CN109972387B - Graphene grafted modified conductive fiber and preparation method and application thereof - Google Patents

Graphene grafted modified conductive fiber and preparation method and application thereof Download PDF

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CN109972387B
CN109972387B CN201711466211.4A CN201711466211A CN109972387B CN 109972387 B CN109972387 B CN 109972387B CN 201711466211 A CN201711466211 A CN 201711466211A CN 109972387 B CN109972387 B CN 109972387B
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fiber
fibers
graphene
graphene oxide
graft
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CN109972387A (en
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曲丽君
田明伟
朱士凤
赵洪涛
赵银桃
周珍卉
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Qingdao University
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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M10/00—Physical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. ultrasonic, corona discharge, irradiation, electric currents, or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements
    • D06M10/04—Physical treatment combined with treatment with chemical compounds or elements
    • D06M10/06—Inorganic compounds or elements
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/73—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof
    • D06M11/74—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof with carbon or graphite; with carbides; with graphitic acids or their salts
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
    • D06M13/12—Aldehydes; Ketones
    • D06M13/127—Mono-aldehydes, e.g. formaldehyde; Monoketones
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/02—Natural fibres, other than mineral fibres
    • D06M2101/04—Vegetal fibres
    • D06M2101/06—Vegetal fibres cellulosic
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/35—Abrasion, pilling or fibrillation resistance

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  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)

Abstract

The invention provides a graphene graft modified conductive fiber, which comprises a matrix fiber part, an activation aid part chemically bonded with the matrix fiber part and a graphene part chemically bonded with the activation aid part, wherein the resistivity of the graphene graft modified conductive fiber is increased by 0.1 to 2 percent after being washed with water for 20 times, and is increased by 0.1 to 5 percent after being rubbed on a YG522 type abrasion tester for 600 to 800 times according to ISO 5470-1-1999, so that the graphene graft modified conductive fiber has excellent water washing resistance, friction resistance and resistance stability. The invention also provides a method for preparing the graphene grafted modified conductive fiber. In addition, the invention also provides application of the graphene grafted modified conductive fiber in intelligent textiles, flexible sensors, electronic devices or electrothermal health-care textiles.

Description

Graphene grafted modified conductive fiber and preparation method and application thereof
Technical Field
The invention relates to a conductive fiber, a preparation method and application thereof, in particular to a graphene grafted modified conductive fiber, a preparation method and application thereof.
Background
In recent years, intelligent fibers and textiles are gradually becoming research hotspots, and conductive fibers are gradually becoming the leading materials of research as important components of signal transmission, sensing response and energy storage in intelligent textiles. The graphene is a carbon nano material with a two-dimensional nano structure, has outstanding performances of electrical conductivity, thermal conductivity, mechanical enhancement and the like, and has wide application prospects in the field of functional fibers.
The graphene conductive fiber is mainly prepared by a blending compounding method and a surface modification method, wherein the blending compounding method mainly comprises the steps of blending graphene and a polymer raw material and then spinning, but the graphene conductive fiber usually needs higher content of graphene, and the obtained fiber has higher resistance and unsatisfactory mechanical properties. The surface modification is to graft graphene oxide on the surface of a common fiber, and then to prepare the graphene conductive composite fiber by reducing the graphene oxide.
For example, in a preparation method (CN103966844A) of a graphene conductive composite fiber, a silane coupling agent is selected to pretreat the fiber, and solution reduction is performed after graphene oxide is grafted. A preparation method (CN102619080A) of a graphene-coated polyacrylonitrile fiber composite material comprises the steps of coating polyacrylonitrile fibers by multilayer graphene oxide, and then reducing by hydrazine hydrate to prepare graphene conductive fibers. However, in the above surface modification method, there are still problems of low grafting ratio, poor interfacial adhesion, poor water washing resistance, poor abrasion resistance, and the like of the graphene-modified fiber.
Therefore, there is still a need in the art for graphene graft-modified conductive fibers having improved grafting rate, wash resistance, and abrasion resistance, and corresponding methods of preparation.
Disclosure of Invention
The invention aims to provide a graphene grafted modified conductive fiber with improved grafting rate, washing resistance, friction resistance and resistance stability and a preparation method thereof, so as to overcome the defects in the prior art.
According to an aspect of the present invention, there is provided a graphene graft-modified conductive fiber comprising: a base fiber portion having one or more functional groups selected from the group consisting of a hydroxyl group, a carboxyl group, an amino group, an isocyanate group, an acid halide group on the surface; an activation aid portion chemically bonded to the base fiber portion and containing a plurality of groups reactive with the functional groups on the surface of the base fiber portion; and a graphene part grafted on the base fiber via chemical bonding with the coagent part, wherein the graphene graft-modified conductive fiber increases the resistivity by 0.1% to 2% after being washed with water 20 times, and increases the resistivity by 0.1% to 5% after being rubbed on a model YG522 abrasion tester 600 times to 800 times according to ISO 5470-1-1999.
In one embodiment, the matrix fiber portion is selected from one or more of the group consisting of: polysaccharide fibers, for example, cotton fibers, absorbent cotton fibers, hemp fibers, flax fibers, ramie fibers, jute fibers, apocynum venetum fibers, flax fibers, viscose fibers, cuprammonium fibers, acetate fibers, alginate fibers, chitosan fibers, sodium alginate fibers, tencel, modal fibers, and tianzhu; and chemical fibers containing the functional group, for example, polyvinyl alcohol fibers, acrylic fibers, polyurethane fibers, polylactic acid fibers, polyacrylonitrile fibers.
In one embodiment, the coagent moiety is derived from a coagent comprising a functional group selected from one or more of a hydroxyl group, a carboxyl group, an amino group, an isocyanate group, an acid halide group, preferably the coagent is selected from one or more of the group consisting of: dopamine, polydopamine, chitosan, sodium alginate, polylactic acid, polyacrylic acid, glutamic tetraacetic acid, ascorbic acid, ethylene diamine tetraacetic acid, polyvinyl alcohol, polyethylene glycol, polypropylene glycol, hydroxypropyl methylcellulose, pentaerythritol, triethylene tetramine, tetraethylene pentamine, melamine, spermine, trimesoyl chloride.
In one embodiment, the graphene graft-modified conductive fiber has a size of 1 × 101Omega m to 1X 105Resistivity of Ω · m and far infrared emissivity of 80% to 95%; and/or wherein the resistivity of the graphene graft modified conductive fibers increases by 0.2% to 1.8%, 0.3% to 1.6%, 0.4% to 1.4%, 0.6% to 1.2%, or 0.8% to 1.0% after washing with water 20 times; and/or the graphene graft modified conductive fiber increases in resistivity by 0.2% to 4.5%, 0.3% to 4.0%, 0.4% to 3.5%, 0.6% to 3.0%, 0.8% to 2.5%, or 1.0% to 800 times after being rubbed 600 times, 700 times, or 800 times on a YG522 type abrasion tester according to ISO 5470-1-19992.0％。
According to another aspect of the present invention, there is provided a method of preparing a graphene graft-modified conductive fiber, the method including: putting the matrix fiber in a polar organic solvent or a water solution thereof for ultrasonic oscillation treatment, and then taking out and drying to obtain a pretreated fiber; chemically bonding a co-agent on the surface of the pre-treated fiber to obtain an activated fiber; preparing graphene oxide into a solution and grafting the graphene oxide onto the activated fiber through chemical bonding with the activating auxiliary agent to obtain a graphene oxide graft-modified fiber; and reducing the graphene oxide graft modification fiber to obtain the graphene graft modification conductive fiber.
In one embodiment, the polar organic solvent is selected from one or more of the group consisting of: ethanol, isopropanol, methyl ethyl ketone, acetone, 1, 4-butanediol and ethylene glycol butyl ether; wherein the weight ratio of the base fiber to the polar organic solvent or aqueous solution thereof is any one selected from the group consisting of: 1:20 to 1:110, 1:30 to 1:100, 1:40 to 1:90, 1:50 to 1:80, 1:60 to 1: 70.
In one embodiment, the activation aid is chemically bonded to the pretreated fiber in the form of a solution, and the concentration of the solution of the activation aid is any one selected from the group consisting of: 0.05 to 12 wt%, 0.1 to 10 wt%, 0.2 to 9 wt%, 0.3 to 8 wt%, 0.4 to 7 wt%, 0.5 to 6 wt%, 0.6 to 5 wt%, 0.7 to 4 wt%, 0.8 to 3 wt%, 0.9 to 2 wt%, 1 to 1.8 wt%.
In one embodiment, the concentration of the solution of graphene oxide is any one selected from the group consisting of: 0.05mg/mL to 110mg/mL, 0.1mg/mL to 100mg/mL, 0.2 mg/mL to 90 mg/mL, 0.4 mg/mL to 80 mg/mL, 0.8 mg/mL to 70 mg/mL, 1.0 mg/mL to 60 mg/mL, 2.0mg/mL to 50 mg/mL, 4.0mg/mL to 40 mg/mL, 8.0 mg/mL to 30 mg/mL, 10.0 mg/mL to 20 mg/mL.
In one embodiment, the process of reducing the graphene oxide graft-modified fiber comprises solution reduction, high-pressure thermal reduction, microwave irradiation reduction, or a combination thereof, wherein the solution reduction comprises reduction using a solution of a reducing agent, and the reducing agent is one or more selected from the group consisting of: hydrazine compounds such as hydrazine hydrate, dimethylhydrazine, phenylhydrazine or p-methylsulfonylhydrazine; metal hydrides such as sodium borohydride, lithium aluminum hydride; active metals, such as aluminum, zinc, iron; reducing acids, such as ascorbic acid, pyrogallic acid; reducing phenols, such as p-diphenol, tea polyphenols; reducing sugars, such as glucose, fructose, sucrose; basic compounds, for example, sodium hydroxide, potassium hydroxide, sodium bicarbonate, ammonia; iodides, such as potassium iodide, ammonium iodide, sodium iodide, ferrous iodide.
According to another aspect of the invention, the application of the graphene grafted modified conductive fiber in intelligent textiles, flexible sensors, electronic devices or electrothermal health textiles is provided
Drawings
FIG. 1 shows an electron microscope image of the base fiber before graft modification.
FIG. 2 shows an electron microscope image of the base fiber after graft modification.
Detailed Description
For the purposes of the following detailed description, it is to be understood that the embodiments provided herein may assume various alternative variations and step sequences, except where expressly specified to the contrary. Furthermore, other than in the operating examples, or where otherwise indicated, all numbers expressing quantities of ingredients used in the specification and claims are to be understood as being modified by the term "about" which refers to variables having a value of ± 10%, ± 5% or ± 3% of the respective value so modified. Accordingly, unless indicated otherwise, the numerical parameters set forth in the specification and attached claims are approximations that may vary depending upon the desired properties to be obtained by the present invention. Each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques.
Moreover, it should be understood that any numerical range recited herein is intended to include all sub-ranges subsumed therein. For example, "1 to 10" is intended to include all sub-ranges between the recited minimum value of 1 and the recited maximum value of 10 (and includes both the endpoints of 1 and 10), such as 1 to 5, 2 to 8, or 4 to 6, and the like.
The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting. "or" means "and/or". As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
According to a first aspect of the present invention, there is provided a graphene graft-modified conductive fiber, which may include: a base fiber portion which may have one or more functional groups selected from hydroxyl group, carboxyl group, amino group, isocyanate group, acid halide group on the surface; an activation aid portion chemically bonded to the base fiber portion and may contain a plurality of groups reactive with the functional groups on the surface of the base fiber portion; and a graphene part which may be grafted on the base fiber via chemical bonding with the co-agent, wherein the graphene graft-modified conductive fiber increases the resistivity by 0.1% to 2% after being washed with water 20 times, and increases the resistivity by 0.1% to 5% after being rubbed on a model YG522 abrasion tester 600 times to 800 times according to ISO 5470-1-1999.
In one embodiment, the graphene graft-modified conductive fibers may also include other additive moieties, such as abrasion resistance agents, colorants, pigments, matting agents, flame retardants, wetting agents, and the like.
In one embodiment, the base fiber portion may be polysaccharide fibers, chemical fibers containing the functional groups, or a combination thereof. In particular embodiments, the matrix fiber portion may be a polysaccharide fiber, such as cotton fiber, absorbent cotton fiber, hemp fiber, flax fiber, ramie fiber, jute fiber, apocynum fiber, flax fiber, viscose fiber, cuprammonium fiber, acetate fiber, alginate fiber, chitosan fiber, sodium alginate fiber, tencel, modal, and bamboo. In another particular embodiment, the matrix fiber portion may be a chemical fiber containing the functional group, for example, a polyvinyl alcohol fiber, an acrylic fiber, a polyurethane fiber, a polylactic acid fiber, a polyacrylonitrile fiber. In a further specific embodiment, the matrix fiber may be one or more of cotton fiber, viscose fiber, hemp fiber, polylactic acid fiber, chitosan fiber, sodium alginate fiber, so as to modify the matrix fiber by chemical modification.
In one embodiment, the co-activator may be derived from a co-activator comprising a functional group selected from one or more of a hydroxyl group, a carboxyl group, an amino group, an isocyanate group, an acid halide group. In another embodiment, the activation aid may be selected from one or more of the group consisting of: dopamine, polydopamine, chitosan, sodium alginate, polylactic acid, polyacrylic acid, glutamic acid tetraacetic acid, ascorbic acid, ethylene diamine tetraacetic acid, polyvinyl alcohol, polyethylene glycol, polypropylene glycol, hydroxypropyl methylcellulose, pentaerythritol, triethylenetetramine, tetraethylenepentamine, melamine, spermine, trimesoyl chloride. Preferably, in particular embodiments, the activation aid may be selected from one or more of the group consisting of: dopamine, polydopamine, chitosan, sodium alginate and polylactic acid. In a further specific embodiment, the activation aid may be polydopamine, such that there are multiple bonding sites with the functional groups on the matrix fiber portion to increase the robustness of the bond.
In one embodiment, the graphene graft-modified conductive fiber may have a resistivity of 1 × 101Omega m to 1X 105Ω·m、2×101Omega m to 8 x 104Ω·m、4×101Omega m to 6X 104Ω·m、6×101Omega m to 4X 104Ω·m、8×101Omega m to 2X 104Ω·m、1×102Omega m to 8 x 103Ω·m、2×102Omega m to 6X 103Ω·m、4×102Omega m to 4X 103Ω·m、8×102Omega m to 2X 103Omega.m. In a particular locationIn an embodiment, the graphene graft-modified conductive fiber may have a resistivity of 1 × 101Omega m to 1X 104Omega m or 1X 102Omega m to 1X 103Omega.m. In a further specific embodiment, the graphene graft-modified conductive fiber may have a resistivity of 1 × 101Omega m to 1X 102Omega m, therefore, the graphene grafted and modified conductive fiber shows good conductivity.
In another embodiment, the resistivity of the graphene graft-modified conductive fibers may increase by 0.1% to 2%, 0.2% to 1.8%, 0.3% to 1.6%, 0.4% to 1.4%, 0.6% to 1.2%, or 0.8% to 1.0% after 20 times of water washing. In particular embodiments, the resistivity of the graphene graft-modified conductive fiber may be increased by 1% to 2% or 0.5% to 1.5% after 20 times of water washing, and thus, the graphene graft-modified conductive fiber exhibits excellent wash resistance. In another embodiment, the resistivity of the graphene graft modified conductive fibers may increase by 0.1% to 5%, 0.2% to 4.5%, 0.3% to 4.0%, 0.4% to 3.5%, 0.6% to 3.0%, 0.8% to 2.5%, or 1.0% to 2.0% after 600, 700, or 800 rubs on a YG 522-type abrasion tester according to ISO 5470-1-1999. In particular embodiments, the resistivity of the graphene graft-modified conductive fibers may increase by 2% to 4.5%, 2.5% to 4.0%, or 3.0% to 3.5% after 600 rubs on a YG 522-type abrasion tester according to ISO 5470-1-1999, whereby the graphene graft-modified conductive fibers exhibit excellent rub resistance. In another particular embodiment, the resistivity of the graphene graft-modified conductive fibers may increase by 1.5% to 4.5%, 2.0% to 4.0%, or 3.0% to 3.5% after 700 rubs on a YG 522-type abrasion tester according to ISO 5470-1-1999. In another particular embodiment, the resistivity of the graphene graft-modified conductive fibers may increase by 2.5% to 5.0%, 3.0% to 4.5%, or 3.5% to 4.0% after 800 rubs on a YG 522-type abrasion tester according to ISO 5470-1-1999.
In one embodiment, the graphene graft-modified conductive fiber may have a far infrared emissivity of 80% to 95%, 81% to 94%, 82% to 93%, 83% to 92%, 84% to 91%, 85% to 90%, 86% to 89%, 87% to 88%. In particular embodiments, the graphene graft-modified conductive fiber may have a far infrared emissivity of 85% to 93%, 87% to 92%, or 88% to 90%, whereby the graphene graft-modified conductive fiber exhibits a good insulation effect.
According to a second aspect of the present invention, there is provided a method for preparing a graphene graft-modified conductive fiber, the method comprising: putting the matrix fiber in a polar organic solvent or a water solution thereof for ultrasonic oscillation treatment, and then taking out and drying to obtain a pretreated fiber; chemically bonding a co-agent on the surface of the pre-treated fiber to obtain an activated fiber; preparing graphene oxide into a solution and grafting the graphene oxide onto the activated fiber through chemical bonding with the activating auxiliary agent to obtain a graphene oxide graft-modified fiber; and reducing the graphene oxide graft modification fiber to obtain the graphene graft modification conductive fiber.
In one embodiment, the base fiber may employ the base fiber portion according to the first aspect; and/or the activating auxiliary may employ the activating auxiliary according to the first aspect.
In one embodiment, the polar organic solvent may be selected from one or more of the group consisting of: ethanol, isopropanol, methyl ethyl ketone, acetone, 1, 4-butanediol, ethylene glycol butyl ether and the like, wherein the polar organic solvent removes grease or sizing agents on the surface of the matrix fiber and permeates into the fiber to reduce the regularity and crystallinity of a molecular chain, so that more functional groups are released from the interior of the fiber, thereby facilitating further activation. In particular embodiments, the polar organic solvent may be selected from isopropanol or acetone. In a further particular embodiment, the polar organic solvent may be acetone.
In one embodiment, the base fibers may be placed in a polar organic solvent or an aqueous solution thereof in a weight ratio, wherein the weight ratio of the base fibers to the polar organic solvent or the aqueous solution thereof may be any one selected from the group consisting of: 1:20 to 1:110, 1:30 to 1:100, 1:40 to 1:90, 1:50 to 1:80, 1:60 to 1: 70. In another embodiment, the weight ratio of the base fiber to the polar organic solvent or aqueous solution thereof may be 1:30 to 1:50 or 1:60 to 1: 100. In particular embodiments, the weight ratio of the base fibers to the polar organic solvent or aqueous solution thereof may be from 1:30 to 1:50, from 1:35 to 1:45, or from 1:38 to 1:40, such that the polar organic solvent or aqueous solution thereof effectively pretreats the base fibers.
In one embodiment, the matrix fiber may be continuously sonicated in the polar organic solvent or aqueous solution thereof for 5 minutes to 110 minutes, 10 minutes to 100 minutes, 20 minutes to 90 minutes, 30 minutes to 80 minutes, 40 minutes to 70 minutes, or 50 minutes to 60 minutes. In particular embodiments, the time of the sonication may be from 10 minutes to 60 minutes, from 20 minutes to 50 minutes, or from 30 minutes to 40 minutes to rapidly and sufficiently facilitate the pre-treatment effect of the polar organic solvent or aqueous solution thereof on the base fibers.
In one embodiment, the ultrasonically treated base fiber may be dried at a temperature of 40 ℃ to 110 ℃, 50 ℃ to 100 ℃, 60 ℃ to 90 ℃, 70 ℃ to 80 ℃. In particular embodiments, the temperature of the drying may be from 50 ℃ to 100 ℃ or from 60 ℃ to 80 ℃. In further particular embodiments, the temperature of the drying may be 50 ℃ to 80 ℃ or 60 ℃ to 100 ℃ to promote more, faster access of the polar organic solvent or aqueous solution thereof to the interior of the fiber, so that functional groups within the fiber are released.
In one embodiment, the activation aid is chemically bonded to the surface of the pretreated fiber in solution, wherein the concentration of the solution of the activation aid may be any one selected from the group consisting of: 0.05 to 12 wt%, 0.1 to 10 wt%, 0.2 to 9 wt%, 0.3 to 8 wt%, 0.4 to 7 wt%, 0.5 to 6 wt%, 0.6 to 5 wt%, 0.7 to 4 wt%, 0.8 to 3 wt%, 0.9 to 2 wt%, 1 to 1.8 wt%. In particular embodiments, the concentration of the solution of the activation aid may be 0.1 wt% to 2.0 wt%, 0.15 wt% to 1.5 wt%, or 0.2 wt% to 1.0 wt%, or 0.3 wt% to 0.5 wt%. In further particular embodiments, the solution of the co-agent may be at a concentration of 0.1 wt.% to 1.0 wt.%, 0.15 wt.% to 0.8 wt.%, 0.2 wt.% to 0.6 wt.%, or 0.3 wt.% to 0.5 wt.% such that the co-agent, when contacted with the pre-treated fiber, causes the functional groups on the surface of the fiber to chemically bond sufficiently with the co-agent to securely attach the co-agent.
In one embodiment, the pre-treated fibers may be activated by soaking in a co-agent solution by a soaking process at a weight ratio, which may be any one selected from the group consisting of: 1:20 to 1:110, 1:30 to 1:100, 1:40 to 1:90, 1:50 to 1:80, 1:60 to 1: 70. In particular embodiments, the weight ratio of the pretreated fiber to the coagent solution may be from 1:30 to 1:80, from 1:40 to 1: 60. In another particular embodiment, the weight ratio of the pretreated fiber to the coagent solution may be from 1:30 to 1: 50. In a further specific embodiment, the weight ratio of the pretreated fiber to the activator solution may be 1:30 to allow sufficient groups in the activator to chemically bond to the functional groups on the surface of the pretreated fiber and leave unbound groups available for further processing.
In another embodiment, the pretreated fiber can be placed in a coagent solution for 2 minutes to 110 minutes, 5 minutes to 100 minutes, 10 minutes to 90 minutes, 20 minutes to 80 minutes, 30 minutes to 70 minutes, or 40 minutes to 60 minutes. In particular embodiments, the pre-treated fiber may be wetted in the co-agent solution for a time period of 10 minutes to 60 minutes, 20 minutes to 50 minutes, 30 minutes to 40 minutes. In a further specific embodiment, the pre-treated fiber may be wetted in the solution of the co-agent for a time period of 10 minutes to 40 minutes to allow the groups in the co-agent to sufficiently chemically bond with the functional groups on the surface of the pre-treated fiber.
In one embodiment, the coagent solution may be uniformly coated on the pretreated fiber surface for activation by a coating process, which may include high pressure spraying, air spraying, thermal spraying, or atomized spraying. Preferably, the coating process may be a high pressure spray process. In another embodiment, the spray pressure of the high pressure spray process may be any one selected from the group consisting of: 0.1 to 10 bar, 0.2 to 8 bar, 0.3 to 8 bar, 0.4 to 7 bar, 0.5 to 6 bar, 0.6 to 5 bar, 0.8 to 4 bar, 0.9 to 3bar, 1 to 2 bar. In particular embodiments, the spray pressure of the high pressure spray process may be from 1 bar to 5 bar or from 2 bar to 4 bar. In a further particular embodiment, the spray pressure of the high pressure spray process may be from 1 bar to 3 bar.
In yet another embodiment, the spray amount of the high pressure spray process may be any one selected from the group consisting of: 5 mL/min to 600 mL/min, 10 mL/min to 550mL/min, 20 mL/min to 500 mL/min, 30 mL/min to 450 mL/min, 40mL/min to 400 mL/min, 50mL/min to 350 mL/min, 60 mL/min to 300mL/min, 70 mL/min to 250 mL/min, 80 mL/min to 200 mL/min, 90mL/min to 150 mL/min, 100 mL/min to 120 mL/min. In particular embodiments, the spray volume of the high pressure spray process can be 200 mL/min to 600 mL/min, 250 mL/min to 550mL/min, 300mL/min to 500 mL/min, 350 mL/min to 450 mL/min. In further particular embodiments, the high pressure spray process may be sprayed at an amount of 300 to 600 mL/min, 350 to 400 mL/min to ensure that the amount of activating aid is sufficient to activate the pretreated fiber.
In one embodiment, graphene oxide may be obtained by hummer's oxidation, and may have a thickness of 1 to 5 layers, 2 to 4 layers, or 3 to 5 layers, and a planar size of any one selected from the group consisting of: 1 μm to 200 μm, 2 μm to 190 μm, 3 μm to 180 μm, 4 μm to 170 μm, 5 μm to 160 μm, 6 μm to 150 μm, 7 μm to 140 μm, 8 μm to 130 μm, 9 μm to 120 μm, 10 μm to 110 μm, 20 μm to 100 μm, 30 μm to 90 μm, 40 μm to 80 μm, 50 μm to 70 μm. In particular embodiments, the graphene oxide may have a thickness of 1 to 3 layers. In a further particular embodiment, the graphene oxide may be 1 layer thick. In yet another embodiment, the planar size of the graphene oxide may be 20 to 120 μm, 40 to 100 μm, or 50 to 80 μm, so that the graphene oxide is uniformly dispersed in a medium for grafting.
In one embodiment, graphene oxide may be configured in a medium as a solution and then grafted on the surface of the activated fiber through a soaking process to rapidly and uniformly graft graphene oxide on the surface of the fiber, wherein the soaking process is to soak the activated fiber in the graphene oxide solution, wherein the weight ratio of the activated fiber to the graphene oxide solution may be any one selected from the group consisting of: 1:20 to 110, 1:30 to 1:100, 1:40 to 1:90, 1:50 to 1:80, 1:60 to 1: 70. In particular embodiments, the weight ratio of the activated fibers to the graphene oxide solution may be 1:30 to 1:80, 1:40 to 1:70, or 1:50 to 1: 60. In further particular embodiments, the weight ratio of the activated fibers to the graphene oxide solution may be from 1:30 to 1:60 or from 1:40 to 1:50 to ensure adequate grafting of graphene oxide on the activated fiber surface.
In another embodiment, the medium may be one or more selected from the group consisting of: ethanol, water, methanol, tetrahydrofuran, dimethyl sulfoxide, N-methyl pyrrolidone and ethylene glycol, so that the graphene oxide is better dispersed in the graphene oxide. In particular embodiments, the medium may be ethanol, water, methanol, tetrahydrofuran. In a further particular embodiment, the medium may be water.
In another embodiment, the graphene oxide solution infiltrated with activated fibers may be sonicated for 1 to 60 minutes, 5 to 55 minutes, 10 to 50 minutes, 15 to 45 minutes, 20 to 40 minutes, 25 to 35 minutes, or 28 to 30 minutes. In particular embodiments, the graphene oxide solution infiltrated with activated fibers may be sonicated for 10 minutes to 40 minutes or 20 minutes to 30 minutes. In another specific embodiment, the graphene oxide solution soaked with the activated fibers is treated with ultrasonic vibration for 10 to 40 minutes to ensure that the graphene oxide is uniformly dispersed in the medium and the activated fibers are sufficiently graft-modified.
In one embodiment, the graphene oxide solution infiltrated with activated fibers may be stirred for 0.5 to 65 minutes, 1 to 60 minutes, 2 to 55 minutes, 4 to 50 minutes, 6 to 45 minutes, 8 to 40 minutes, 10 to 35 minutes, 12 to 30 minutes, 14 to 25 minutes, or 16 to 20 minutes. In particular embodiments, the stirring time of the graphene oxide solution impregnated with the activated fibers may be 10 to 40 minutes or 20 to 30 minutes, so that the fibers are always in a moving and dispersed state during the grafting process.
In one embodiment, the temperature of the graphene oxide solution impregnated with the activated fiber may be controlled to be 30 ℃ to 110 ℃, 40 ℃ to 100 ℃, 45 ℃ to 95 ℃, 50 ℃ to 90 ℃, 55 ℃ to 85 ℃, 60 ℃ to 80 ℃, or 65 ℃ to 75 ℃. In particular embodiments, the temperature may be from 50 ℃ to 80 ℃ or from 60 ℃ to 70 ℃. In a further particular embodiment, the temperature may be between 50 ℃ and 60 ℃ in order to advantageously promote rapid grafting of graphene oxide to the activated fibers.
In one embodiment, the graphene oxide solution may be uniformly coated on the surface of the activated fiber by a coating process, which may include high pressure spraying, air spraying, thermal spraying, or atomized spraying, to graft the graphene oxide on the surface of the fiber. In another embodiment, the spray pressure of the high pressure spray process is the spray pressure of the first aspect; and/or the amount of spray from the high pressure spray process is the amount of spray from the first aspect.
In one embodiment, the concentration of the graphene oxide solution used for the wetting process or the coating process may be any one selected from the group consisting of: 0.05mg/mL to 110mg/mL, 0.1mg/mL to 100mg/mL, 0.2 mg/mL to 90 mg/mL, 0.4 mg/mL to 80 mg/mL, 0.8 mg/mL to 70 mg/mL, 1.0 mg/mL to 60 mg/mL, 2.0mg/mL to 50 mg/mL, 4.0mg/mL to 40 mg/mL, 8.0 mg/mL to 30 mg/mL, 10.0 mg/mL to 20 mg/mL. In particular embodiments, the graphene oxide solution may have a concentration of 0.1mg/mL to 0.5 mg/mL or 0.2 mg/mL to 0.3 mg/mL. In further particular embodiments, the graphene oxide solution may have a concentration of 0.1mg/mL to 0.3 mg/mL to facilitate uniform dispersion of the graphene oxide in the solution.
In one embodiment, the prepared graphene oxide solution may be sonicated at a power of 10W to 1000W, 20W to 900W, 40W to 800W, 80W to 700W, 100W to 600W, 200W to 500W, or 300W to 400W, and stirred at a speed of 10 rpm to 1000 rpm, 20 rpm to 900 rpm, 40 rpm to 800 rpm, 80 rpm to 700 rpm, 100 rpm to 600 rpm, 200 rpm to 500 rpm, or 300 rpm to 400 rpm. In particular embodiments, the power of the ultrasound may be 400W to 1000W, 500W to 900W, or 600W to 800W. In a further specific embodiment, the power of the ultrasound may be 600W to 800W. In yet another embodiment, the speed of the agitation may be from 500 rpm to 800 rpm.
In one embodiment, the process in which the graphene oxide graft-modified fiber is reduced may include solution reduction, high-pressure thermal reduction, microwave irradiation reduction, or a combination thereof. In particular embodiments, the process of reduction may be high pressure thermal reduction, microwave irradiation reduction, or a combination thereof. In another embodiment, the graphene oxide graft-modified fiber may be subjected to a reduction treatment using solution reduction in which the graphene oxide graft-modified fiber is immersed in a solution of a reducing agent to obtain the graphene graft-modified conductive fiber, and the weight ratio of the graphene oxide graft-modified fiber to the solution of the reducing agent may be any one selected from the group consisting of: 1:5 to 1:110, 1:10 to 1:100, 1:20 to 1:90, 1:30 to 1:80, 1:40 to 1:70, 1:50 to 1:60, to sufficiently reduce the graphene oxide on the graft-modified fiber. In particular embodiments, the weight ratio of the graphene oxide graft-modified fiber to the solution of the reducing agent may be 1:20 to 1:60, 1:30 to 1:50, or 1:40 to 1: 45.
In yet another embodiment, the concentration of the solution of the reducing agent may be any one selected from the group consisting of: 0.05 to 6 wt%, 0.1 to 5 wt%, 0.2 to 4 wt%, 0.4 to 3 wt%, 0.6 to 2 wt%, 0.8 to 1 wt%. In particular embodiments, the concentration of the solution of the reducing agent may be 1 to 10 wt.%, 2 to 8 wt.%, or 4 to 6 wt.%. In yet another embodiment, the graphene oxide graft-modified fiber immersed in the reducing agent solution is reduced at a temperature of 60 ℃ to 140 ℃, 70 ℃ to 130 ℃, 80 ℃ to 120 ℃, 85 ℃ to 115 ℃, 90 ℃ to 110 ℃, 95 ℃ to 100 ℃ for a reduction time of 1 hour to 10 hours, 2 hours to 8 hours, 3 hours to 6 hours. In particular embodiments, the temperature of the reduction is from 60 ℃ to 120 ℃ or from 80 ℃ to 100 ℃. In another embodiment, the reduction time is from 2 hours to 6 hours or from 3 hours to 4 hours.
In yet another embodiment, the reducing agent may be one or more selected from the group consisting of: hydrazine compounds such as hydrazine hydrate, dimethylhydrazine, phenylhydrazine, p-methylsulfonylhydrazine, etc.; metal hydrides such as sodium borohydride, lithium aluminum hydride, and the like; active metals such as aluminum, zinc, iron, and the like; reducing acids such as ascorbic acid, pyrogallic acid, etc.; reducing phenols, such as p-diphenol, tea polyphenol, etc.; reducing sugars, such as glucose, fructose, sucrose, and the like; basic compounds such as sodium hydroxide, potassium hydroxide, sodium hydrogencarbonate, aqueous ammonia and the like; iodides such as potassium iodide, ammonium iodide, sodium iodide, ferrous iodide, and the like; or a combination thereof. In another embodiment, the reducing agent may be a hydrazine-based compound, a reducing acid, or a combination thereof. In a specific embodiment, the reducing agent may preferably be one or more of hydrazine hydrate, ascorbic acid, glucose, sodium bicarbonate, and tea polyphenol, so that the reduction degree of graphene oxide is high without destroying the structure of graphene sheets. In a further particular embodiment, the reducing agent may be hydrazine hydrate.
In one embodiment, the graphene oxide graft modified fiber may be subjected to a reduction treatment using high-pressure thermal reduction, in which the graphene oxide graft modified fiber is placed between two hot plates and subjected to heating reduction at a certain temperature and pressure to obtain the graphene graft modified conductive fiber. In another embodiment, the reduction temperature may be 80 ℃ to 220 ℃, 90 ℃ to 210 ℃, 100 ℃ to 200 ℃, 110 ℃ to 190 ℃, 120 ℃ to 180 ℃, 130 ℃ to 170 ℃ or 140 ℃ to 160 ℃, and the pressure may be 0.1 Mpa to 10 Mpa, 0.2 Mpa to 9.0 Mpa, 0.4 Mpa to 8.0 Mpa, 0.6 Mpa to 7.0 Mpa, 0.8 Mpa to 6.0Mpa, 1.0 Mpa to 5.0 Mpa, or 2.0 Mpa to 4.0 Mpa to rapidly reduce the graphene oxide without a reducing agent. In particular embodiments, the reduction temperature may be 120 ℃ to 160 ℃, 130 ℃ to 150 ℃, 140 ℃ to 145 ℃ to enable sufficient reduction of graphene oxide without destroying the structure of the fibers and graphene oxide. In further particular embodiments, the reduction temperature can be from 120 ℃ to 140 ℃. In another embodiment, the pressure may be from 1.0 MPa to 4.0 MPa or from 2.0 MPa to 3.0 MPa. In particular embodiments, the pressure may be 3.0 Mpa.
In yet another embodiment, the heating time for the autoclaving reduction may be 5 minutes to 10 minutes, 10 minutes to 100 minutes, 20 minutes to 90 minutes, 30 minutes to 80 minutes, 40 minutes to 70 minutes, or 50 minutes to 60 minutes to ensure that the graphene oxide on the graft-modified fibers is sufficiently reduced. In particular embodiments, the heating time for the autoclaving reduction may be 10 minutes to 40 minutes or 20 minutes to 30 minutes. In further particular embodiments, the heating time of the autoclaving reduction can be 10 minutes to 20 minutes.
In one embodiment, the graphene oxide graft-modified fiber may be subjected to reduction treatment using microwave irradiation reduction, in which the graphene oxide graft-modified fiber is placed in a microwave irradiation device and reduced at a certain irradiation power and irradiation time to obtain the graphene graft-modified conductive fiber. In another embodiment, the irradiation power may be 10W to 1000W, 20W to 900W, 30W to 800W, 40W to 700W, 50W to 600W, 60W to 500W, 70W to 400W, 80W to 300W, 90W to 200W. In particular embodiments, the irradiation power may be 500W to 1000W or 600W to 800W. In a further specific embodiment, the irradiation power may be 500W to 600W to rapidly reduce the graphene oxide without the need for a reducing agent.
In yet another embodiment, the irradiation time may be 5 minutes to 70 minutes, 10 minutes to 60 minutes, 20 minutes to 50 minutes, or 30 minutes to 40 minutes. In particular embodiments, the irradiation time may be from 10 minutes to 50 minutes or from 20 minutes to 40 minutes. In further particular embodiments, the irradiation time may be 10 minutes to 20 minutes to ensure that the graphene oxide on the graft-modified fiber is sufficiently and efficiently reduced.
According to a third aspect of the present invention, there is provided a use of graphene graft modified conductive fibres in smart textiles, flexible sensors, electronic devices or electro-thermal health textiles.
In one embodiment, the smart textile may be a wearable device, a temperature regulating textile, a color changing textile, a shape memory textile, a flame retardant textile, a far infrared health textile, a corrosion resistant functional textile, or a light emitting textile, among others.
In another embodiment, the sensor may be a PH sweat sensor, a blood pressure pulse sensor, a respiration rate sensor, a joint flexion sensor, a human motion detection sensor, electronic skin, or the like.
In yet another embodiment, the electronic device may be a music electronic device, a communication electronic device, a liquid crystal display, a light emitting display, a flexible light emitting garment, a fibrous solid state supercapacitor, or the like.
In yet another embodiment, the electro-thermal health textile may be an electro-thermal health neck guard, waist guard, knee guard, eye shield, mask, far infrared heating carpet textile, and the like.
With respect to these characteristics, the graphene graft-modified conductive fiber of the present invention ensures lower electrical resistivity, higher water and abrasion resistance, and far-infrared emissivity. Therefore, the graphene grafted modified conductive fiber and the preparation method thereof are obviously valuable in industry.
Examples
The present invention is described in more detail below with reference to examples. However, the present invention is not limited to the following examples.
Example 1
Preparation of graphene grafted modified conductive cotton fiber
Placing cotton fibers in an acetone aqueous solution according to a weight ratio of 1:30, carrying out ultrasonic oscillation treatment for 10 minutes, taking out, and drying at 80 ℃ to obtain the pretreated cotton fibers.
The pre-treated cotton fibers were then soaked in a 1 wt% solution of polydopamine for 10 minutes, with the weight ratio of pre-treated cotton fibers to solution being 1:30, to obtain activated cotton fibers coated with polydopamine.
Graphene oxide was prepared by Hummer's oxidation, wherein the graphene oxide sheets obtained had a thickness of 1 layer and a planar size of 20 μm. The obtained graphene oxide is prepared into an aqueous solution with the concentration of 0.1mg/mL under the ultrasonic power of 600W and the magnetic stirring rotating speed of 500 rpm. Soaking activated cotton fibers in a graphene oxide aqueous solution in a weight ratio of 1:30 by a solution infiltration process, and carrying out probe type high-power ultrasonic treatment on the graphene oxide aqueous solution soaked with the activated cotton fibers for 10 minutes; meanwhile, a magnetic stirrer is adopted to stir for 10 minutes at the bottom of the aqueous solution through a magnetic rotor, so that the fibers are always in a moving and dispersing state in the grafting treatment process; and controlling the temperature of the graphene oxide graft modification reaction to be about 60 ℃ by adopting an external constant-temperature water bath system so as to obtain the graphene oxide graft modified cotton fiber.
And placing the graphene oxide grafted modified cotton fiber between two hot flat plates, and heating and reducing the graphene oxide grafted modified cotton fiber at the temperature of 160 ℃ for 10 minutes under the pressure of 1MPa to obtain the graphene grafted modified conductive cotton fiber.
The resistivity of the graphene grafted modified conductive cotton fiber is 1.0 multiplied by 103Ω · m, the resistivity after 20 washes increases by 2%, and after 600 rubs on a model YG522 abrasion tester according to ISO 5470-1-1999 by 3%; the far infrared emissivity is 85 percent.
Example 2
Preparation of graphene grafted modified conductive adhesive fiber
Placing the viscose fibers in an acetone aqueous solution according to a weight ratio of 1:30, carrying out ultrasonic oscillation treatment for 20 minutes, taking out, and drying at 80 ℃ to obtain the pretreated viscose fibers.
And then uniformly coating the 1 wt% polydopamine solution on the surface of the pretreated viscose fiber by a high-pressure spraying process to obtain the activated viscose fiber, wherein the spraying pressure is 1 bar, and the spraying amount is 300 mL/min.
Graphene oxide was prepared by Hummer's oxidation, wherein the graphene oxide sheets obtained had a thickness of 1 layer and a planar size of 50 μm. The obtained graphene oxide is prepared into an aqueous solution with the concentration of 0.5 mg/mL under the ultrasonic power of 800W and the magnetic stirring rotating speed of 800 rpm. Soaking the activated viscose fibers in a graphene oxide aqueous solution in a weight ratio of 1:30 by a solution infiltration process, carrying out probe type high-power ultrasonic treatment on the graphene oxide aqueous solution soaked with the activated cotton fibers, and carrying out ultrasonic oscillation for 40 minutes; meanwhile, a magnetic stirrer is adopted to stir for 40 minutes at the bottom of the aqueous solution through a magnetic rotor, so that the fibers are always in a moving and dispersing state in the grafting treatment process; and controlling the temperature of the graphene oxide graft modification reaction to be about 80 ℃ by adopting an external constant-temperature water bath system so as to obtain the graphene oxide graft modification viscose fiber.
Placing the graphene oxide grafted modified viscose fiber between two hot plates, and heating and reducing for 10 minutes at 160 ℃ under the pressure of 2 MPa; and then placing the fiber in a microwave irradiation device to be irradiated for 10 minutes at the power of 600W, so as to obtain the graphene grafted modified conductive adhesive fiber.
The resistivity of the graphene grafted modified conductive adhesive fiber is 1.0 multiplied by 104Ω · m, the resistivity after 20 washes increases by 1%, and after 600 rubs on a model YG522 abrasion tester according to ISO 5470-1-1999 by 2%; the far infrared emissivity is 90%.
Example 3
Preparation of graphene grafted modified conductive hemp fiber
Placing the hemp fiber in an acetone aqueous solution according to a weight ratio of 1:50, carrying out ultrasonic oscillation treatment for 50 minutes, taking out, and drying at 100 ℃ to obtain the pretreated hemp fiber.
And then uniformly coating 0.1 weight percent polydopamine solution on the surface of the pretreated hemp fiber by a high-pressure spraying process to obtain the activated hemp fiber, wherein the spraying pressure is 1 bar, and the spraying amount is 300 mL/min.
Graphene oxide was prepared by Hummer's oxidation, wherein the graphene oxide sheets obtained had a thickness of 1 layer and a planar size of 100 μm. The obtained graphene oxide is prepared into an aqueous solution with the concentration of 0.1mg/mL under the ultrasonic power of 800W and the magnetic stirring rotating speed of 800 rpm. Uniformly coating a 0.1mg/mL graphene oxide aqueous solution on the surface of the activated hemp fiber through a high-pressure spraying process to obtain the graphene oxide grafted modified hemp fiber, wherein the spraying pressure is 1 bar, and the spraying amount is 600 mL/min.
And placing the graphene oxide grafted and modified hemp fiber between two hot flat plates, and heating and reducing the mixture at 120 ℃ for 10 minutes under the pressure of 3 MPa to obtain the graphene grafted and modified conductive hemp fiber.
The resistivity of the graphene grafted modified conductive hemp fiber is 1.0 multiplied by 103Ω · m, the resistivity after 20 washes increases by 1.5%, and after 600 rubs on a model YG522 abrasion tester according to ISO 5470-1-1999 increases by 5%; the far infrared emissivity is 91%.
Example 4
Preparation of graphene grafted modified conductive polylactic acid fiber
Putting the polylactic acid fiber into an acetone aqueous solution according to the weight ratio of 1:40, carrying out ultrasonic oscillation treatment for 60 minutes, taking out, and drying at 100 ℃ to obtain the pretreated polylactic acid fiber.
And then uniformly coating 0.2 wt% polydopamine solution on the surface of the pretreated polylactic acid fiber by a high-pressure spraying process to obtain the activated polylactic acid fiber, wherein the spraying pressure is 1 bar, and the spraying amount is 350 mL/min.
Graphene oxide was prepared by Hummer's oxidation, wherein the graphene oxide sheets obtained had a thickness of 1 layer and a planar size of 120 μm. The obtained graphene oxide is prepared into an aqueous solution with the concentration of 0.3 mg/mL under the ultrasonic power of 800W and the magnetic stirring rotating speed of 800 rpm. Uniformly coating 0.3 mg/mL of graphene oxide aqueous solution on the surface of the activated polylactic acid fiber by a high-pressure spraying process to obtain the graphene oxide grafted modified polylactic acid fiber, wherein the spraying pressure is 1 bar, and the spraying amount is 600 mL/min.
And placing the graphene oxide grafted modified polylactic acid fiber between two hot flat plates, and heating and reducing the graphene oxide grafted modified polylactic acid fiber at the temperature of 120 ℃ for 10 minutes under the pressure of 3 MPa to obtain the graphene grafted modified conductive polylactic acid fiber.
The resistivity of the graphene grafted modified conductive polylactic acid fiber is 1.0 multiplied by 102Ω · m, the resistivity after 20 washes increases by 2%, and after 600 rubs on a model YG522 abrasion tester according to ISO 5470-1-1999 by 4%; the far infrared emissivity is 90%.
Example 5
Preparation of graphene grafted modified conductive chitosan fiber
Placing chitosan fibers in an acetone solution according to the weight ratio of 1:45, carrying out ultrasonic oscillation treatment for 40 minutes, taking out, and drying at 100 ℃ to obtain the pretreated chitosan fibers.
And then uniformly coating 0.15 wt% polydopamine solution on the surface of the pretreated chitosan fiber by a high-pressure spraying process to obtain the activated chitosan fiber, wherein the spraying pressure is 1 bar, and the spraying amount is 400 mL/min.
Graphene oxide was prepared by Hummer's oxidation, wherein the graphene oxide sheets obtained had a thickness of 1 layer and a planar size of 120 μm. The obtained graphene oxide is prepared into an aqueous solution with the concentration of 0.3 mg/mL under the ultrasonic power of 800W and the magnetic stirring rotating speed of 800 rpm. Uniformly coating 0.3 mg/mL of graphene oxide aqueous solution on the surface of the activated chitosan fiber through a high-pressure spraying process to obtain the graphene oxide grafted modified chitosan fiber, wherein the spraying pressure is 1 bar, and the spraying amount is 600 mL/min.
And placing the graphene oxide grafted modified chitosan fiber between two hot flat plates, and heating and reducing the graphene oxide grafted modified chitosan fiber at the temperature of 120 ℃ for 10 minutes under the pressure of 3 MPa to obtain the graphene grafted modified conductive chitosan fiber.
The resistivity of the graphene grafted modified conductive chitosan fiber is 1 multiplied by 101Ω · m, an increase in resistivity of 2% after 20 washes, an increase in resistivity of 4.5% after 600 rubs on a model YG522 abrasion tester according to ISO 5470-1-1999; the far infrared emissivity is 92 percent.
Example 6
Preparation of graphene grafted modified conductive sodium alginate fiber
Placing sodium alginate fiber in acetone solution at a weight ratio of 1:50, performing ultrasonic oscillation treatment for 40 minutes, taking out, and drying at 50 ℃ to obtain the pretreated sodium alginate fiber.
And then uniformly coating 0.2 wt% polydopamine solution on the surface of the pretreated sodium alginate fiber by a high-pressure spraying process to obtain the activated sodium alginate fiber, wherein the spraying pressure is 1 bar, and the spraying amount is 350 mL/min.
Graphene oxide was prepared by Hummer's oxidation, wherein the graphene oxide sheets obtained had a thickness of 1 layer and a planar size of 120 μm. The obtained graphene oxide is prepared into an aqueous solution with the concentration of 0.3 mg/mL under the ultrasonic power of 800W and the magnetic stirring rotating speed of 800 rpm. And uniformly coating 0.3 mg/mL of graphene oxide aqueous solution on the surface of the activated sodium alginate fiber by a high-pressure spraying process to obtain the graphene oxide grafted modified sodium alginate fiber, wherein the spraying pressure is 1 bar, and the spraying amount is 600 mL/min.
And placing the graphene oxide grafted modified sodium alginate fiber between two heat flat plates, and heating and reducing the graphene oxide grafted modified sodium alginate fiber at the temperature of 120 ℃ for 10 minutes under the pressure of 3 MPa to obtain the graphene grafted modified conductive sodium alginate fiber.
The resistivity of the graphene grafted modified conductive sodium alginate fiber is 1 multiplied by 103Omega. m, after washing 20 times with waterIncreases the resistivity by 1%, by 4% after 600 rubs on a model YG522 abrasion tester according to ISO 5470-1-1999; the far infrared emissivity is 93%.
Example 7
Preparation of graphene grafted modified conductive cotton fiber by solution reduction
Graphene oxide graft-modified cotton fibers were prepared in the same manner as in example 1, and then the obtained graphene oxide graft-modified cotton fibers were placed in a hydrazine hydrate aqueous solution having a concentration of 0.1% at a weight ratio of 1:50, and were reduced by heating in a water bath environment at 100 ℃ for 60 minutes to obtain graphene graft-modified conductive cotton fibers.
The resistivity of the graphene grafted modified conductive cotton fiber is 1.0 multiplied by 102Ω · m, the resistivity after 20 washes increases by 1%, and after 800 rubs on a model YG522 abrasion tester according to ISO 5470-1-1999 increases by 2.5%; the far infrared emissivity is 88%.
Example 8
Graphene grafted modified conductive adhesive fiber prepared by solution reduction
Graphene oxide graft-modified viscose fibers were prepared in the same manner as in example 2, and then the obtained graphene oxide graft-modified viscose fibers were placed in a hydrazine hydrate aqueous solution having a concentration of 0.2% at a weight ratio of 1:60, and were reduced by heating in a water bath environment at 90 ℃ for 80 minutes to obtain graphene graft-modified conductive viscose fibers.
The resistivity of the graphene grafted modified conductive adhesive fiber is 5.0 multiplied by 103Ω · m, the resistivity after 20 washes increases by 0.5%, the resistivity after 700 rubs on a model YG522 abrasion tester according to ISO 5470-1-1999 increases by 1.5%; the far infrared emissivity is 91%.
Example 9
Preparation of graphene grafted modified conductive hemp fiber by solution reduction
Graphene oxide graft-modified hemp fibers were prepared in the same manner as in example 3, and then the obtained graphene oxide graft-modified hemp fibers were placed in a hydrazine hydrate aqueous solution having a concentration of 0.15% at a weight ratio of 1:40, and were reduced by heating in a water bath environment at 90 ℃ for 120 minutes to obtain graphene graft-modified conductive hemp fibers.
The resistivity of the graphene grafted modified conductive adhesive fiber is 5.0 multiplied by 102Ω · m, the resistivity after 20 washes increases by 2%, the resistivity after 600 rubs on a model YG522 abrader according to ISO 5470-1-1999 increases by 4%; the far infrared emissivity is 90%.
Fig. 1 to 2 respectively show electron microscope images of the matrix fiber before and after graft modification, which indicate that graphene is effectively grafted on the fiber surface.
The above embodiments and examples are merely illustrative of specific embodiments of the present disclosure, but the embodiments of the present disclosure are not limited by the above. Any changes, modifications, substitutions, combinations, and simplifications which do not materially depart from the spirit and principles of the inventive concepts disclosed herein are intended to be equivalent permutations and to be included within the scope of the invention as defined by the following claims.

Claims (6)

1. A graphene graft-modified conductive fiber comprising:
a base fiber portion having one or more functional groups selected from the group consisting of a hydroxyl group, a carboxyl group, an amino group, an isocyanate group, an acid halide group on the surface;
an activation aid portion chemically bonded to the base fiber portion and containing a plurality of groups reactive with the functional groups on the surface of the base fiber portion; and
a graphene moiety grafted on the base fiber via chemical bonding with the co-agent moiety,
wherein the graphene graft-modified conductive fibers increase in resistivity by 0.1% to 2% after being washed with water for 20 times and increase in resistivity by 0.1% to 5% after being rubbed on a YG522 type abrasion tester according to ISO 5470-1-1999 for 600 times to 800 times; the graphene grafted modified conductive fiber has the structure of 1 multiplied by 101Omega m to 1X 105Resistivity of omega mAnd a far infrared emissivity of 80% to 95%.
2. The graphene graft modified conductive fiber according to claim 1, wherein the base fiber portion is selected from one or more of the group consisting of: polysaccharide fibers, cotton fibers, absorbent cotton fibers, hemp fibers, flax fibers, ramie fibers, jute fibers, apocynum venetum fibers, flax fibers, viscose fibers, cuprammonium fibers, acetate fibers, seaweed fibers, chitosan fibers, sodium alginate fibers, tencel, modal fibers and tianzhu; and chemical fibers containing the functional groups, including polyvinyl alcohol fibers, acrylic fibers, polyurethane fibers, polylactic acid fibers and polyacrylonitrile fibers.
3. The graphene graft-modified conductive fiber according to claim 1, wherein the activation aid moiety is derived from an activation aid comprising a functional group selected from one or more of a hydroxyl group, a carboxyl group, an amino group, an isocyanate group, an acid halide group, the activation aid being selected from one or more of the group consisting of: dopamine, polydopamine, chitosan, sodium alginate, polylactic acid, polyacrylic acid, glutamic acid tetraacetic acid, ascorbic acid, ethylene diamine tetraacetic acid, polyvinyl alcohol, polyethylene glycol, polypropylene glycol, hydroxypropyl methylcellulose, pentaerythritol, triethylenetetramine, tetraethylenepentamine, melamine, spermine, trimesoyl chloride.
4. A method of preparing the graphene graft modified conductive fiber of claim 1, comprising:
putting the matrix fiber in a polar organic solvent or a water solution thereof for ultrasonic oscillation treatment, and then taking out and drying to obtain a pretreated fiber;
chemically bonding a co-agent to the surface of the pre-treated fiber to obtain an activated fiber;
preparing graphene oxide into a solution and grafting the graphene oxide onto the activated fiber through chemical bonding with the activating auxiliary agent to obtain a graphene oxide graft modified fiber; and
reducing the graphene oxide graft-modified fiber to obtain the graphene graft-modified conductive fiber;
wherein the polar organic solvent is selected from one or more of the group consisting of: ethanol, isopropanol, methyl ethyl ketone, acetone, 1, 4-butanediol and ethylene glycol butyl ether; wherein the weight ratio of the base fiber to the polar organic solvent or aqueous solution thereof is 1:20 to 1: 110;
wherein the activation aid is chemically bonded to the pretreated fiber in the form of a solution, and the concentration of the solution of the activation aid is 0.05 wt% to 12 wt%;
wherein the concentration of the graphene oxide solution is 0.05mg/mL to 110 mg/mL.
5. The method of claim 4, wherein the process of reducing the graphene oxide graft-modified fibers comprises solution reduction, autoclaving, microwave irradiation reduction, or a combination thereof, wherein the solution reduction comprises reduction using a solution of a reducing agent, and the reducing agent is one or more selected from the group consisting of: hydrazine compounds including hydrazine hydrate, dimethylhydrazine, phenylhydrazine or p-methylsulfonyl hydrazide; metal hydrides including sodium borohydride, lithium aluminum hydride; active metals including aluminum, zinc, iron; reducing acids including ascorbic acid, pyrogallic acid; reducing phenols including p-diphenol and tea polyphenol; reducing sugars including glucose, fructose, sucrose; alkaline compounds including sodium hydroxide, potassium hydroxide, sodium bicarbonate, ammonia; iodides including potassium iodide, ammonium iodide, sodium iodide, ferrous iodide.
6. Use of the graphene graft modified conductive fiber according to any one of claims 1 to 3 or prepared according to the method of any one of claims 4 to 5 in smart textiles, flexible sensors, electronics or electro thermal health textiles.
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