | 2020-12-08 | 2021-03-09 | 浩珂科技有限公司 | Graphene quantum dot modified polymer master batch for functional fibers and preparation method thereof |
| CN113493942A (en) * | 2020-04-03 | 2021-10-12 | 天津市职业大学 | Nanofiber material and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102409424A (en) * | 2011-12-13 | 2012-04-11 | 中原工学院 | Method for preparing bamboo charcoal and polyamide composite fibers by in situ polymerization |
| CN103215689A (en) * | 2013-05-09 | 2013-07-24 | 苏州大学 | Preparation method of graphene modified nylon 6 fiber |
| CN104963022A (en) * | 2015-07-07 | 2015-10-07 | 中国科学院重庆绿色智能技术研究院 | Preparation method and product of high-strength and high-modulus polyvinyl alcohol-graphene quantum dot compound fiber |
| CN105063796A (en) * | 2015-07-21 | 2015-11-18 | 中国科学院宁波材料技术与工程研究所 | High-molecular composite conductive fiber and preparation method thereof |
-
2015
- 2015-12-17 CN CN201510953236.1A patent/CN105463613B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102409424A (en) * | 2011-12-13 | 2012-04-11 | 中原工学院 | Method for preparing bamboo charcoal and polyamide composite fibers by in situ polymerization |
| CN103215689A (en) * | 2013-05-09 | 2013-07-24 | 苏州大学 | Preparation method of graphene modified nylon 6 fiber |
| CN104963022A (en) * | 2015-07-07 | 2015-10-07 | 中国科学院重庆绿色智能技术研究院 | Preparation method and product of high-strength and high-modulus polyvinyl alcohol-graphene quantum dot compound fiber |
| CN105063796A (en) * | 2015-07-21 | 2015-11-18 | 中国科学院宁波材料技术与工程研究所 | High-molecular composite conductive fiber and preparation method thereof |
Cited By (23)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106192192B (en) * | 2016-08-24 | 2017-04-12 | 福建省百凯经编实业有限公司 | Method for preparing patterned warp-knitted lace fabric |
| CN106192192A (en) * | 2016-08-24 | 2016-12-07 | 福建省百凯经编实业有限公司 | The preparation method of patterned tricot lace fabric |
| CN106435827A (en) * | 2016-09-21 | 2017-02-22 | 东莞市联洲知识产权运营管理有限公司 | Ceramic/resin/graphene quantum dot composite fibers and preparation method thereof |
| CN106435827B (en) * | 2016-09-21 | 2019-02-26 | 上海东北亚新纺织科技有限公司 | A kind of ceramics/resin/graphite alkene quantum dot composite fibre and preparation method thereof |
| CN106480532A (en) * | 2016-11-10 | 2017-03-08 | 过冬 | A kind of preparation method of Graphene reinforcing fiber |
| CN106675006A (en) * | 2017-01-05 | 2017-05-17 | 上海华峰超纤材料股份有限公司 | Conductive microfiber synthetic leather and production method thereof |
| CN108951177A (en) * | 2017-05-18 | 2018-12-07 | 安安(中国)有限公司 | A kind of processing method of the suede superfine fiber synthetic leather with higher scratch resistance wear-resisting property |
| CN107674385A (en) * | 2017-10-31 | 2018-02-09 | 西南石油大学 | A kind of preparation method of toughness reinforcing drop resistance carbon fibre composite |
| CN110511375A (en) * | 2018-05-22 | 2019-11-29 | 上海杰事杰新材料(集团)股份有限公司 | A kind of static resistant polyamide composite material and preparation method |
| CN109592670A (en) * | 2018-12-20 | 2019-04-09 | 湖北工程学院 | The dispersing method of single-walled carbon nanotube |
| CN109930188A (en) * | 2019-01-31 | 2019-06-25 | 山东金宝电子股份有限公司 | A method of holey copper is prepared based on conductive fiber |
| CN110230110A (en) * | 2019-07-09 | 2019-09-13 | 杭州高烯科技有限公司 | A kind of low cost, the terylene of antistatic and preparation method thereof |
| CN110306250A (en) * | 2019-07-09 | 2019-10-08 | 杭州高烯科技有限公司 | A kind of compound nylon fabric of long-acting antistatic and preparation method thereof |
| CN110359121A (en) * | 2019-07-09 | 2019-10-22 | 杭州高烯科技有限公司 | A kind of fire-resistant antistatic polyamide fibre and preparation method thereof |
| CN110230109A (en) * | 2019-07-09 | 2019-09-13 | 杭州高烯科技有限公司 | A kind of low cost, the polyamide fibre of antistatic and preparation method thereof |
| CN110230109B (en) * | 2019-07-09 | 2021-09-10 | 杭州高烯科技有限公司 | Low-cost antistatic chinlon and preparation method thereof |
| CN110306250B (en) * | 2019-07-09 | 2021-09-24 | 杭州高烯科技有限公司 | Long-acting anti-static composite nylon fabric and preparation method thereof |
| CN111411519A (en) * | 2020-03-27 | 2020-07-14 | 东华大学 | Early-warning type flame-retardant polylactic acid fabric and preparation method thereof |
| CN111411519B (en) * | 2020-03-27 | 2021-11-26 | 东华大学 | Early-warning type flame-retardant polylactic acid fabric and preparation method thereof |
| CN113493942A (en) * | 2020-04-03 | 2021-10-12 | 天津市职业大学 | Nanofiber material and preparation method thereof |
| CN112030269A (en) * | 2020-09-04 | 2020-12-04 | 安徽瑜合警用装备有限公司 | Special lasting electric heating self-heating composite functional fiber material for military police and preparation method and application thereof |
| CN112030269B (en) * | 2020-09-04 | 2023-02-03 | 安徽德和织造有限公司 | Special lasting electric heating self-heating composite functional fiber material for military police and preparation method and application thereof |
| CN112457558A (en) * | 2020-12-08 | 2021-03-09 | 浩珂科技有限公司 | Graphene quantum dot modified polymer master batch for functional fibers and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105463613B (en) | 2018-03-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105463613A (en) | Polyamide6-graphene quantum dot/carbon nanotube anti-static fiber and preparation | |
| Yang et al. | Recycling of high-value-added aramid nanofibers from waste aramid resources via a feasible and cost-effective approach | |
| US10106420B2 (en) | Method for manufacturing graphene fiber | |
| Du et al. | The present status and key problems of carbon nanotube based polymer composites | |
| Choudhary et al. | Polymer/carbon nanotube nanocomposites | |
| CN1226472C (en) | Conducting fiber containing nano car bon tube and its prepn. method | |
| CN102409421B (en) | Preparation method of carbon nanotubes/nano ATO (antimony tin oxide)/polypropylene electroconductive fibers | |
| Su et al. | Chain conformation, crystallization behavior, electrical and mechanical properties of electrospun polymer-carbon nanotube hybrid nanofibers with different orientations | |
| CN105463612A (en) | Graphene quantum dot reinforced polyarmide fiber and preparation method thereof | |
| WO2016127465A1 (en) | Preparation method for high-strength polyacrylonitrile nano composite fibres | |
| CN104672502B (en) | Cyanoethyl cellulose based high-dielectric flexible nano-composite film and preparation method thereof | |
| Xia et al. | Research on high electromagnetic interference shielding effectiveness of a foldable buckypaper/polyacrylonitrile composite film via interface reinforcing | |
| CN106968026A (en) | A kind of preparation method of graphene carbon black composite conducting fiber | |
| CN103046157B (en) | A kind of carbon nano tube/polyurethane/polypropylene conductive fiber and preparation method thereof | |
| CN109763210A (en) | The method that ionic liquid prepares cellulose base carbon fiber or carbon film | |
| CN103031617A (en) | Carbon nanotube/polyurethane/polyacrylonitrile composite conductive fiber and preparation method thereof | |
| CN106567157A (en) | Preparation method of graphene nanoribbon in situ toughened nano carbon fiber | |
| CN106012093A (en) | Preparation method of compound conductive fibers | |
| WO2017201987A1 (en) | Antistatic composite nanomaterial film and preparation method thereof | |
| CN106003934A (en) | Anti-static nanofiber non-woven material and preparation method | |
| Liu et al. | A review of multifunctional nanocomposite fibers: design, preparation and applications | |
| CN110284259B (en) | Composite thermoelectric thin film material and preparation method thereof | |
| CN103668616A (en) | Carbon nanotube modified polyvinyl akohol nano-fiber yarn and preparing method thereof | |
| Lee et al. | A review of high-performance carbon nanotube-based carbon fibers | |
| CN102604186B (en) | High-tenacity conducting nanocomposite material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20180309 Termination date: 20211217 |