CN109553087B - Modified carbon nanotube array, carbon nanotube fiber, and preparation method and application thereof - Google Patents

Modified carbon nanotube array, carbon nanotube fiber, and preparation method and application thereof Download PDF

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CN109553087B
CN109553087B CN201811519054.3A CN201811519054A CN109553087B CN 109553087 B CN109553087 B CN 109553087B CN 201811519054 A CN201811519054 A CN 201811519054A CN 109553087 B CN109553087 B CN 109553087B
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carbon nanotube
nanotube array
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oxazoline
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CN109553087A (en
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邓飞
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Shenzhen Cone Technology Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/158—Carbon nanotubes
    • C01B32/16—Preparation
    • C01B32/162—Preparation characterised by catalysts
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/158—Carbon nanotubes
    • C01B32/159—Carbon nanotubes single-walled
    • 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
    • D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
    • D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
    • D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
    • D01F9/127—Carbon filaments; Apparatus specially adapted for the manufacture thereof by thermal decomposition of hydrocarbon gases or vapours or other carbon-containing compounds in the form of gas or vapour, e.g. carbon monoxide, alcohols
    • D01F9/1271—Alkanes or cycloalkanes
    • 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
    • D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
    • D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
    • D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
    • D01F9/127—Carbon filaments; Apparatus specially adapted for the manufacture thereof by thermal decomposition of hydrocarbon gases or vapours or other carbon-containing compounds in the form of gas or vapour, e.g. carbon monoxide, alcohols
    • D01F9/1273—Alkenes, alkynes
    • D—TEXTILES; PAPER
    • D03—WEAVING
    • D03D—WOVEN FABRICS; METHODS OF WEAVING; LOOMS
    • D03D15/00—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04B—KNITTING
    • D04B1/00—Weft knitting processes for the production of fabrics or articles not dependent on the use of particular machines; Fabrics or articles defined by such processes
    • D04B1/14—Other fabrics or articles characterised primarily by the use of particular thread materials
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04B—KNITTING
    • D04B21/00—Warp knitting processes for the production of fabrics or articles not dependent on the use of particular machines; Fabrics or articles defined by such processes
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2202/00—Structure or properties of carbon nanotubes
    • C01B2202/02—Single-walled nanotubes
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2202/00—Structure or properties of carbon nanotubes
    • C01B2202/06—Multi-walled nanotubes
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    • C01B2202/00—Structure or properties of carbon nanotubes
    • C01B2202/20—Nanotubes characterized by their properties
    • C01B2202/26—Mechanical properties

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Abstract

The invention relates to a modified carbon nanotube array, a carbon nanotube fiber, and a preparation method and application thereof. The preparation method of the modified carbon nanotube array comprises the following steps: and under the protective gas atmosphere, carrying out ultraviolet irradiation treatment on the first substrate with the carbon nanotube array and the second substrate with the high molecular polymer to enable the high molecular polymer and the carbon nanotube array to carry out grafting reaction to obtain the modified carbon nanotube array, wherein the high molecular polymer is a copolymer of a 2-oxazoline monomer and a nitrogen-containing heterocyclic ring monomer, the 2-oxazoline monomer is selected from at least one of 2-vinyl-2-oxazoline and 5-methyl-2-vinyl-2-oxazoline, and the nitrogen-containing heterocyclic ring monomer is selected from at least one of N-acryloyl morpholine and N-vinyl caprolactam. The modified carbon nanotube array prepared by the preparation method can be used for preparing carbon nanotube fibers with lower density.

Description

Modified carbon nanotube array, carbon nanotube fiber, and preparation method and application thereof
Technical Field
The invention relates to the technical field of materials, in particular to a modified carbon nanotube array, a carbon nanotube fiber, and a preparation method and application thereof.
Background
With the rise and continuous discovery of information technology and bioengineering, nanometer functional materials and nanotechnology become research hotspots. Due to the uniqueness of the structure and performance of nanomaterials and the wide practical application prospects, nanotechnology has penetrated various fields of life and production, such as cosmetics, coatings, energy sources, and the like. Nanotechnology enables many traditional products to be improved or to obtain a series of new functions, and enhances the market competitiveness of the products. In the textile industry, the nano material and the technology have wide application prospect. The cloth prepared by adopting the nano material has multiple functions of electric conduction, static resistance, high strength and wear resistance and the like. The carbon nano tube is used as a one-dimensional nano material, is light in weight, has perfect connection of a hexagonal structure, and has many abnormal mechanical, electrical and chemical properties. In recent years, the extensive application prospect of the carbon nano-tube and the nano-material is continuously shown along with the research of the carbon nano-tube and the nano-material. However, the carbon nanotube fiber prepared by using the conventional carbon nanotube has a high fiber density, so that the prepared cloth is not soft enough, and the quality of the cloth is affected.
Disclosure of Invention
Therefore, there is a need for a method for preparing a carbon nanotube array, and the modified carbon nanotube array obtained by the method can be used for preparing carbon nanotube fibers with low density.
In addition, a modified carbon nanotube array and carbon nanotube fiber, and preparation methods and applications thereof are also provided.
A preparation method of a modified carbon nanotube array comprises the following steps:
forming a carbon nanotube array on a first substrate;
forming a high molecular polymer on the second substrate, wherein the high molecular polymer is a copolymer of a 2-oxazoline monomer and a nitrogen-containing heterocyclic monomer, the 2-oxazoline monomer is selected from at least one of 2-vinyl-2-oxazoline and 5-methyl-2-vinyl-2-oxazoline, and the nitrogen-containing heterocyclic monomer is selected from at least one of N-acryloyl morpholine and N-vinyl caprolactam; and
and under the protective gas atmosphere, carrying out ultraviolet irradiation treatment on the first substrate for forming the carbon nanotube array and the second substrate for forming the high molecular polymer so as to carry out grafting reaction on the high molecular polymer and the carbon nanotube array, thereby obtaining the modified carbon nanotube array.
The preparation method of the modified carbon nanotube array adopts ultraviolet light to graft a high molecular polymer or a decomposition product of the high molecular polymer on the surface of the carbon nanotube array, the high molecular polymer is a copolymer of a 2-oxazoline monomer and a nitrogen-containing heterocyclic monomer, the 2-oxazoline monomer is at least one selected from 2-vinyl-2-oxazoline and 5-methyl-2-vinyl-2-oxazoline, the nitrogen-containing heterocyclic monomer is at least one selected from N-acryloyl morpholine and N-vinyl caprolactam to increase the distance between the carbon nanotubes, thereby reducing the agglomeration caused by Van der Waals force between the carbon nanotubes to obtain the modified carbon nanotube array which is easy to disperse, and further leading the density of carbon nanotube fibers prepared by the carbon nanotubes to be lower, the cloth prepared by the carbon nanotube fiber is softer. Tests prove that the density of the carbon nano tube fiber prepared by adopting the modified carbon nano tube array is 1.6g/cm2～2.0g/cm2Low density, energyCan be used for preparing cloth with higher quality.
In one embodiment, the irradiation power of the ultraviolet light is 15mW to 35mW, the ultraviolet light is monochromatic narrow-band light with the irradiation wavelength of 196nm to 350nm, and the irradiation time of the ultraviolet light is 10min to 35 min.
In one embodiment, before the step of forming the high molecular polymer on the second substrate, the method further comprises the step of preparing the high molecular polymer as follows: carrying out free radical polymerization reaction on the 2-oxazoline monomer and the nitrogen-containing heterocyclic monomer to obtain a reactant; and adding a solvent into the reactant, and collecting the precipitate after solid-liquid separation to obtain the high molecular polymer.
In one embodiment, the step of performing radical polymerization on the 2-oxazoline monomer and the nitrogen-containing heterocyclic monomer is specifically: and carrying out polymerization reaction on the 2-oxazoline monomer and the nitrogen-containing heterocyclic monomer under the irradiation of ultraviolet light, controlling the reaction temperature to be 20-45 ℃, controlling the power of the ultraviolet light to be 45-55W, and controlling the reaction time to be 30-50 min.
In one embodiment, the weight average molecular weight of the high molecular polymer is 3500-30000; and/or the presence of a catalyst in the reaction mixture,
the molar ratio of the 2-oxazoline monomer to the nitrogen-containing heterocyclic monomer is 0.75-3.2.
In one embodiment, the step of forming the carbon nanotube array on the first substrate comprises:
depositing a catalyst layer on the first substrate; and
heating the first substrate forming the catalyst layer to 550-900 ℃ in a protective gas atmosphere, and introducing a carbon source gas for reaction to obtain the carbon nanotube array; the carbon source gas comprises ethylene and hexane, the gas partial pressure ratio of the ethylene to the hexane is 1.25: 1-8: 1, the flow rate of the carbon source gas is 5-15 mL/min, and the time for introducing the carbon source gas to react is 10-25 min.
A modified carbon nanotube array is prepared by the preparation method of the modified carbon nanotube array.
The preparation method of the carbon nanotube fiber comprises the step of spinning the modified carbon nanotube array to obtain the carbon nanotube fiber.
A carbon nanotube fiber is prepared by the preparation method of the carbon nanotube fiber.
The carbon nanotube fiber is applied to the preparation of cloth.
Detailed Description
In order that the invention may be more fully understood, reference will now be made to the following description. The present invention may be embodied in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
A method for manufacturing a carbon nanotube fiber according to an embodiment includes steps S110 to S140 of:
and S110, preparing the modified carbon nanotube array.
In one embodiment, the step of preparing the modified carbon nanotube array includes steps S111 to S113:
s111, depositing a carbon nano tube array on the first substrate.
In one embodiment, the step of depositing the carbon nanotube array on the first substrate includes steps S1111 to S1112:
s1111, depositing a catalyst layer on the first substrate.
In one embodiment, a catalyst layer is formed on a surface of a first substrate using an electron beam evaporation method. Further, the material of the catalyst layer is selected from at least one of iron, cobalt, and nickel. The thickness of the catalyst layer is 20nm to 23 nm.
And S1112, heating the first substrate with the catalyst layer to 550-900 ℃ in a protective gas atmosphere, and introducing a carbon source gas for reaction to obtain the carbon nanotube array.
In one embodiment, the first substrate deposited with the catalyst layer is placed in a chemical vapor reaction furnace for reaction. Further, protective gas is introduced into the chemical vapor reaction furnace, and then the temperature of the chemical vapor reaction furnace is raised to 550-900 ℃ so that the catalyst layer uniformly nucleates on the first substrate; then carbon source gas is introduced into the reaction kettle for reaction.
Further, the carbon source gas comprises ethylene and hexane, and the gas partial pressure ratio of ethylene to hexane is 1.25:1 to 8: 1. The flow rate of the carbon source gas is 5mL/min to 15mL/min, and the time for introducing the carbon source gas to react is 10min to 25 min. Through the arrangement, the obtained carbon nanotube array has good mechanical property, so that carbon nanotube fibers with low density and high tensile strength are obtained.
In one embodiment, the protective gas is selected from at least one of nitrogen, hydrogen, argon, and helium.
In one embodiment, the carbon nanotube array deposited on the first substrate is a single-walled carbon nanotube array. It should be noted that the carbon nanotube array deposited on the first substrate may also be a multi-walled carbon nanotube array. It should be noted that, when the preparation method of the modified carbon nanotube array is adopted, the surface of the single-walled carbon nanotube array is more difficult to modify than the surface of the carbon nanotube array.
In one embodiment, the carbon nanotube array deposited on the first substrate has a length of 650 μm to 1200 μm. The diameter of the carbon nano tube in the carbon nano tube array is 10 nm-15 nm.
In one embodiment, the first substrate is an alumina plate. The first substrate mainly plays a role in carrying the carbon nanotube array. In one embodiment, the first substrate is 8 feet in size. Of course, in other embodiments, the size of the first substrate may be any other size.
In one embodiment, the first substrate has a first working surface. And depositing and forming a carbon nano tube array layer on the first working surface.
And S112, depositing a high molecular polymer on the second substrate.
In one embodiment, the high molecular polymer is a copolymer of a 2-oxazoline monomer and a nitrogen-containing heterocyclic monomer, the 2-oxazoline monomer is at least one selected from the group consisting of 2-vinyl-2-oxazoline and 5-methyl-2-vinyl-2-oxazoline, and the nitrogen-containing heterocyclic monomer is at least one selected from the group consisting of N-acryloylmorpholine and N-vinylcaprolactam.
In one embodiment, the weight average molecular weight of the high molecular polymer is 3500-30000. Further, the weight average molecular weight of the high molecular polymer is 5000-20000.
In one embodiment, the molar ratio of the 2-oxazoline monomer to the nitrogen-containing heterocyclic monomer is 0.75 to 3.2. The high molecular polymer obtained by the molar ratio is easier to graft on the surface of the carbon nanotube array, and the obtained modified carbon nanotube fiber has lower density and better tensile strength.
In one embodiment, the 2-oxazoline monomer is composed of 2-vinyl-2-oxazoline and 5-methyl-2-vinyl-2-oxazoline, and the molar ratio of the 2-vinyl-2-oxazoline to the 5-methyl-2-vinyl-2-oxazoline is 0.7 to 1.3. The modified carbon nanotube fiber obtained by the arrangement can be used for preparing modified carbon nanotube fibers with higher density, lower density and better tensile strength. Further, the molar ratio of 2-vinyl-2-oxazoline to 5-methyl-2-vinyl-2-oxazoline was 1.
In one embodiment, the nitrogen-containing heterocyclic monomer is composed of N-acryloyl morpholine and N-vinyl caprolactam, and the molar ratio of N-acryloyl morpholine to N-vinyl caprolactam is 0.8-1.2. The modified carbon nanotube fiber obtained by the arrangement can be used for preparing modified carbon nanotube fibers with higher density, lower density and better tensile strength. Further, the molar ratio of N-acryloyl morpholine to N-vinyl caprolactam is 1.
In one embodiment, the second substrate is a nickel or copper sheet. The second substrate is mainly used for bearing high molecular polymers, and the nickel sheet and the copper sheet have good chemical stability and cannot react with the high molecular polymers. Further, the size of the second substrate is 50mm by 50mm, but in other embodiments, the size of the second substrate may be any other size.
In one embodiment, the method for forming the polymer on the second substrate may be a method for forming a polymer film on the second substrate, and of course, in other embodiments, a method for cutting the polymer material and then placing the polymer material on the second substrate may be used.
In one embodiment, the thickness of the high molecular polymer deposited on the second substrate is 1mm to 5 mm. Further, the second substrate has a second working surface. And depositing to form a high molecular polymer film on the second working surface. The high molecular polymer film completely covers the second working surface.
In one embodiment, before S112, the method further includes a step of preparing a high molecular weight polymer: carrying out free radical polymerization reaction on a 2-oxazoline monomer and a nitrogen-containing heterocyclic monomer to obtain a reactant; adding a solvent into the reactant, carrying out solid-liquid separation, and collecting the precipitate to obtain the high molecular polymer.
Further, the step of carrying out free radical polymerization reaction on the 2-oxazoline monomer and the nitrogen-containing heterocyclic monomer is specifically as follows: polymerizing 2-oxazoline monomer and nitrogen heterocyclic monomer under the irradiation of ultraviolet light, controlling the reaction temperature to be 20-45 ℃, controlling the power of the ultraviolet light to be 45-55W, and controlling the reaction time to be 30-50 min.
In one embodiment, the solvent is selected from at least one of carbon tetrachloride, tetrahydrofuran, and dichloromethane.
In one embodiment, after the step of collecting the precipitate after the solid-liquid separation, the method further comprises a step of drying the precipitate to obtain a dried high molecular polymer. It should be noted that the step of drying the precipitate may be omitted if the precipitate is sufficient.
S113, under the protective gas atmosphere, carrying out ultraviolet irradiation treatment on the first substrate with the carbon nanotube array and the second substrate with the high molecular polymer to enable the high molecular polymer and the carbon nanotube array to carry out grafting reaction, and obtaining the modified carbon nanotube array.
In one embodiment, a first substrate formed with a carbon nanotube array and a second substrate formed with a high molecular polymer are placed in the same reaction chamber. The reaction chamber can be closed, and the reaction chamber is provided with an air inlet and an air outlet. Be equipped with the ultraviolet ray subassembly in the reaction chamber, can carry out ultraviolet irradiation to the reaction chamber and handle.
Furthermore, the first substrate with the carbon nanotube array and the second substrate with the high molecular polymer are placed in the reaction chamber side by side. Furthermore, the first substrate formed with the carbon nanotube array and the second substrate formed with the high molecular polymer are placed side by side, so that the carbon nanotube array is in contact with the high molecular polymer.
In one embodiment, in the process of performing ultraviolet irradiation treatment on the first substrate on which the carbon nanotube array is formed and the second substrate on which the high molecular polymer is formed, the gas inlet and the gas outlet of the reaction chamber are first closed, and the reaction chamber is vacuumized to reduce the pressure in the reaction chamber to 10 deg.f-2The Torr is less. Preferably, the gas pressure in the reaction chamber is reduced to 10-6The Torr is less. And secondly, introducing protective gas into the reaction cavity through the gas inlet until the pressure reaches normal atmospheric pressure, opening the gas outlet, and continuously introducing the protective gas to maintain the pressure of the system.
In one embodiment, the flow rate of the protective gas is 2L/min to 3L/min. The protective gas is selected from at least one of nitrogen, helium, neon and argon.
In one embodiment, when the first substrate on which the carbon nanotube array is formed and the second substrate on which the high molecular polymer is formed are subjected to ultraviolet irradiation, the irradiation power of ultraviolet light is 15mW to 35 mW. Under the irradiation power, the heat effect of the reaction system is improved, the temperature of the system is increased to a state that the high molecular polymer forms a gas state, and the gas moves to the surface of the carbon nano tube array to perform graft polymerization reaction with the carbon nano tube array under the action of protective gas flow.
In one embodiment, the ultraviolet light is monochromatic (monochromatic) narrow band light with an illumination wavelength of 196nm to 350 nm. Further, the monochromatic narrow-band light is monochromatic light with the bandwidth of 218 nm-298 nm.
In one embodiment, the distance between the ultraviolet light source and the first substrate on which the carbon nanotube array is formed and the second substrate on which the high molecular polymer is formed is 2mm to 20 mm.
In one embodiment, the ultraviolet irradiation treatment is performed for 10min to 35 min. In one embodiment, the ultraviolet irradiation treatment is performed for 15min to 430 min. In one embodiment, the ultraviolet irradiation treatment is performed for 23 min.
In one embodiment, the first substrate on which the carbon nanotube array is formed and the second substrate on which the high molecular polymer is formed are subjected to ultraviolet irradiation treatment, wherein the irradiation power of ultraviolet light is 15 mW-35 mW, the ultraviolet light is monochromatic narrow-band light of 196 nm-350 nm, and the time of the ultraviolet irradiation treatment is 10 min-30 min. Under the condition, the damage of ultraviolet light to the high molecular polymer and the carbon nano tube array structure is reduced under the condition that the high molecular polymer can be grafted to the carbon nano tube array, so that the mechanical property of the carbon nano tube array is ensured.
In one embodiment, after the ultraviolet irradiation treatment is performed on the first substrate on which the carbon nanotube array is formed and the second substrate on which the high molecular polymer is formed, the operation of placing the first substrate in a protective gas atmosphere for natural cooling is further included. It should be noted that, in other embodiments, the natural cooling operation of the first substrate under the protective gas atmosphere may be omitted.
In one embodiment, the first substrate is naturally cooled by being placed in a protective gas atmosphere, and the protective gas is at least one selected from the group consisting of nitrogen, argon, and helium. Placing the first substrate in a protective gas atmosphere for natural cooling can prevent the carbon nanotube array from being oxidized by exposure to air.
And S120, spinning the modified carbon nanotube array to obtain the carbon nanotube fiber.
In one embodiment, the operation of S120 is specifically: and clamping the modified carbon nanotube array from the edge of the modified carbon nanotube array by using a clamping tool, and dragging and rotating the modified carbon nanotube array along a direction perpendicular to the growth direction of the modified carbon nanotube array to obtain the carbon nanotube fiber.
When the clamping tool stretches the carbon nanotube, the carbon nanotube drives the modified carbon nanotube array to be continuously pulled out through van der waals force and non-covalent bond interaction force between the high molecular polymer or decomposition products of the high molecular polymer modified on the surface of the modified carbon nanotube array, so that filamentous carbon nanotubes, namely carbon nanotube fibers, are formed.
In one embodiment, the modified carbon nanotube array is clamped from the edge of the modified carbon nanotube array, and the clamping width is 50 μm to 200 μm. Furthermore, when the modified carbon nanotube array is clamped from the edge of the modified carbon nanotube array, the clamping width is 100-150 μm.
In one embodiment, the speed of dragging along the direction perpendicular to the growth direction of the modified carbon nanotube array is 0.05-0.5 mm/s. Further, the speed of dragging along the direction vertical to the growth direction of the modified carbon nanotube array is 0.1-0.4 mm/s. Furthermore, the speed of dragging along the direction vertical to the growth direction of the modified carbon nano tube array is 0.2-0.3 mm/s.
In one embodiment, the speed of rotation when the modified carbon nanotube array is dragged and rotated in a direction perpendicular to the growth direction of the modified carbon nanotube array is 1000rpm to 3000 rpm. Further, the rotational speed when the modified carbon nanotube array was dragged and rotated in a direction perpendicular to the growth direction thereof was 2000 rpm.
In one embodiment, the carbon nanotube fibers have a diameter of 10 μm to 200 μm.
In one embodiment, the length of the carbon nanotube fiber is 100m to 6000 m. The length of the carbon nanotube fiber is not limited to the above length, and may be set as needed.
The preparation method of the carbon nanotube fiber comprises the steps of grafting a high molecular polymer or a decomposition product of the high molecular polymer onto the surface of the carbon nanotube array by using ultraviolet light, wherein the high molecular polymer is a copolymer of a 2-oxazoline monomer and a nitrogen-containing heterocyclic monomer, the 2-oxazoline monomer is at least one selected from 2-vinyl-2-oxazoline and 5-methyl-2-vinyl-2-oxazoline, and the nitrogen-containing heterocyclic monomer is at least one selected from N-acryloyl morpholine and N-vinyl caprolactam, so as to increase the distance between the carbon nanotubes, reduce the agglomeration caused by van der Waals force between the carbon nanotubes, obtain a modified carbon nanotube array which is easy to disperse, and further lower the fiber density of the carbon nanotube fiber prepared by using the carbon nanotubes, the cloth prepared by the carbon nanotube fiber is softer. Tests prove that the density of the carbon nano tube fiber prepared by adopting the modified carbon nano tube array is 1.6g/cm2～2.0g/cm2And the density is low, and the method can be used for preparing cloth with high quality.
In addition, the preparation method does not need to disperse the carbon nanotube array in a solvent for subsequent treatment, does not damage the array structure of the carbon nanotube array, is favorable for ensuring the mechanical properties of the modified carbon nanotube array and the carbon nanotube fiber, and avoids the harm to human bodies and the environment caused by using toxic reagents. In addition, in general, the structure of the carbon nanotubes is damaged to some extent during the spinning process of the carbon nanotubes, so as to affect the mechanical properties of the carbon nanotubes. In the research, the carbon nanotube fiber obtained by optimizing the high molecular polymer and the experimental parameters has lower density and better tensile strength.
Finally, the preparation method takes the high molecular polymer as the raw material to prepare the modified carbon nanotube array, is convenient for operation and reaction control, can directly modify the high molecular polymer on the surface of the carbon nanotube array, does not need multiple modification and treatment, reduces reaction procedures, is beneficial to improving the reaction efficiency and reducing the synthesis cost, and simultaneously, because the preparation method does not need to disperse the carbon nanotube array in a solvent and then carry out subsequent treatment, namely, does not need to remove the solvent, the process is simplified, meanwhile, no solvent and other residues exist, and the purity of the modified carbon nanotube array is higher.
The following are portions of specific embodiments.
Unless otherwise specified, the following examples contain no other components not specifically indicated except for inevitable impurities. The first substrate is an alumina plate. The second substrate is a copper sheet. When the first substrate with the carbon nano tube array and the second substrate with the high molecular polymer are subjected to ultraviolet irradiation treatment, the ultraviolet light is monochromatic light with the bandwidth of 298 nm.
Example 1
(1) Taking a first substrate, depositing a catalyst layer with the thickness of 20nm on the first substrate, wherein the catalyst layer is a mixed material of nickel and cobalt (the mass ratio of nickel to cobalt is 1: 1), placing the first substrate in a chemical vapor deposition reaction furnace, passing nitrogen, heating to 900 ℃, introducing a carbon source gas (the carbon source gas comprises ethylene and hexane, and the gas partial pressure ratio of ethylene to hexane is 1.25:1) into the chemical vapor deposition reaction furnace, controlling the flow of the carbon source gas at 15L/min, reacting for 25min, and enabling the surface of the first substrate to be completely covered with a carbon nanotube array which is a single-wall carbon nanotube array, wherein the length of the carbon nanotube array is 650 mu m, and the diameter of the carbon nanotube in the carbon nanotube array is 15 nm.
(2) A second substrate was taken, and a high molecular polymer film having a thickness of 1mm was formed on the second substrate. The preparation process of the high molecular polymer is as follows: polymerizing 2-oxazoline monomers and nitrogen-containing heterocyclic monomers for 50min under the irradiation of ultraviolet light with the power of 55W, and controlling the reaction temperature to be 20 ℃ to obtain reactants; and adding a solvent into the reactant, carrying out solid-liquid separation, collecting the precipitate, and drying the precipitate to obtain the high molecular polymer. The 2-oxazoline monomer is 2-vinyl-2-oxazoline, the nitrogen-containing heterocyclic monomer is N-acryloyl morpholine, and the molar ratio of the 2-oxazoline monomer to the nitrogen-containing heterocyclic monomer is 3.2. The weight average molecular weight of the high molecular weight polymer was 3500. The solvent is carbon tetrachloride.
(3) A first substrate formed with carbon nanotube array and a polymerThe second substrates are arranged in the reaction chamber side by side, the first substrate with the carbon nanotube array and the second substrate with the high molecular polymer are positioned on the same horizontal plane, the carbon nanotube array is contacted with the high molecular polymer, the reaction chamber is vacuumized until the air pressure is reduced to 10-2After the Torr is carried out, introducing nitrogen, keeping the flow rate of the nitrogen at 2L/min, carrying out ultraviolet irradiation treatment on a first substrate on which a carbon nanotube array is formed and a second substrate on which a high molecular polymer is formed, wherein the distance between an ultraviolet light source and the first substrate on which the carbon nanotube array is formed and the second substrate on which the high molecular polymer is formed is 2mm, the irradiation power of the ultraviolet light is 35mW, the ultraviolet light is monochromatic narrow-band light with the irradiation wavelength of 196nm, and the irradiation time is 35 min; and closing the ultraviolet light assembly, and exposing the first substrate to the nitrogen atmosphere until the first substrate is naturally cooled to obtain the modified carbon nanotube array.
(4) And clamping the modified carbon nanotube array from the edge of the modified carbon nanotube array by using a clamping tool, dragging the modified carbon nanotube array along a growth direction vertical to the modified carbon nanotube array, and rotating the modified carbon nanotube array to obtain the carbon nanotube fiber. When the modified carbon nanotube array is clamped from the edge of the modified carbon nanotube array, the clamping width is 200 μm. The drawing speed was 0.5mm/s and the rotational speed was 3000 rpm.
Example 2
(1) Taking a first substrate, depositing and forming a catalyst layer with the thickness of 23nm on the first substrate, wherein the catalyst layer is a mixed material of iron, nickel and cobalt (the mass ratio of nickel to cobalt is 1: 1), placing the first substrate in a chemical vapor deposition reaction furnace, passing nitrogen, heating to 550 ℃, introducing a carbon source gas (the carbon source gas comprises ethylene and hexane, and the gas partial pressure ratio of ethylene to hexane is 8:1) into the chemical vapor deposition reaction furnace, controlling the flow of the carbon source gas at 5L/min, reacting for 10min, and enabling the surface of the first substrate to be completely covered with a carbon nanotube array which is a single-wall carbon nanotube array, wherein the length of the carbon nanotube array is 1180 mu m, and the diameter of the carbon nanotubes in the carbon nanotube array is 15 nm.
(2) A second substrate was taken, and a polymer film having a thickness of 5mm was formed on the second substrate. The preparation process of the high molecular polymer is as follows: polymerizing 2-oxazoline monomers and nitrogen-containing heterocyclic monomers for 30min under the irradiation of ultraviolet light with the power of 45W, and controlling the reaction temperature to be 45 ℃ to obtain reactants; and adding a solvent into the reactant, carrying out solid-liquid separation, collecting the precipitate, and drying the precipitate to obtain the high molecular polymer. Wherein, the 2-oxazoline monomer is 5-methyl-2-vinyl-2-oxazoline, the nitrogen-containing heterocyclic monomer is N-vinyl caprolactam, and the molar ratio of the 2-oxazoline monomer to the nitrogen-containing heterocyclic monomer is 0.75. The weight average molecular weight of the high molecular weight polymer was 30000. The solvent is tetrahydrofuran.
(3) Placing a first substrate formed with a carbon nanotube array and a second substrate formed with a high molecular polymer in a reaction chamber side by side, wherein the first substrate formed with the carbon nanotube array and the second substrate formed with the high molecular polymer are in the same horizontal plane, the carbon nanotube array and the high molecular polymer are contacted, and the reaction chamber is vacuumized until the air pressure is reduced to 10-2After the Torr is carried out, introducing nitrogen, keeping the flow rate of the nitrogen at 3L/min, carrying out ultraviolet irradiation treatment on a first substrate on which a carbon nanotube array is formed and a second substrate on which a high molecular polymer is formed, wherein the distance between an ultraviolet light source and the first substrate on which the carbon nanotube array is formed and the second substrate on which the high molecular polymer is formed is 10mm, the irradiation power of the ultraviolet light is 15mW, the ultraviolet light is monochromatic narrow-band light with the irradiation wavelength of 350nm, and the irradiation time is 10 min; and closing the ultraviolet light assembly, and exposing the first substrate to the nitrogen atmosphere until the first substrate is naturally cooled to obtain the modified carbon nanotube array.
(4) And clamping the modified carbon nanotube array from the edge of the modified carbon nanotube array by using a clamping tool, dragging the modified carbon nanotube array along a growth direction vertical to the modified carbon nanotube array, and rotating the modified carbon nanotube array to obtain the carbon nanotube fiber. When the modified carbon nanotube array is clamped from the edge of the modified carbon nanotube array, the clamping width is 50 μm. The drawing speed was 0.05mm/s and the rotational speed was 1000 rpm.
Example 3
(1) Taking a first substrate, depositing a catalyst layer with the thickness of 21nm on the first substrate, wherein the catalyst layer is a mixed material of iron, nickel and cobalt (the mass ratio of nickel to cobalt is 1: 1), placing the first substrate in a chemical vapor deposition reaction furnace, passing nitrogen, heating to 700 ℃, introducing a carbon source gas (the carbon source gas comprises ethylene and hexane, and the gas partial pressure ratio of ethylene to hexane is 4:1) into the chemical vapor deposition reaction furnace, controlling the flow of the carbon source gas at 10L/min, reacting for 20min, and enabling the surface of the first substrate to be completely covered with a carbon nanotube array which is a single-wall carbon nanotube array, wherein the length of the carbon nanotube array is 800 mu m, and the diameter of the carbon nanotube in the carbon nanotube array is 12 nm.
(2) A second substrate was taken, and a polymer film having a thickness of 3mm was formed on the second substrate. The preparation process of the high molecular polymer is as follows: polymerizing 2-oxazoline monomers and nitrogen-containing heterocyclic monomers for 40min under the irradiation of ultraviolet light with the power of 50W, and controlling the reaction temperature to be 30 ℃ to obtain reactants; adding a solvent into the reactant, carrying out solid-liquid separation, collecting the precipitate, and drying the precipitate to obtain a high molecular polymer; the 2-oxazoline monomer is composed of 2-vinyl-2-oxazoline and 5-methyl-2-vinyl-2-oxazoline, and the molar ratio of the 2-vinyl-2-oxazoline to the 5-methyl-2-vinyl-2-oxazoline is 1; the nitrogen-containing heterocyclic monomer consists of N-acryloyl morpholine and N-vinyl caprolactam, and the molar ratio of the N-acryloyl morpholine to the N-vinyl caprolactam is 1; the molar ratio of the 2-oxazoline monomer to the nitrogen-containing heterocyclic monomer is 2; the weight average molecular weight of the high molecular weight polymer was 15000. The solvent is carbon dichloride.
(3) Placing a first substrate formed with a carbon nanotube array and a second substrate formed with a high molecular polymer in a reaction chamber side by side, wherein the first substrate formed with the carbon nanotube array and the second substrate formed with the high molecular polymer are in the same horizontal plane, the carbon nanotube array and the high molecular polymer are contacted, and the reaction chamber is vacuumized until the air pressure is reduced to 10-2Introducing nitrogen after Torr, keeping the flow rate of the nitrogen at 2.5L/min, performing ultraviolet irradiation treatment on the first substrate with the carbon nanotube array and the second substrate with the high molecular polymer, wherein the distance between an ultraviolet light source and the first substrate with the carbon nanotube array and the second substrate with the high molecular polymer is 5mm, and the ultraviolet light is applied to the first substrate and the second substrateThe irradiation power is 25mW, the ultraviolet light is monochromatic narrow-band light with the irradiation wavelength of 218nm, and the irradiation time is 23 min; and closing the ultraviolet light assembly, and exposing the first substrate to the nitrogen atmosphere until the first substrate is naturally cooled to obtain the modified carbon nanotube array.
(4) And clamping the modified carbon nanotube array from the edge of the modified carbon nanotube array by using a clamping tool, dragging the modified carbon nanotube array along a growth direction vertical to the modified carbon nanotube array, and rotating the modified carbon nanotube array to obtain the carbon nanotube fiber. When the modified carbon nanotube array is clamped from the edge of the modified carbon nanotube array, the clamping width is 130 μm. The drawing speed was 0.3mm/s and the rotational speed was 2000 rpm.
Example 4
The carbon nanotube fiber of this example was prepared in substantially the same manner as in example 3, except that: the 2-oxazoline monomer is composed of 2-vinyl-2-oxazoline and 5-methyl-2-vinyl-2-oxazoline, and the molar ratio of the 2-vinyl-2-oxazoline to the 5-methyl-2-vinyl-2-oxazoline is 0.7; the nitrogen-containing heterocyclic monomer consists of N-acryloyl morpholine and N-vinyl caprolactam, and the molar ratio of the N-acryloyl morpholine to the N-vinyl caprolactam is 1.2.
Example 5
The carbon nanotube fiber of this example was prepared in substantially the same manner as in example 3, except that: the 2-oxazoline monomer is composed of 2-vinyl-2-oxazoline and 5-methyl-2-vinyl-2-oxazoline, and the molar ratio of the 2-vinyl-2-oxazoline to the 5-methyl-2-vinyl-2-oxazoline is 1.3; the nitrogen-containing heterocyclic monomer consists of N-acryloyl morpholine and N-vinyl caprolactam, and the molar ratio of the N-acryloyl morpholine to the N-vinyl caprolactam is 0.8.
Example 6
The carbon nanotube fiber of this example was prepared in substantially the same manner as in example 3, except that: carrying out free radical polymerization reaction on a 2-oxazoline monomer to obtain a reactant; adding a solvent into the reactant, carrying out solid-liquid separation, collecting the precipitate, and drying the precipitate to obtain a high molecular polymer; the 2-oxazoline monomer is composed of 2-vinyl-2-oxazoline and 5-methyl-2-vinyl-2-oxazoline, and the molar ratio of the 2-vinyl-2-oxazoline to the 5-methyl-2-vinyl-2-oxazoline is 1.
Example 7
The carbon nanotube fiber of this example was prepared in substantially the same manner as in example 3, except that: carrying out free radical polymerization on a nitrogen-containing heterocyclic monomer to obtain a reactant; adding a solvent into the reactant, carrying out solid-liquid separation, collecting the precipitate, and drying the precipitate to obtain a high molecular polymer; the nitrogen-containing heterocyclic monomer consists of N-acryloyl morpholine and N-vinyl caprolactam, and the molar ratio of the N-acryloyl morpholine to the N-vinyl caprolactam is 1.
Example 8
(1) Taking a first substrate, depositing a catalyst layer with the thickness of 21nm on the first substrate, wherein the catalyst layer is a mixed material of iron, nickel and cobalt (the mass ratio of nickel to cobalt is 1: 1), placing the first substrate in a chemical vapor deposition reaction furnace, passing nitrogen, heating to 700 ℃, introducing a carbon source gas (the carbon source gas comprises ethylene and hexane, and the gas partial pressure ratio of ethylene to hexane is 4:1) into the chemical vapor deposition reaction furnace, controlling the flow of the carbon source gas at 10L/min, reacting for 20min, and enabling the surface of the first substrate to be completely covered with a carbon nanotube array which is a single-wall carbon nanotube array, wherein the length of the carbon nanotube array is 800 mu m, and the diameter of the carbon nanotube in the carbon nanotube array is 12 nm.
(2) Clamping the carbon nanotube array from the edge of the carbon nanotube array by using a clamping tool, dragging and rotating the carbon nanotube array along a direction perpendicular to the growth direction of the carbon nanotube array to obtain primary fibers, and placing the primary fibers on a first substrate. When the carbon nanotube array was gripped from the edge of the carbon nanotube array, the gripping width was 130 μm. The drawing speed was 0.3mm/s and the rotational speed was 2000 rpm.
(3) A second substrate was taken, and a polymer film having a thickness of 3mm was formed on the second substrate. The preparation process of the high molecular polymer is as follows: polymerizing 2-oxazoline monomers and nitrogen-containing heterocyclic monomers for 40min under the irradiation of ultraviolet light with the power of 50W, and controlling the reaction temperature to be 30 ℃ to obtain reactants; adding a solvent into the reactant, carrying out solid-liquid separation, collecting the precipitate, and drying the precipitate to obtain a high molecular polymer; the 2-oxazoline monomer is composed of 2-vinyl-2-oxazoline and 5-methyl-2-vinyl-2-oxazoline, and the molar ratio of the 2-vinyl-2-oxazoline to the 5-methyl-2-vinyl-2-oxazoline is 1; the nitrogen-containing heterocyclic monomer consists of N-acryloyl morpholine and N-vinyl caprolactam, and the molar ratio of the N-acryloyl morpholine to the N-vinyl caprolactam is 1; the molar ratio of the 2-oxazoline monomer to the nitrogen-containing heterocyclic monomer is 2; the weight average molecular weight of the high molecular weight polymer was 15000. The solvent is carbon dichloride.
(4) Placing a first substrate with primary fibers and a second substrate with high molecular polymer in a reaction cavity side by side, wherein the first substrate with the primary fibers and the second substrate with the high molecular polymer are in the same horizontal plane, the primary fibers and the high molecular polymer are in contact, and vacuumizing the reaction cavity until the air pressure is reduced to 10-2After the Torr is carried out, introducing nitrogen, keeping the flow rate of the nitrogen at 2.5L/min, carrying out ultraviolet irradiation treatment on the first substrate with the primary fibers and the second substrate with the high molecular polymer, wherein the distance between an ultraviolet source and the first substrate with the primary fibers and the second substrate with the high molecular polymer is 5mm, the irradiation power of ultraviolet is 25mW, the ultraviolet is monochromatic narrow-band light with the wavelength of 218nm, and the irradiation time is 23 min; and closing the ultraviolet light assembly, and exposing the first substrate to the nitrogen atmosphere until the first substrate is naturally cooled to obtain the carbon nanotube fiber.
Example 9
(1) Taking a first substrate, depositing a catalyst layer with the thickness of 21nm on the first substrate, wherein the catalyst layer is a mixed material of nickel and cobalt (the mass ratio of nickel to cobalt is 1: 1), placing the first substrate in a chemical vapor deposition reaction furnace, passing nitrogen, heating to 700 ℃, introducing a carbon source gas (the carbon source gas comprises ethylene and hexane, and the gas partial pressure ratio of ethylene to hexane is 4:1) into the chemical vapor deposition reaction furnace, controlling the flow of the carbon source gas at 10L/min, reacting for 20min, and enabling the surface of the first substrate to be completely covered with a carbon nanotube array which is a single-wall carbon nanotube array, wherein the length of the carbon nanotube array is 800 mu m, and the diameter of the carbon nanotube in the carbon nanotube array is 12 nm.
(2) A second substrate was taken, and a polymer film having a thickness of 3mm was formed on the second substrate. The high molecular polymer is polystyrene.
(3) Placing a first substrate with a carbon nano tube array and a second substrate with a high molecular polymer in a reaction cavity side by side, wherein the first substrate with the carbon nano tube array and the second substrate with the high molecular polymer are positioned on the same horizontal plane, the first substrate with the carbon nano tube array and the second substrate with the high molecular polymer are contacted, and vacuumizing the reaction cavity until the air pressure is reduced to 10 DEG-2After the Torr is carried out, introducing nitrogen, keeping the flow rate of the nitrogen at 2.5L/min, carrying out ultraviolet irradiation treatment on the first substrate with the carbon nanotube array and the second substrate with the high molecular polymer, wherein the distance between an ultraviolet source and the first substrate with the carbon nanotube array and the second substrate with the high molecular polymer is 5mm, the irradiation power of the ultraviolet is 25mW, the ultraviolet is monochromatic narrow-band light with the wavelength of 218nm, and the irradiation time is 35 min; and closing the ultraviolet light assembly, and exposing the first substrate to the nitrogen atmosphere until the first substrate is naturally cooled to obtain the modified carbon nanotube array.
(4) And clamping the modified carbon nanotube array from the edge of the modified carbon nanotube array by using a clamping tool, dragging the modified carbon nanotube array along a growth direction vertical to the modified carbon nanotube array, and rotating the modified carbon nanotube array to obtain the carbon nanotube fiber. When the modified carbon nanotube array is clamped from the edge of the modified carbon nanotube array, the clamping width is 130 μm. The drawing speed was 0.3mm/s and the rotational speed was 2000 rpm.
And (3) testing:
the density of the carbon nanotube fibers and the tensile strength of the carbon nanotubes of examples 1 to 9 were measured. The results are shown in Table 1.
Specifically, the density of the carbon nanotube fiber was measured using the archimedes method (canola oil);
the tensile strength of the carbon nanotube fibers was tested using a tensile test method.
TABLE 1 Density and tensile Strength of carbon nanotube fibers of examples 1-9
Density (g/cm)2) Tensile Strength (GPa)
Example 1 2.00 7.62
Example 2 2.05 8.06
Example 3 1.60 8.65
Example 4 1.82 7.37
Example 5 1.77 7.59
Example 6 2.33 7.58
Example 7 2.18 7.88
Example 8 1.96 8.78
Example 9 1.71 2.98
As can be seen from Table 1, the carbon nanotube fibers of examples 1 to 5 had a density of 1.6g/cm2～2.0g/cm2The tensile strength is 7.5 GPa-8.7 GPa, which shows that the carbon nanotube fiber with lower density and higher tensile strength can be prepared by preparing the modified carbon nanotube according to the embodiment, so that the carbon nanotube fiber can be used for preparing a softer cloth with better elasticity.
The tensile strength of the carbon nanotube fibers of examples 6 to 7 is lower than that of example 3, and the density of the carbon nanotube fibers of examples 6 to 7 is higher than that of example 3, which shows that the high molecular polymer formed by polymerizing the 2-oxazoline monomer and the nitrogen-containing heterocyclic monomer is more favorable for improving the tensile strength of the carbon nanotube fibers, reducing the density of the carbon nanotube fibers, and obtaining a softer cloth with better elasticity. The tensile strength of the carbon nanotube fiber of example 8 is approximately equivalent to that of example 3, but the density of the carbon nanotube fiber of example 8 is increased by 23% compared to example 3, which shows that the carbon nanotube fiber is prepared and modified to reduce the density of the carbon nanotube fiber, so as to obtain a softer cloth. The density of the carbon nanotube fiber of example 9 is approximately equivalent to that of example 3, but the tensile strength of the carbon nanotube fiber of example 9 is significantly lower than that of example 3, which shows that the selection of the copolymer of the 2-oxazoline monomer and the nitrogen-containing heterocyclic monomer as the high molecular polymer is more advantageous for ensuring the tensile strength of the carbon nanotube fiber.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.

Claims (10)

1. A preparation method of a modified carbon nanotube array is characterized by comprising the following steps:
forming a carbon nanotube array on a first substrate;
forming a high molecular polymer on the second substrate, wherein the high molecular polymer is a copolymer of a 2-oxazoline monomer and a nitrogen-containing heterocyclic monomer, the 2-oxazoline monomer is selected from at least one of 2-vinyl-2-oxazoline and 5-methyl-2-vinyl-2-oxazoline, and the nitrogen-containing heterocyclic monomer is selected from at least one of N-acryloyl morpholine and N-vinyl caprolactam; and
under the protective gas atmosphere, carrying out ultraviolet irradiation treatment on the first substrate forming the carbon nanotube array and the second substrate forming the high molecular polymer so as to carry out grafting reaction on the high molecular polymer and the carbon nanotube array to obtain a modified carbon nanotube array;
the preparation method of the high molecular polymer comprises the following steps: carrying out free radical polymerization reaction on the 2-oxazoline monomer and the nitrogen-containing heterocyclic monomer to obtain a reactant; adding a solvent into the reactant, and collecting the precipitate after solid-liquid separation to obtain the high molecular polymer;
wherein: the weight average molecular weight of the high molecular polymer is 3500-30000;
the molar ratio of the 2-oxazoline monomer to the nitrogen-containing heterocyclic monomer is 0.75-3.2.
2. The method for preparing a modified carbon nanotube array according to claim 1, wherein the irradiation power of the ultraviolet light is 15mW to 35mW, the ultraviolet light is monochromatic narrowband light having an irradiation wavelength of 196nm to 350nm, and the irradiation time of the ultraviolet light is 10min to 35 min.
3. The method of claim 1, wherein the weight average molecular weight of the high molecular weight polymer is 5000 to 20000.
4. The method for preparing the modified carbon nanotube array of claim 3, wherein the step of performing radical polymerization on the 2-oxazoline monomer and the nitrogen-containing heterocyclic monomer comprises the following steps: and carrying out polymerization reaction on the 2-oxazoline monomer and the nitrogen-containing heterocyclic monomer under the irradiation of ultraviolet light, controlling the reaction temperature to be 20-45 ℃, controlling the power of the ultraviolet light to be 45-55W, and controlling the reaction time to be 30-50 min.
5. The method of claim 1, wherein the molar ratio of N-acryloyl morpholine to N-vinyl caprolactam is 0.8-1.2.
6. The method of claim 1, wherein the step of forming the carbon nanotube array on the first substrate comprises:
depositing a catalyst layer on the first substrate; and
heating the first substrate forming the catalyst layer to 550-900 ℃ in a protective gas atmosphere, and introducing a carbon source gas for reaction to obtain the carbon nanotube array; the carbon source gas comprises ethylene and hexane, the gas partial pressure ratio of the ethylene to the hexane is 1.25: 1-8: 1, the flow rate of the carbon source gas is 5-15 mL/min, and the time for introducing the carbon source gas to react is 10-25 min.
7. A modified carbon nanotube array, characterized in that it is prepared by the method for preparing a modified carbon nanotube array according to any one of claims 1 to 6.
8. A method for producing a carbon nanotube fiber, comprising spinning the modified carbon nanotube array of claim 7 to obtain a carbon nanotube fiber.
9. A carbon nanotube fiber produced by the method for producing a carbon nanotube fiber according to claim 8.
10. Use of the carbon nanotube fiber of claim 9 in the preparation of a cloth.
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