CN111636114B - Preparation of high-strength high-conductivity polyvinyl alcohol/graphene composite fiber - Google Patents
Preparation of high-strength high-conductivity polyvinyl alcohol/graphene composite fiber Download PDFInfo
- Publication number
- CN111636114B CN111636114B CN202010534565.3A CN202010534565A CN111636114B CN 111636114 B CN111636114 B CN 111636114B CN 202010534565 A CN202010534565 A CN 202010534565A CN 111636114 B CN111636114 B CN 111636114B
- Authority
- CN
- China
- Prior art keywords
- bath
- polyvinyl alcohol
- graphene
- temperature
- fiber
- 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.)
- Active
Links
Images
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
- D01F6/44—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
- D01F6/50—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 polyalcohols, polyacetals or polyketals
-
- 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
- D01D10/00—Physical treatment of artificial filaments or the like during manufacture, i.e. during a continuous production process before the filaments have been collected
- D01D10/02—Heat treatment
-
- 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
- D01D10/00—Physical treatment of artificial filaments or the like during manufacture, i.e. during a continuous production process before the filaments have been collected
- D01D10/06—Washing or drying
-
- 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
- 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
- D01D5/12—Stretch-spinning methods
- D01D5/14—Stretch-spinning methods with flowing liquid or gaseous stretching media, e.g. solution-blowing
-
- 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
- D01D5/28—Formation of filaments, threads, or the like while mixing different spinning solutions or melts during the spinning operation; Spinnerette packs therefor
- D01D5/30—Conjugate filaments; Spinnerette packs therefor
-
- 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
Abstract
The invention relates to a preparation method of a high-strength high-conductivity polyvinyl alcohol/graphene composite fiber. The method comprises the following steps: preparing a spinning solution; preparing polyvinyl alcohol/graphene nascent composite fibers, and preparing polyvinyl alcohol/graphene composite fibers. The method realizes the continuous preparation of the high-conductivity polyvinyl alcohol/graphene composite fiber, and the prepared composite fiber has high conductivity and high strength.
Description
Technical Field
The invention belongs to the field of preparation of conductive composite materials, and particularly relates to a preparation method of a high-strength high-conductivity polyvinyl alcohol/graphene composite fiber.
Background
Graphene is a two-dimensional lamellar material composed of single atoms, and has excellent electric conduction and heat conduction properties. The composite filled conductive fiber material using graphene as conductive filler is widely researched and reported. However, the conductivity of the obtained conductive fiber is not high, and the bottleneck problems are mainly poor dispersibility and low addition concentration. Although the addition concentration is slightly improved after the treatment by adopting a chemical modification method, an in-situ polymerization method and the like, the addition concentration is far lower than that of the carbon black conductive composite material (about 40 percent). And the original SP of the modified graphene2The hybrid structure is destroyed and the intrinsic conductivity properties are lost significantly. Physical method for processing graphene (surface activation)Sex agent, etc.), although the addition amount is increased, the residue of the dispersion stabilizer influences the conductivity of the matrix, and meanwhile, the approach of improving the addition amount in a pure physical way leads the mechanical property of the material to become brittle, the modulus to be greatly increased, the serviceability and the knittability of the fiber are influenced, and the problem of pain in the industry is that the polymer/graphene composite fiber with high strength, high conductivity and high flexibility is prepared.
Disclosure of Invention
The invention aims to solve the technical problem of providing a preparation method of a high-strength high-conductivity polyvinyl alcohol/graphene composite fiber, so as to overcome the defect of low conductivity of a graphene conductive fiber in the prior art.
The invention provides a preparation method of polyvinyl alcohol/graphene composite fibers, which comprises the following steps:
(1) mixing the graphene dispersion liquid, PEDOT (polyethylene glycol oxide), namely PSS (Polyacrylonitrile) dispersion liquid, polyvinyl alcohol and water, defoaming, and standing to obtain a spinning solution, wherein the spinning solution comprises the following components in percentage by mass: 12-15% of polyvinyl alcohol, 1-4% of graphene, 1-4% of PEDOT, namely PSS, and 77-86% of water;
(2) extruding the spinning solution obtained in the step (1) from a spinneret plate, allowing the obtained nascent fiber to enter a first cross-linking coagulation bath, performing cross-linking coagulation, then entering a second coagulation bath for coagulation, then entering an acidolysis drafting bath for drafting, and then performing immersion bath, water washing bath, drying and winding to obtain a polyvinyl alcohol/graphene nascent composite fiber;
(3) and (3) carrying out constant-temperature crystallization on the polyvinyl alcohol/graphene nascent composite fiber in the step (2) on a constant-temperature hot roller pair by utilizing a fiber post-processing all-in-one machine to expand and grow the microcrystal, then carrying out dry-hot drawing on the hot roller pair to enable the molecular chain and the microcrystal orientation to induce the graphene sheet layer to be directionally arranged along an external force to construct a conductive network, and then relaxing and heat setting to eliminate internal stress and winding to obtain the polyvinyl alcohol/graphene composite fiber.
The mass percentage concentration of the graphene dispersion liquid in the step (1) is 0.8-1.5%. The graphene dispersion liquid is a water phase system.
In the step (1), the mass percentage concentration of the PEDOT to PSS dispersion liquid is 1-2 wt%; the polyvinyl alcohol is PVA-2099.
And (2) defoaming in the step (1) is carried out at normal temperature and under reduced pressure.
The aperture of the spinneret plate in the step (2) is 0.1-0.2mm, and preferably 0.15 mm.
The extrusion speed in the step (2) is 5-10 m/min.
The first crosslinking coagulation bath in the step (2) comprises the following components in percentage by mass: 25-30% Na2SO4，0.5-1％NaOH，69-74.5％H2O。
The components of the second coagulating bath in the step (2) are as follows: na with the mass percentage concentration of 25-30%2SO4An aqueous solution.
The temperature of the first cross-linking coagulation bath in the step (2) is 25-45 ℃.
The temperature of the second coagulation bath in the step (2) is 35-45 ℃; the draft multiple is 1-2 times.
The acidolysis drafting bath in the step (2) comprises the following components in percentage by mass: 25-27% Na2SO4，1-5％HCl，68-74％H2O。
The immersion bath in the step (2) comprises the following components in percentage by mass: 70-80% DMSO, 20-30% H2O。
And (3) the water bath in the step (2) is standard industrial tap water.
The temperature of the acidolysis drafting bath in the step (2) is 85-95 ℃.
The temperature of the immersion bath in the step (2) is 45-55 ℃, and the temperature of the water bath is room temperature.
The drying in the step (2) comprises the following steps: drying with hot air at 220 deg.C for 2 m.
The fiber post-processing integrated machine in the step (2) is wet spinning multifunctional post-processing integrated equipment disclosed by Chinese patent CN107687029A, the equipment comprises an integrated floor type rack, and a drying area, a drafting area and a shaping area are sequentially arranged on the rack from left to right; a tension frame and a yarn inlet channel are arranged on the left side wall of the drying area, a first channel is arranged on the side wall of the drying area adjacent to the drafting area, a second channel is arranged on the side wall of the drafting area adjacent to the shaping area, and a yarn outlet channel and an upper oiling wheel are arranged on the right side wall of the shaping area; the continuous two-stage tension cohesion drafting mode is arranged in the drafting zone, the drafting rollers are arranged in an isosceles triangle and are designed into a 2-3-2 combined structure, the two groups of stepped 0.4-0.45m long pair roller combined shaping mode are arranged in the shaping zone, and the drafting rollers are arranged in a stepped field shape.
The temperature of the constant-temperature hot roller pair in the step (3) is 190-210 ℃; the constant temperature crystallization time is 10-70 s.
The hot pair roller dry heat drafting multiple in the step (3) is 1-4 times; the shrinkage rate of the relaxation heat setting is controlled to be 0.1-1%.
The invention also provides the polyvinyl alcohol/graphene composite fiber prepared by the method.
The invention also provides an application of the polyvinyl alcohol/graphene composite fiber prepared by the method.
The invention realizes the continuous preparation of the composite fiber by utilizing a spinning technology of fractional solidification and multistage drafting (which is beneficial to the regulation and control of fiber micropores, a microfiber structure and a fiber skin-core structure and ensures that a stock solution trickle is quickly solidified into nascent fiber), and simultaneously realizes the preparation of the polyvinyl alcohol/graphene high-conductivity composite fiber by jointly constructing a conductive network in the fiber by utilizing the expansion and orientation of microcrystals in the fiber.
According to the invention, the polyvinyl alcohol/graphene composite fiber with high conductivity and high strength is continuously prepared by compounding graphene as a conductive modifier, an auxiliary conductive polymer as a conductive reinforcing agent and polyvinyl alcohol through a wet spinning technology by using Chinese-style large-scale equipment. According to the invention, through the design of a formula and a fiber forming process, microcrystals in the fiber are expanded and grown in the post-processing process and are oriented along the direction of an external force, and a conductive network in the fiber is constructed by the oriented graphene sheet layers, so that the monofilament conductivity of the fiber reaches 33.6s/m, the mechanical strength is 3.16-4.82cN/dtex, and the industrial textile requirements are met. The fiber downstream product has wide application in the fields of military electromagnetic shielding, civil electrostatic protection, intelligent clothing, wearable equipment and the like.
Advantageous effects
(1) The invention realizes the continuous preparation of the high-conductivity polyvinyl alcohol/graphene composite fiber, and the conductivity of the single fiber of the fiber is as high as 33.6S/m.
(2) The invention realizes high conductivity and high strength of the fiber, and the mechanical strength is 3.16-4.82 cN/dtex.
Drawings
Fig. 1(a) is a drawing of a filament of a polyvinyl alcohol/graphene conductive fiber prepared in a formula scale according to the present invention, (b) is a drawing of a conductivity of a polyvinyl alcohol/graphene conductive fiber fabric according to the present invention, and (c) is an optical photograph of a polyvinyl alcohol/graphene conductive fiber yarn according to the present invention.
Fig. 2 is a graph of the conductivity of the polyvinyl alcohol/graphene composite fiber prepared in example 1.
FIG. 3 is a schematic structural view of the fiber post-processing integrated machine of the present invention.
FIG. 4 is a cross-sectional view of the draft zone of the fiber finishing assembly of the present invention.
In the figure: 1. tension frame, 2 drying zone, 3 drafting zone, 4 sizing zone, 5 lifting door, 6 air outlet, 7 oil feeding wheel, 8 air inlet, 9 humidifier, 10 godet roller, 11 drafting roller, 12 sizing roller, 13 lifting door power motor, 14 balance weight, 15 fan, 16 heater, 17 lifting door guide wheel.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
Polyvinyl alcohol is purchased from Anhui vitamin, graphene is purchased from Heizhou sixth element, and other chemical reagents are purchased from national medicine reagents.
Example 1
(1) Preparation of spinning solution: adding a graphene dispersion liquid with the mass percentage concentration of 1%, a PEDOT/PSS dispersion liquid with the mass percentage concentration of 1.5 wt%, PVA-2099 and deionized water into a reaction kettle according to the proportion that the mass percentage composition is 14% of polyvinyl alcohol, 2.5% of graphene, 4% of PEDOT/PSS and 79.5% of water, uniformly dissolving, defoaming under reduced pressure at normal temperature, and standing for later use.
(2) Forming fibers: extruding the nascent fiber from a spinneret plate with the aperture of 0.15mm, wherein the extrusion speed is 8m/min, feeding the extruded stock solution trickle directly into a first cross-linking coagulation bath system with the temperature of 35 ℃, feeding the extruded stock solution trickle into a second coagulation bath system with the temperature of 40 ℃ after cross-linking coagulation, then feeding the extruded stock solution trickle into an acidolysis drafting bath system with the temperature of 90 ℃, drafting the spun stock solution by 1.2 times, and finally carrying out processes of dipping bath with the temperature of 50 ℃, normal-temperature water bath, drying, winding and the like to obtain the polyvinyl alcohol/graphene nascent composite fiber, wherein the drying condition in the drying process is 220 ℃ vertical hot air drying, and the drying stroke is 2 m.
(3) Post-processing of the fibers and perfecting of the conductive network: and (3) carrying out constant temperature crystallization on the nascent fiber on a constant temperature hot roller pair at the temperature of 200 ℃ by using a fiber post-processing all-in-one machine (shown in figures 3 and 4), wherein the constant temperature crystallization time is 60s, so that the microcrystal is expanded and grown. And then carrying out dry heat drafting on a hot pair roller, wherein the hot roller dry heat drafting is 1.5 times, so that the molecular chain and the microcrystal orientation induced graphene sheet layer are directionally arranged along an external force to construct a conductive network. Finally, after the relaxation heat setting, the shrinkage rate of the relaxation heat setting is controlled to be 0.5 percent, and the internal stress is eliminated. And winding the obtained product on a barrel to obtain the final conductive polyvinyl alcohol/graphene composite fiber for spinning.
Wherein the first cross-linking coagulation bath consists of 27 mass percent of Na2SO4，0.7％NaOH，72.3％H2And O. The second coagulating bath is composed of 27% by mass of Na2SO4An aqueous solution. The acidolysis drafting bath consists of 26 mass percent of Na2SO4、2％HCl、72％H2And O. The soaking bath comprises 75% of DMSO and 25% of H2And O. The water bath was standard industrial tap water and the conductivity of the resulting conductive fibers (tested using a broadband dielectric spectrometer model Concept 40, frequency range 10)-1Hz to 106Hz, relative humidity of 40% at 20 ℃) is 33.6S/m, the mechanical property is tested by an XS08XT-3 type carbon fiber strength tester, the holding distance is 10mm, and the stretching speed is 2 mm.min-1The mechanical strength was found to be 4.28 cN/dtex.
FIG. 1 shows that: the fiber forming process can realize the mass preparation of the conductive fiber filament, and the prepared filament has good weaving property and conductivity.
FIG. 2 shows that: the polyvinyl alcohol/graphene composite fiber has excellent conductivity, the conductivity test result is 33.6S/m, and the conductivity stability is good.
Example 2
(1) Adding the polyvinyl alcohol 12%, the graphene 1%, the PEDOT 1% and the water 86% into a reaction kettle according to the mass percentage, uniformly dissolving, and obtaining the spinning solution in the same way as the example 1 except that the mixture is dissolved uniformly.
(2) Forming fibers: extruding the nascent fiber from a spinneret plate with the aperture of 0.1mm, wherein the extrusion speed is 5m/min, feeding the extruded stock solution trickle directly into a first cross-linking coagulation bath system with the temperature of 25 ℃, feeding the extruded stock solution trickle into a second coagulation bath system with the temperature of 35 ℃ after cross-linking coagulation, then feeding the extruded stock solution trickle into an acidolysis drafting bath system with the temperature of 85 ℃, wherein the drafting multiple is 1.2 times, and finally obtaining the polyvinyl alcohol/graphene nascent composite fiber through processes of dipping bath with the temperature of 45 ℃, normal-temperature water bathing, drying, winding and the like, wherein the drying condition in the drying process is 220 ℃ vertical hot air drying, and the drying stroke is 2 m.
(3) Post-processing of the fibers and perfecting of the conductive network: and (3) carrying out constant temperature crystallization on the nascent fiber on a constant temperature hot roller at 190 ℃ by using a fiber post-processing all-in-one machine (as shown in figures 3 and 4), wherein the constant temperature crystallization time is 10s, so that the microcrystal is expanded and grown. And then carrying out dry heat drafting on a hot pair roller, wherein the hot roller is subjected to dry heat drafting by 1 time, so that the molecular chain and the microcrystal orientation induced graphene sheet layer are directionally arranged along an external force to construct a conductive network. Finally, after the relaxation heat setting, the shrinkage rate of the relaxation heat setting is controlled to be 0.1 percent, and the internal stress is eliminated. And winding the obtained product on a barrel to obtain the final conductive polyvinyl alcohol/graphene composite fiber for spinning.
Wherein the first crosslinking coagulation bath consists of Na with the mass percentage concentration of 25 percent2SO4，0.5％NaOH，74.5％H2And O. The second coagulating bath is composed of 25 wt% Na2SO4An aqueous solution. The acidolysis drafting bath consists of 25 percent of Na by mass percentage2SO4、1％HCl、74H2And O. The soaking bath comprises 70% of DMSO and 30% of H2And O. The water bath is standard industrial tap water, the conductivity of the obtained conductive fiber is 0.032S/m, the mechanical property of the conductive fiber is tested by an XS08XT-3 type carbon fiber strength tester, the holding distance is 10mm, the stretching speed is 2 mm.min-1The mechanical strength was found to be 4.01 cN/dtex.
Example 3
(1) Adding 15% of polyvinyl alcohol, 4% of graphene, 4% of PEDOT (PolyEthylenediamine terephthalate), and 77% of water into a reaction kettle according to the mass percentage for uniform dissolution, and obtaining the spinning solution in the same way as in the example 1 except for the above.
(2) Forming fibers: extruding the nascent fiber from a spinneret plate with the aperture of 0.2mm, wherein the extrusion speed is 10m/min, feeding the extruded stock solution trickle directly into a first cross-linking coagulation bath system with the temperature of 45 ℃, feeding the extruded stock solution trickle into a second coagulation bath system with the temperature of 45 ℃ after cross-linking coagulation, then feeding the extruded stock solution trickle into an acidolysis drafting bath system with the temperature of 95 ℃, wherein the drafting multiple is 1.2 times, and finally obtaining the polyvinyl alcohol/graphene nascent composite fiber through the processes of immersion bath with the temperature of 55 ℃, normal-temperature water bath, drying, winding and the like, wherein the drying condition in the drying process is 220 ℃ vertical hot air drying, and the drying stroke is 2 m.
(3) Post-processing of the fibers and perfecting of the conductive network: and (3) carrying out constant temperature crystallization on the nascent fiber on a constant temperature hot roller at 210 ℃ by using a fiber post-processing all-in-one machine (shown in figures 3 and 4), wherein the constant temperature crystallization time is 70s, so that the microcrystal is expanded and grown. And then carrying out dry heat drafting on a hot pair roller, wherein the hot roller is subjected to dry heat drafting by 4 times, so that the molecular chain and the microcrystal orientation induced graphene sheet layer are directionally arranged along an external force to construct a conductive network. And finally, after the relaxation heat setting, the shrinkage rate of the relaxation heat setting is controlled to be 1 percent, and the internal stress is eliminated. And winding the obtained product on a barrel to obtain the final conductive polyvinyl alcohol/graphene composite fiber for spinning.
Wherein the first crosslinking coagulating bath consists of Na with the mass percentage concentration of 30 percent2SO4，1％NaOH，69％H2O。The second coagulating bath is composed of Na with the mass percentage concentration of 30 percent2SO4An aqueous solution. The acidolysis drafting bath consists of 27 mass percent of Na2SO4、5％HCl、68H2And O. The soaking bath comprises 80% of DMSO and 20% of H2And O. The water bath is standard industrial tap water, the conductivity of the obtained conductive fiber is 5.23S/m, the mechanical property of the conductive fiber is tested by an XS08XT-3 type carbon fiber strength tester, the holding distance is 10mm, the stretching speed is 2 mm.min-1The mechanical strength was found to be 3.16 cN/dtex.
Claims (9)
1. A preparation method of polyvinyl alcohol/graphene composite fibers comprises the following steps:
(1) mixing the graphene dispersion liquid, PEDOT (polyethylene glycol oxide), namely PSS (Polyacrylonitrile) dispersion liquid, polyvinyl alcohol and water, defoaming, and standing to obtain a spinning solution, wherein the spinning solution comprises the following components in percentage by mass: 12-15% of polyvinyl alcohol, 1-4% of graphene, 1-4% of PEDOT, namely PSS, and 77-86% of water;
(2) extruding the spinning solution obtained in the step (1) from a spinneret plate, allowing the obtained nascent fiber to enter a first cross-linking coagulation bath, performing cross-linking coagulation, then entering a second coagulation bath for coagulation, then entering an acidolysis drafting bath for drafting, and then performing immersion bath, water washing bath, drying and winding to obtain the polyvinyl alcohol/graphene nascent composite fiber, wherein the first cross-linking coagulation bath comprises the following components in percentage by mass: 25-30% Na2SO4，0.5-1％NaOH，69-74.5％H2O; the components of the second coagulating bath are as follows: na with the mass percentage concentration of 25-30%2SO4The acidolysis drawing bath comprises the following components in percentage by mass: 25-27% Na2SO4，1-5％HCl，68-74％H2O；
(3) And (3) carrying out constant-temperature crystallization on the polyvinyl alcohol/graphene nascent composite fiber in the step (2) on a constant-temperature hot pair roller by using a fiber post-processing all-in-one machine, then carrying out dry-hot drawing on the hot pair roller, and then carrying out relaxation heat setting and winding to obtain the polyvinyl alcohol/graphene composite fiber.
2. The method according to claim 1, wherein the graphene dispersion liquid in the step (1) has a mass percentage concentration of 0.8-1.5%; the mass percentage concentration of the PEDOT and PSS dispersion liquid is 1-2 wt%; the polyvinyl alcohol is PVA-2099.
3. The method of claim 1, wherein the diameter of the spinneret hole in step (2) is 0.1-0.2 mm; the extrusion speed is 5-10 m/min.
4. The method according to claim 1, wherein the temperature of the first crosslinking coagulation bath in the step (2) is 25-45 ℃; the temperature of the second coagulation bath is 35-45 ℃; the draft multiple is 1-2 times.
5. The method according to claim 1, wherein the components of the immersion bath in the step (2) are as follows by mass percent: 70-80% DMSO, 20-30% H2O; the water bath was standard industrial tap water.
6. The method as claimed in claim 1, wherein the acid hydrolysis drawing bath temperature in the step (2) is 85-95 ℃; the temperature of the soaking bath is 45-55 ℃; the water bath temperature is room temperature.
7. The method as claimed in claim 1, wherein the constant temperature hot-rolling temperature in the step (3) is 190 ℃ to 210 ℃; the constant temperature crystallization time is 10-70s, and the hot-roller dry heat drafting multiple is 1-4 times; the shrinkage rate of the relaxation heat setting is controlled to be 0.1-1%.
8. A polyvinyl alcohol/graphene composite fiber prepared by the method of claim 1.
9. Use of the polyvinyl alcohol/graphene composite fiber prepared by the method according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010534565.3A CN111636114B (en) | 2020-06-12 | 2020-06-12 | Preparation of high-strength high-conductivity polyvinyl alcohol/graphene composite fiber |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010534565.3A CN111636114B (en) | 2020-06-12 | 2020-06-12 | Preparation of high-strength high-conductivity polyvinyl alcohol/graphene composite fiber |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111636114A CN111636114A (en) | 2020-09-08 |
| CN111636114B true CN111636114B (en) | 2021-08-31 |
Family
ID=72327582
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010534565.3A Active CN111636114B (en) | 2020-06-12 | 2020-06-12 | Preparation of high-strength high-conductivity polyvinyl alcohol/graphene composite fiber |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111636114B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113862853B (en) * | 2021-10-27 | 2022-09-02 | 内蒙古爱立特纺织股份有限公司 | Cashmere graphene blended yarn capable of preventing static reactance pilling and preparation process thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1197858A (en) * | 1998-04-14 | 1998-11-04 | 中国石油化工总公司 | Wet PVA-crosslinking spinning technology |
| CN103930612A (en) * | 2011-11-17 | 2014-07-16 | 日本电信电话株式会社 | Conductive polymer fibers, method and device for producing conductive polymer fibers, biological electrode,device for measuring biological signals, and implanted electrode |
| 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 |
| CN107687029A (en) * | 2017-09-13 | 2018-02-13 | 上海绪光纤维材料科技有限公司 | The multi-functional post processing integration apparatus of wet spinning and processing method |
| CN110565197A (en) * | 2019-09-20 | 2019-12-13 | 株洲时代新材料科技股份有限公司 | Preparation method of heterocyclic aramid 1313 fiber |
-
2020
- 2020-06-12 CN CN202010534565.3A patent/CN111636114B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1197858A (en) * | 1998-04-14 | 1998-11-04 | 中国石油化工总公司 | Wet PVA-crosslinking spinning technology |
| CN103930612A (en) * | 2011-11-17 | 2014-07-16 | 日本电信电话株式会社 | Conductive polymer fibers, method and device for producing conductive polymer fibers, biological electrode,device for measuring biological signals, and implanted electrode |
| 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 |
| CN107687029A (en) * | 2017-09-13 | 2018-02-13 | 上海绪光纤维材料科技有限公司 | The multi-functional post processing integration apparatus of wet spinning and processing method |
| CN110565197A (en) * | 2019-09-20 | 2019-12-13 | 株洲时代新材料科技股份有限公司 | Preparation method of heterocyclic aramid 1313 fiber |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111636114A (en) | 2020-09-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Zhuang et al. | Solution blowing of submicron-scale cellulose fibers | |
| CN107313126B (en) | Method for producing graphene modified polyamide-6 fiber through high-speed spinning | |
| US9476147B2 (en) | Gel spinning process for producing a pan-based precursor fiber | |
| CN107151835B (en) | A kind of Flexible graphene fiber and its continuous preparation method | |
| US9771669B2 (en) | Use, stabilization and carbonization of polyacrylonitrile/carbon composite fibers | |
| CN103882547B (en) | A kind of flat acrylic fiber and production method thereof | |
| CN101161880A (en) | Method for preparing polyacrylonitrile-based carbon fiber precursor fiber | |
| WO2016127833A1 (en) | Acetic nitrile fibre and preparation method therefor | |
| CN111636114B (en) | Preparation of high-strength high-conductivity polyvinyl alcohol/graphene composite fiber | |
| CN103526330B (en) | The preparation method of strain sensing nano fibre yarn | |
| WO2016060929A2 (en) | Use, stabilization and carbonization of polyacrylonitrile/carbon composite fibers | |
| Yan et al. | Structures and mechanical properties of plied and twisted polyacrylonitrile nanofiber yarns fabricated by a multi-needle electrospinning device | |
| US20140106167A1 (en) | Method for hybrid dry-jet gel spinning and fiber produced by that method | |
| KR20210052553A (en) | Elastic composite fiber and its manufacturing method | |
| CN113215669B (en) | Thermoplastic polyurethane fiber and manufacturing method thereof | |
| CN104562270A (en) | Wet spinning method for improving acrylic fiber glossiness | |
| CN1338011A (en) | Method for producing polyester-based combined filament yarn | |
| CN107723830A (en) | A kind of preparation method and application of high-tenacity graphene oxide grafting nylon fibre | |
| CN111560662A (en) | Preparation method of modified graphene PTT antistatic composite elastic fiber | |
| CN101906677B (en) | Preparation method of anti-ultraviolet aging polyphenylene benzodioxazole fiber | |
| CN108560079A (en) | From curling conductive fiber and preparation method thereof | |
| WO2012017453A1 (en) | High luster acrylic fiber and process for manufacturing the same | |
| CN107502972B (en) | Graphene in-situ polymerization modified polyamide 6 fully drawn yarn and preparation method thereof | |
| KR100713781B1 (en) | A process for preparing polyvinylalcohol yarn with high strength, and polyvinylalcohol yarn prepared therefrom | |
| CN110230137A (en) | A kind of organic carbon black conductive yarn and its preparation process |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20220707 Address after: Building 12a, Zilang science and Technology City, No. 60, Chongzhou Avenue, Nantong City, Jiangsu Province, 226000 Patentee after: Jiangsu Jicui advanced fiber material Research Institute Co.,Ltd. Address before: 201620 No. 2999 North Renmin Road, Songjiang new town, Songjiang District, Shanghai. Patentee before: DONGHUA University |