CN115045107A - Preparation method of antistatic carbon nanotube modified wool fiber - Google Patents
Preparation method of antistatic carbon nanotube modified wool fiber Download PDFInfo
- Publication number
- CN115045107A CN115045107A CN202210552603.7A CN202210552603A CN115045107A CN 115045107 A CN115045107 A CN 115045107A CN 202210552603 A CN202210552603 A CN 202210552603A CN 115045107 A CN115045107 A CN 115045107A
- Authority
- CN
- China
- Prior art keywords
- carbon nanotube
- dopamine
- wool fiber
- wool
- fibers
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- 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
- 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
- D06M11/58—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 nitrogen or compounds thereof, e.g. with nitrides
- D06M11/59—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 nitrogen or compounds thereof, e.g. with nitrides with ammonia; with complexes of organic amines with inorganic substances
- D06M11/60—Ammonia as a gas or in solution
-
- 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
- D06M15/61—Polyamines polyimines
-
- 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
- D06M2101/10—Animal fibres
- D06M2101/12—Keratin fibres or silk
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
The invention relates to a preparation method of antistatic carbon nanotube modified wool fibers, and belongs to the technical field of preparation of conductive fibers. The preparation method comprises the following steps: (1) pretreating the wool fibers; (2) modifying the pretreated wool fibers by (dopamine) or (dopamine-like) or derivatives thereof; (3) and (3) soaking the wool fiber modified by dopamine (like) or derivatives thereof in the dispersion liquid of the carbon nano tube or the derivatives thereof, drying, washing and drying to obtain the carbon nano tube modified wool fiber. The addition of dopamine or dopamine derivatives improves the problems of poor dispersibility and easy agglomeration of the carbon nano tubes, solves the problem of bonding firmness of the conductive filler and the matrix in the wool fibers, and simultaneously forms a continuous conductive path in the wool fiber matrix, thereby greatly improving the antistatic property and the water washing resistance of the wool fibers.
Description
Technical Field
The invention belongs to the technical field of conductive fiber preparation, and particularly relates to a preparation method of antistatic carbon nanotube modified wool fibers.
Background
The textile material is an electrical insulator material, has high resistance generally, especially has fibers such as wool, low polyester, acrylic fiber, polyvinyl chloride fiber and the like with good elasticity, strong hygroscopicity and good heat retention, is widely applied to textile raw materials, plays an increasingly important role in textile processing, and is characterized by plump texture, smooth hand feeling, good drapability, noble, light, comfortable and the like, so that the textile material is popular with consumers all the time. However, during the textile process, there is intimate contact and friction between the fibers or between the fibers and the machine parts. Resulting in the transfer of charge to the surface of the object and the consequent generation of static electricity. The fibers with the same charge repel each other, and the fibers with different charges attract the machine parts, so that the sliver is hairy, the fiber hairiness is increased, the package forming is poor, the fibers are adhered to the machine parts, the yarn broken ends are increased, and a dispersive streak is formed on the cloth surface. After the fibers are charged, a large amount of dust is adsorbed, the fibers are easy to stain, and the fibers and human bodies, and the fibers can also be entangled or generate electric sparks. Therefore, the electrostatic interference affects the smooth proceeding of the fiber processing, and further affects the wearability thereof. When the static electricity phenomenon is serious, the static voltage is up to thousands of volts, sparks are generated due to discharge, and fire disasters are caused, so that serious consequences are caused. Therefore, the effective reduction or removal of the electrostatic phenomenon in the fiber material is a technical problem to be solved at present.
In recent years, attention has been paid to electrostatic hazard at home and abroad. People make a great deal of research and test on the aspect of fiber antistatic property, and obtain remarkable results, particularly make a great deal of attempts in the technical field of antistatic wool fiber preparation. The current methods for preparing antistatic wool fibers are mainly three: firstly, an antistatic agent (such as nano MgO) is sprayed or impregnated on the surface of wool fibers, a layer of antistatic agent can be formed on the surface of the wool fibers, but the antistatic performance is temporary, and the antistatic agent falls off from the surface of the fibers after washing, so that the durability of the antistatic effect of the antistatic agent is influenced; and secondly, the conductive fiber with good conductivity is added in the process of processing the wool fiber product in a blending or embedding manner, so that the volume specific resistance of the fiber can be greatly reduced, and further, the generation of static electricity can be effectively prevented. Patent CN112239905A mentions a preparation process of blended wool conductive fibers, wherein blended wool conductive fibers are successfully prepared by blending Belltron organic conductive fibers and wool fibers, and the process not only can improve the fiber processing operation condition, but also can produce the blended wool fibers with excellent antistatic performance. However, the embedding of the Belltron organic conductive fiber in the patent can greatly reduce the original excellent characteristics of the cashmere fiber due to the influence of the fineness and the flexibility of the Belltron organic conductive fiber, so that the application of the Belltron organic conductive fiber is limited within a certain range; thirdly, the nano-filler (such as carbon nano-tube) is bonded to the wool fiber macromolecules by a physical or chemical modification method by means of the conductivity of the nano-filler, so that the purpose of lasting antistatic function is achieved. In-situ polymerization of dopamine is equally adopted in Liu, so that a layer of discontinuous dopamine hydrophilic film is covered on the surface of wool fibers, the hydrophobicity of the surface layer of the fibers is reduced, and meanwhile, the carbon nanotubes are loaded by utilizing the super-strong adhesion of the dopamine, and the antistatic effect is achieved by utilizing the conductivity of the carbon nanotubes. However, the problem of adhesion effect between conductive materials and wool fiber matrix is not mentioned (dopamine-carbon nanotubes for composite antistatic finishing of wool fabrics [ J ] knitting industry, 2020(04): 41-44.).
The bonding force between the conductive filler (such as carbon nano tube) and the matrix in the antistatic wool fiber prepared by the existing method is poor, and the bonding degree between the conductive layer and the wool fiber matrix is not high, so that the conductive layer falls off due to the change of external environment (such as high temperature and humidity, air and concentrated alkali action and the like), and the antistatic durability and water washing resistance of the antistatic wool fiber are further influenced.
Disclosure of Invention
The invention aims to solve the technical problem of providing a preparation method of antistatic carbon nanotube modified wool fibers, which solves the problem of bonding firmness of a conductive filler and a matrix of the wool fibers, and simultaneously forms a continuous conductive path in the matrix of the wool fibers, thereby greatly improving the antistatic performance and the washing resistance of the wool fibers.
In order to solve the technical problems, the invention adopts a technical scheme that: the preparation method of the antistatic carbon nanotube modified wool fiber comprises the following steps:
(1) performing ammonia/salt pretreatment on the wool fibers to obtain the wool fibers subjected to the ammonia/salt pretreatment;
(2) modifying the wool fibers pretreated by the ammonia/salt in the step (1) by using dopamine (class) or derivatives thereof to obtain the wool fibers modified by the dopamine (class) or derivatives thereof;
(3) and (3) soaking the wool fiber modified by the dopamine (like) or the derivative thereof obtained in the step (2) in a dispersion liquid of the carbon nano tube or the derivative thereof, drying, washing and drying to obtain the carbon nano tube modified wool fiber.
Further, the ammonia/salt pretreatment in the step (1) is to immerse the wool fibers in a solution containing 0.5-5.5g/L of ammonia water and 5-60 g/L of salt, immerse the wool fibers at a constant temperature of 50 ℃ for 40-90min, take out the wool fibers, wash the wool fibers with water, dry the wool fibers and weigh the wool fibers for later use, wherein the bath ratio is 1: 50.
Further, the salt in the step (1) is one of sodium chloride, calcium chloride, sodium sulfate and the like.
Further, the dopamine (like) or the derivative thereof in the step (2) comprises one or more of gallic acid, dopamine hydrochloride, polydopamine (DATA), N-3, 4-Dihydroxyphenethylacrylamide (DAA) and MOA.
Further, the modification in the step (2) is that the wool fiber after ammonia/salt pretreatment is soaked in a mixed solution containing dopamine or derivatives thereof and tris buffer solution, the pH value of the solution is 8-10, and the wool fiber is obtained by water washing and drying; wherein the concentration of the dopamine or the derivative thereof in the mixed solution is 0.5-6.5mg/m L; the concentration of tris buffer was 0.5-4.5M.
Further, the dipping in the modification process in the step (2) is carried out at room temperature of 20-30 ℃ and under the magnetic stirring of 60-100rpm for 24-48 h.
Further, the concentration of the carbon nano tube and the derivative thereof in the step (3) is 5-45 mM.
Further, the temperature of the impregnation in the step (3) is 65-85 ℃ and the time is 30-90 min.
Further, the pH of the dispersion of the carbon nanotubes or the derivatives thereof in the step (3) is 3.5 to 6.5.
Further, the carbon nano-tube and the derivative thereof in the step (3) comprise one or more of aminated carbon nano-tube, acidified carbon nano-tube, acrylamide aminated carbon nano-tube (AM-CNTs) and 2, 2-dimethylolpropionic acid carbon nano-tube (DMPA-CNTs).
The advantages of the invention are as follows:
(1) the antistatic carbon nanotube modified wool fiber is prepared by taking the antistatic carbon nanotube modified wool fiber modified by dopamine or derivative functions thereof as a matrix and utilizing an alternate intercalation assembly composite technology on the surface of the matrix; the modification of the dopamine(s) or the derivatives thereof means that amino groups, imino groups and phenolic hydroxyl groups in the dopamine(s) or the derivatives thereof can be bonded with carboxyl groups, amino groups and hydroxyl groups in wool fibers through coordination, hydrogen bond association, electrostatic interaction, hydrophobic interaction or even covalent reaction, and the modified dopamine(s) or the derivatives thereof are firmly adhered to the surfaces of the wool fibers; the alternate intercalation assembly composite technology is a process of alternately intercalating two different substances by a bonding driving force to obtain a highly-oriented and continuous conductive path, and the alternate intercalation effect not only increases the contact area of the carbon nano tube or the derivative thereof and the matrix, but also enhances the adhesion effect of the carbon nano tube or the derivative thereof and the matrix.
(2) The antistatic carbon nanotube modified wool fiber has an interface dynamic synergistic bonding mode: amino, imino, phenolic hydroxyl and the like in the polydopamine on the surface of the substrate and oxygen-containing groups in the conductive filler deposited on the substrate form covalent bonds and non-covalent bonds in a cooperative bonding mode.
(3) The method for quickly depositing the dopamine not only solves the problems of dispersity and reunion of the conductive nano filler, but also enhances the adhesion between the conductive filler layer and the wool fibers, does not need a large amount of chemical adhesion reagents, and has the advantages of environmental friendliness, simplicity in operation and low cost compared with the existing chemical method.
(4) The antistatic carbon nanotube modified wool fiber prepared by adopting the alternate intercalation assembly composite technology not only enhances the adhesiveness between the conductive layer and the matrix, but also solves the problems of poor dispersibility and easy agglomeration of the carbon nanotube or the derivative thereof, enables the conductive filler to be uniformly dispersed, and provides a new idea for the development of the antistatic fiber. The preparation method has the advantages of wide applicability, strong flexibility, high efficiency and the like, is an excellent way for efficiently and controllably preparing the high-performance antistatic wool fiber, and is convenient for industrial production.
(5) The volume specific resistance of the antistatic carbon nanotube modified wool fiber prepared by the method is below 21.4 Ω & cm, and after 500 times of friction, the volume specific resistance is below 68.5 Ω & cm; after 150 times of water washing, the volume specific resistance is 56.7 Ω · cm; the modified wool fiber has good washing fastness and antistatic property and is suitable for preparing antistatic fabrics.
Drawings
Fig. 1 is a schematic diagram of a preparation process of an acidified carbon nanotube modified wool fiber according to embodiment 1 of the present invention.
FIG. 2 is a scanning electron microscope image of acidified carbon nanotube modified wool fibers of example 1; wherein a-b, c-d and e-f are respectively the electron microscope images of 100 micrometers and 50 micrometers of wool fibers, dopamine modified wool fibers and acidified carbon nanotube modified wool fibers.
FIG. 3 is an infrared spectrum of the wool fibers before and after modification, wherein a, b, and c are respectively the wool fibers, the dopamine-modified wool fibers, and the acidified carbon nanotube-modified wool fibers.
FIG. 4 is an XRD (X-ray diffraction) diagram of the wool fibers before and after modification, wherein a, b and c are respectively the wool fibers, the dopamine-modified wool fibers and the acidified carbon nanotube-modified wool fibers.
FIG. 5 shows a process for preparing an acidified carbon nanotube-modified wool fiber 1 according to example 1; wherein a and b are respectively the preparation process of the acidified carbon nanotube modified wool fiber and the synthesis mechanism of the acidified carbon nanotube and the dopamine 2 modified wool fiber 3.
FIG. 6 is a synthetic mechanism of acidified carbon nanotubes and polydopamine modified wool fibers of example 1; wherein 2 is polydopamine; 4 is a hydrogen bond; 3 is wool fiber; 1 is an acidified carbon nanotube; 5. 7 is pi-pi conjugation and 8 is a chemical bond (esterification).
Fig. 7 is a schematic view of a preparation process of an acidified carbon nanotube modified wool fiber according to embodiment 2 of the present invention.
FIG. 8 is a scanning electron microscope image of acidified carbon nanotube modified wool fibers of example 2; wherein a-b, c-d and e-f are respectively the electron microscope images of 100 mu m and 50 mu m of wool fibers, wool fibers modified by gallic acid and hexamethylenediamine, and acidified carbon nanotube modified wool fibers.
FIG. 9 is the infrared spectra of the wool fibers before and after modification, wherein a, b, c are respectively wool fibers, gallic acid and hexamethylenediamine modified wool fibers, and acidified carbon nanotube modified wool fibers.
Fig. 10 is an XRD chart of the wool fibers before and after modification, wherein a, b, and c are wool fibers, wool fibers modified with gallic acid in cooperation with hexamethylenediamine, and wool fibers modified with acidified carbon nanotubes, respectively.
FIG. 11 shows a process for preparing acidified CNT-modified wool 1 according to example 2; wherein a and b are respectively the preparation process of the acidified carbon nanotube modified wool fiber and the synthesis mechanism of the acidified carbon nanotube and the gallic acid 2 in cooperation with the hexamethylenediamine 3 modified wool fiber 4.
FIG. 12 is a synthetic mechanism of acidified carbon nanotubes and polydopamine modified wool fibers of example 2; wherein 2 is hexamethylenediamine; 5 is a hydrogen bond; 4 is wool fiber; 1 is an acidified carbon nanotube; 9 is amidation, 8 is hydroxylamino, 3 is hexamethylenediamine and 6 is esterification.
FIG. 13 is a scanning electron microscope image of acidified carbon nanotube-modified wool fibers of comparative example 3; wherein a-b and c-d are electron microscope images of the wool fibers and the acidified carbon nanotube modified wool fibers at 100 micrometers and 50 micrometers respectively.
FIG. 14 is an infrared spectrum of the wool fibers before and after modification, wherein a and b are respectively wool fibers and acidified carbon nanotube modified wool fibers.
FIG. 15 is an XRD pattern of the wool fibers before and after modification, wherein a and b are respectively wool fibers and acidified carbon nanotube modified wool fibers.
Detailed Description
In order to make the aforementioned objects, features and advantages of the present invention more comprehensible, embodiments accompanying figures are described in detail below.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, however, the present invention may be embodied in other specific forms than those described herein, and it will be apparent to those skilled in the art that the present invention may be practiced without departing from the spirit and scope of the present invention.
The wool fibers adopted in the embodiment are purchased from saussurea involucrate cashmere, and the carbon nanotube dispersion liquid is prepared by taking sodium dodecyl benzene sulfonate as a solvent, wherein the carbon nanotubes are purchased from Nanjing Xiancheng nanometer material science and technology limited; other solutions not specifically mentioned are those in which water is used as the solvent.
The preparation method of the acidified carbon nano tube comprises the following steps: mixing carbon nano tubes and concentrated nitric acid with the mass concentration of 75% according to the mass-volume ratio of 1 g: stirring and mixing 90mL of the mixture evenly, reacting for 12 hours at 135 ℃, filtering and washing the obtained product to be neutral, and drying in vacuum to obtain the acidified carbon nano tube.
The test method comprises the following steps:
and (3) friction resistance test: the test was performed with reference to the national standard GB/T21196.
Testing specific resistance: measuring the specific resistance value of the modified fiber by using a fiber specific resistance instrument, weighing 15g of fiber, uniformly filling the fiber into a fiber test box, and placing a tested fiber sample in an environment with room temperature and relative humidity of 65% +/-10% for balancing for 4h for testing.
Measurement of washing durability: the water washing durability test was performed with reference to literature (chengwenqing. preparation and performance of conductive cashmere fiber [ D ]. beijing clothing academy 2014).
Example 1: a method for preparing antistatic carbon nanotube modified wool fiber, comprising the following steps, as shown in fig. 1:
(1) soaking wool fibers in a solution containing ammonia water (2 g/L) and salt (10 g/L), soaking at a constant temperature of 50 ℃ for 60min, taking out, washing with water, drying, and weighing for later use, wherein the bath ratio is 1:50 to obtain the ammonia/salt pretreated wool fibers;
(2) immersing the wool fiber pretreated by ammonia/salt obtained in the step (1) in a mixed solution containing dopamine hydrochloride (2 mg/mL) and tris buffer solution (1M), wherein the pH value of the solution is 8.5; followed by magnetic stirring at 80rpm for 24h at room temperature 25 ℃;
(3) dipping the polydopamine modified wool fiber obtained in the step (2) in acidified carbon nanotube dispersion liquid 35mM, wherein the pH value of the solution is 4, the dipping temperature is 80 ℃, the dipping time is 60min, then, drying is carried out for 30min at the temperature of 60 ℃, and then, the dipping-drying operation is repeated for 3 times; the acidified carbon nanotube modified wool fiber is obtained, and the scanning electron microscope image is shown in fig. 2.
And (3) carrying out performance test and structure characterization on the obtained acidified carbon nanotube modified wool fiber, wherein the test results are as follows:
FIG. 3 is an infrared spectrum of wool fibers before and after modification. Through comparison, the N-H base stretching vibration (v N-H) of the three wool fibers is 3273.5cm -1 The N-H base flexural vibration (. delta.N-H) was 1514.30, and the C = O base flexural vibration (. nu.C = O) was 1630.5cm -1 There was no change in the characteristic absorption peak position of (a). The modification treatment of the acidified carbon nano tube can not damage the structure of the wool fiber, and the acidified carbon nano tube modified fiber is 1712cm -1 The C = O group stretching vibration characteristic peak of the acidified carbon nanotube appears, which indicates that the acidified carbon nanotube is successfully attached to the wool fiber. In addition, from the XRD test results of fig. 4, it was found that the modification of dopamine and acidified carbon nanotubes on the surface of wool fibers did not affect the structural properties thereof.
FIG. 5 shows the synthetic mechanism and chemical structure of dopamine and acidified carbon nanotubes and wool fibers, respectively; fig. 5 (a) and 5 (b) show the preparation process of the acidified carbon nanotube-modified wool fiber 1 and the synthesis mechanism of the acidified carbon nanotube and the dopamine 2-modified wool fiber 3, respectively. As can be seen from fig. 5: the prepared acidified carbon nanotube modified wool fiber has a covalent bond and non-covalent bond cooperative bonding action mode and a mesh conductive network structure.
As can be seen from fig. 6, the acidified carbon nanotube 1 can be intercalated in the matrix coated with the polydopamine 2 modified wool fiber 3 to serve as a nano space barrier, so that stacking of the acidified carbon nanotube is further inhibited, and the oxygen-containing group of the acidified carbon nanotube and the amine group, the imine group, the phenolic hydroxyl group and the like in the polydopamine 2 are also embedded in the matrix in a manner that the chemical bond 8 and the hydrogen bond 4 are cooperatively combined.
The method promotes the acidified carbon nanotubes to be uniformly and tightly adhered to the dopamine modified wool fiber substrate, enhances the adhesion effect between interfaces, and simultaneously improves the stability and durability of the acidified carbon nanotubes. In addition, regarding the construction of the mesh-like conductive network structure: on one hand, amino, imino, phenolic hydroxyl and the like in the polydopamine 1 on the surface of the matrix and hydroxyl, amino, carboxyl and other groups on the wool fiber form chemical bonds 8 and are in interface dynamic cooperative bonding with hydrogen bonds 4; on the other hand, the acidified carbon nano tube and the polydopamine are alternately intercalated on the wool fibers by the bonding driving force between the acidified carbon nano tube and the polydopamine, so that a highly-oriented and continuously-conductive reticular conductive network structure is obtained.
Tables 1 and 2 are the results of the friction and water wash resistance tests of the acidified carbon nanotube modified wool fibers, and it can be seen from tables 1 and 2 that: after 600 times of friction, the volume specific resistance of the acidified carbon nanotube modified wool fiber is only 84.50 Ω · cm; after being washed by water for 150 times, the volume specific resistance is only 56.7 Ω & cm, which indicates that the modified wool fiber has good washing fastness and antistatic property and is suitable for preparing antistatic fabrics.
TABLE 1 Friction resistance test results for acidified carbon nanotube modified wool fibers
TABLE 2 test results of water washing resistance of acidified carbon nanotube modified wool fibers
Example 2: a method for preparing antistatic carbon nanotube modified wool fiber, as shown in fig. 7, comprising the following steps:
(1) soaking wool fibers in a solution containing 2g/L of ammonia water and 10g/L of salt at a constant temperature of 50 ℃ for 60min, taking out, washing with water, drying, and weighing for later use, wherein the bath ratio is 1:50, so as to obtain the ammonia/salt pretreated wool fibers;
(2) immersing the wool fiber pretreated by ammonia/salt obtained in the step (1) in a mixed solution containing 2mg/mL of gallic acid, 1mg/mL of hexamethylene diamine and 1M of tris buffer solution, wherein the pH value of the solution is 8.5; followed by magnetic stirring at 80rpm for 24h at room temperature 25 ℃;
(3) dipping the polydopamine modified wool fiber obtained in the step (2) in acidified carbon nanotube dispersion liquid 35mM, wherein the pH value of the solution is 4, the dipping temperature is 80 ℃, the dipping time is 60min, then, drying is carried out for 30min at the temperature of 60 ℃, and then, the dipping-drying operation is repeated for 3 times; the acidified carbon nanotube-modified wool fibers are obtained, and the scanning electron microscope image is shown in fig. 8.
And (3) carrying out performance test and structure characterization on the obtained acidified carbon nanotube modified wool fiber, wherein the test results are as follows:
FIG. 9 is an infrared spectrum of wool fibers before and after modification. Through comparison, the N-H base stretching vibration (v N-H) of the three wool fibers is 3273.5cm -1 The N-H base flexural vibration (. delta.N-H) was 1514.30, and the C = O base flexural vibration (. nu.C = O) was 1630.5cm -1 There was no change in the characteristic absorption peak position of (a). The modification treatment of the acidified carbon nano tube can not damage the structure of the wool fiber, and the acidified carbon nano tube modified fiber is 1712cm -1 The C = O group stretching vibration characteristic peak of the acidified carbon nano tube appears, which indicates that the acidified carbon nano tubeThe rice-tube was successfully attached to the wool fibers. In addition, from the XRD test results of fig. 10, it was found that the modification of gallic acid and acidified carbon nanotubes on the surface of wool fiber did not affect the structural properties thereof.
FIG. 11 shows the synthetic mechanism and chemical structure of Galla Turcica in combination with hexamethylenediamine and acidified carbon nanotubes, respectively, and wool fibers; fig. 11 (a) and 11 (b) respectively show the preparation process of the acidified carbon nanotube-modified wool fiber 1 and the synthesis mechanism of the acidified carbon nanotube and gallic acid 2 in cooperation with hexamethylenediamine 3-modified wool fiber 4. As can be seen from fig. 11: the prepared acidified carbon nanotube modified wool fiber has a covalent bond and non-covalent bond cooperative bonding action mode and a mesh conductive network structure.
As can be seen from fig. 12, the acidified carbon nanotube 1 can be intercalated in the matrix coated with the gallic acid 3 to synergistically modify the wool fibers 4 to act as a nano space barrier, so that stacking of the acidified carbon nanotube is further inhibited, and the oxygen-containing group of the acidified carbon nanotube and the carboxyl group and phenolic hydroxyl group in the gallic acid 3 are also embedded on the matrix in a way that the chemical bond and the hydrogen bond 5 are cooperatively combined. The method promotes the acidified carbon nanotubes to be uniformly and tightly adhered to the gallic acid and the hexamethylene diamine modified wool fiber matrix, enhances the adhesion effect between interfaces, and simultaneously promotes the stability and durability of the acidified carbon nanotubes. In addition, regarding the construction of the mesh-like conductive network structure: on one hand, carboxyl and phenolic hydroxyl in gallic acid 3 on the surface of the substrate and hydroxyl, amido, carboxyl and other groups on the wool fiber form chemical bonds 8, 6 and 9 and hydrogen bond 5 interface dynamic cooperative bonding; on the other hand, the acidified carbon nano-tubes and the gallic acid are alternately intercalated on the wool fibers by the bonding driving force, so that a highly-oriented and continuously-conductive mesh-shaped conductive network structure is obtained.
Tables 3 and 4 are the results of the abrasion and water wash resistance tests of the acidified carbon nanotube modified wool fibers, as can be seen from tables 3 and 4: after 600 times of friction, the volume specific resistance of the acidified carbon nanotube modified wool fiber is only 55.4 Ω · cm; after washing 150 times, the volume specific resistance is only 42.3 Ω & cm, which shows that the modified wool fiber has good washing fastness and antistatic property and is suitable for preparing antistatic fabrics.
TABLE 3 Friction resistance test results for acidified carbon nanotube modified wool fibers
TABLE 4 test results of water washing resistance of acidified carbon nanotube modified wool fibers
Comparative example 3:
step (2) is omitted, and the rest is the same as that of examples 1 and 2, so as to obtain the acidified carbon nanotube modified wool fiber, and a scanning electron microscope image is shown in fig. 13.
And (3) carrying out performance test and structure characterization on the obtained acidified carbon nanotube modified wool fiber, wherein the test results are as follows:
FIGS. 14 and 15 are infrared spectra of wool fibers before and after modification. By comparison, the N-H base stretching vibration (v N-H) of the two wool fibers is 3273.5cm -1 The N-H base flexural vibration (. delta.N-H) was 1514.30, and the C = O base flexural vibration (. nu.C = O was 1630.5 cm) -1 There was no change in the characteristic absorption peak position of (a). The modification treatment of the acidified carbon nano tube can not damage the structure of the wool fiber, and the acidified carbon nano tube modified fiber is 1712cm -1 The C = O group stretching vibration characteristic peak of the acidified carbon nanotube appears, which indicates that the acidified carbon nanotube is successfully attached to the wool fiber. In addition, from the XRD test results of fig. 15, it was found that the modification of the acidified carbon nanotubes on the surface of the wool fiber did not affect the structural properties thereof.
Tables 5 and 6 are the results of the friction and water wash resistance tests of the acidified carbon nanotube modified wool fibers, as can be seen from tables 5 and 6: after 600 times of friction, the volume specific resistance of the acidified carbon nanotube modified wool fiber is 1545.8 Ω · cm; after 150 times of water washing, the volume specific resistance is 1348.6 Ω & cm, which indicates that the wool fiber has poor washing resistance and rubbing resistance.
TABLE 5 Friction resistance test results for acidified carbon nanotube modified wool fibers
TABLE 6 test results of water-washing resistance of acidified carbon nanotube modified wool fibers
The invention provides a low-temperature green impregnation process based on interface dynamic synergistic bonding effect, provides a method for preparing antistatic carbon nanotube modified wool fibers by using an alternate intercalation assembly composite technology, solves the problem of bonding firmness of conductive fillers and a matrix in the wool fibers, and simultaneously forms a continuous conductive path in the wool fiber matrix, thereby greatly improving the antistatic performance and the water washing resistance of the wool fibers.
The preparation method of the antistatic carbon nanotube modified wool fiber provided by the application is described in detail above, and the principle and the implementation mode of the application are explained by applying specific examples, and the description of the examples is only used for helping to understand the method and the core idea of the application; meanwhile, for a person skilled in the art, according to the idea of the present application, there may be variations in the specific embodiments and the application scope, and in summary, the content of the present specification should not be construed as a limitation to the present application.
Claims (10)
1. A preparation method of antistatic carbon nanotube modified wool fibers is characterized by comprising the following steps:
(1) performing ammonia/salt pretreatment on the wool fibers to obtain the wool fibers subjected to the ammonia/salt pretreatment;
(2) modifying the wool fibers pretreated by ammonia/salt in the step (1) by using dopamine (class) or derivatives thereof to obtain modified wool fibers of dopamine (class) or derivatives thereof;
(3) and (3) soaking the wool fiber modified by the dopamine (like) or the derivative thereof obtained in the step (2) in a dispersion liquid of the carbon nano tube or the derivative thereof, drying, washing and drying to obtain the carbon nano tube modified wool fiber.
2. The method for preparing antistatic carbon nanotube modified wool fiber according to claim 1, wherein the method comprises the following steps: the ammonia/salt pretreatment in the step (1) is to soak wool fibers in a solution containing 0.5-5.5g/L of ammonia water and 5-60 g/L of salt for 40-90min at a constant temperature of 50 ℃, take out, wash with water, dry and weigh for later use, wherein the bath ratio is 1: 50.
3. The method for preparing antistatic carbon nanotube modified wool fiber according to claim 1, wherein the method comprises the following steps: the salt in the step (1) is one of sodium chloride, calcium chloride, sodium sulfate and the like.
4. The method for preparing antistatic carbon nanotube modified wool fiber according to claim 1, wherein the method comprises the following steps: the dopamine (or dopamine-like) or dopamine derivative in the step (2) comprises one or more of gallic acid, dopamine hydrochloride, polydopamine (DATA), N-3, 4-dihydroxy phenethyl acrylamide (DAA) and MOA.
5. The method for preparing the antistatic carbon nanotube modified wool fiber according to claim 1, wherein the method comprises the following steps: the modification in the step (2) is that the wool fiber after ammonia/salt pretreatment is dipped in a mixed solution containing dopamine or derivatives thereof and tris buffer solution, the pH value of the solution is 8-10, and the wool fiber is obtained by water washing and drying; wherein the concentration of the dopamine or the derivative thereof in the mixed solution is 0.5-6.5mg/m L; the concentration of tris buffer was 0.5-4.5M.
6. The method for preparing antistatic carbon nanotube modified wool fiber according to claim 1, wherein the method comprises the following steps: the dipping in the modification process of the step (2) is carried out at room temperature of 20-30 ℃ and under the magnetic stirring of 60-100rpm for 24-48 h.
7. The method for preparing antistatic carbon nanotube modified wool fiber according to claim 1, wherein the method comprises the following steps: and (4) the concentration of the carbon nano tube and the derivative thereof in the step (3) is 5-45 mM.
8. The method for preparing the antistatic carbon nanotube modified wool fiber according to claim 1, wherein the method comprises the following steps: the dipping temperature in the step (3) is 65-85 ℃, and the time is 30-90 min.
9. The method for preparing antistatic carbon nanotube modified wool fiber according to claim 1, wherein the method comprises the following steps: and (3) the pH of the dispersion liquid of the carbon nano tube or the derivative thereof in the step (3) is 3.5-6.5.
10. The method for preparing antistatic carbon nanotube modified wool fiber according to claim 1, wherein the method comprises the following steps: the carbon nano tube and the derivative thereof in the step (3) comprise one or more of aminated carbon nano tubes, acidified carbon nano tubes, acrylamide aminated carbon nano tubes (AM-CNTs) and 2, 2-dimethylolpropionic acid carbon nano tubes (DMPA-CNTs).
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210552603.7A CN115045107A (en) | 2022-05-19 | 2022-05-19 | Preparation method of antistatic carbon nanotube modified wool fiber |
| PCT/CN2022/100959 WO2023221235A1 (en) | 2022-05-19 | 2022-06-24 | Preparation method for antistatic carbon-nanotube-modified wool fibers |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210552603.7A CN115045107A (en) | 2022-05-19 | 2022-05-19 | Preparation method of antistatic carbon nanotube modified wool fiber |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115045107A true CN115045107A (en) | 2022-09-13 |
Family
ID=83160351
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210552603.7A Pending CN115045107A (en) | 2022-05-19 | 2022-05-19 | Preparation method of antistatic carbon nanotube modified wool fiber |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN115045107A (en) |
| WO (1) | WO2023221235A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115787286A (en) * | 2022-11-14 | 2023-03-14 | 福建星海通信科技有限公司 | Preparation method of conductive cotton fabric for electromagnetic shielding |
| CN116590918A (en) * | 2023-07-18 | 2023-08-15 | 无锡太平针织有限公司 | Preparation method of antistatic wool fiber |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113152088A (en) * | 2021-04-25 | 2021-07-23 | 江南大学 | Flexible fabric-based strain sensor and preparation method thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006342476A (en) * | 2005-06-07 | 2006-12-21 | Kanehisa:Kk | Antistatic production process of fiber structure comprising wool |
| JP5557992B2 (en) * | 2008-09-02 | 2014-07-23 | 国立大学法人北海道大学 | Conductive fiber, conductive yarn, fiber structure having carbon nanotubes attached thereto, and manufacturing method thereof |
| CN108660742A (en) * | 2018-05-21 | 2018-10-16 | 北京化工大学常州先进材料研究院 | A kind of preparation method of polyimide fiber surface chemical modification carbon nanotube |
-
2022
- 2022-05-19 CN CN202210552603.7A patent/CN115045107A/en active Pending
- 2022-06-24 WO PCT/CN2022/100959 patent/WO2023221235A1/en unknown
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113152088A (en) * | 2021-04-25 | 2021-07-23 | 江南大学 | Flexible fabric-based strain sensor and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| 刘让同等: "多巴胺-碳纳米管对羊毛织物复合抗静电整理", 《针织工业》, no. 4, 28 April 2020 (2020-04-28), pages 41 - 44 * |
| 滑钧凯: "《毛和仿毛产品的染色与印花》", vol. 1, 31 December 1996, 中国纺织出版社, pages: 90 - 91 * |
| 谭苗苗: "NEMS传感器的研制与应用", vol. 1, 冶金工业出版社, pages: 24 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115787286A (en) * | 2022-11-14 | 2023-03-14 | 福建星海通信科技有限公司 | Preparation method of conductive cotton fabric for electromagnetic shielding |
| CN116590918A (en) * | 2023-07-18 | 2023-08-15 | 无锡太平针织有限公司 | Preparation method of antistatic wool fiber |
| CN116590918B (en) * | 2023-07-18 | 2023-10-20 | 无锡太平针织有限公司 | Preparation method of antistatic wool fiber |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2023221235A1 (en) | 2023-11-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN115045107A (en) | Preparation method of antistatic carbon nanotube modified wool fiber | |
| Zhou et al. | A knittable fiber-shaped supercapacitor based on natural cotton thread for wearable electronics | |
| CN113152088B (en) | Flexible fabric-based strain sensor and preparation method thereof | |
| Zou et al. | The optimization of nanocomposite coating with polyaniline coated carbon nanotubes on fabrics for exceptional electromagnetic interference shielding | |
| Hu et al. | Hydrophobic adsorption of surfactants on water-soluble carbon nanotubes: a simple approach to improve sensitivity and antifouling capacity of carbon nanotubes-based electrochemical sensors | |
| Kim et al. | Carbon Nanotube‐Adsorbed Electrospun Nanofibrous Membranes of Nylon 6 | |
| CN108330684A (en) | A kind of Multifunctional cotton fabric and preparation method thereof | |
| Wang et al. | Surface-conductive UHMWPE fibres via in situ reduction and deposition of graphene oxide | |
| JP2010059561A (en) | Electroconductive fibers with carbon nanotubes deposited thereon, electroconductive threads, fiber structure, and process for producing same | |
| CN107022895B (en) | Fabric with flame-retardant coating and preparation method thereof | |
| CN102808327A (en) | Method for preparing nylon-PEDOT (poly(3,4-ethylenedioxythiophene)) compound conductive fabric through in-situ polymerization | |
| CN103556452A (en) | Elastic conductive composite fiber and preparation method thereof | |
| CN101613943A (en) | A kind of preparation method of layer-by-layer self-assembly polyaniline amine/nylon composite conductive fabric | |
| Varesano et al. | A systematic study on the effects of doping agents on polypyrrole coating of fabrics | |
| CN108774879A (en) | A kind of preparation method of graphene coated conductive fiber | |
| CN103184579A (en) | Preparation method of electrospun polysulfonamide/multi-wall carbon nano tube complex fiber | |
| CN113089126B (en) | Conductive network remodeling method based on SBS conductive fiber, conductive composite fiber prepared by using method and preparation method thereof | |
| CN111926563B (en) | Strain sensing fabric and preparation method thereof | |
| JP6095159B2 (en) | Method for producing conductive cellulose fiber material | |
| CN113152074A (en) | Spandex covered yarn, preparation method thereof and underwear fabric applying covered yarn | |
| Zhao et al. | Iodine-steam functionalized reduced graphene oxide/oxidized carbon yarn electrodes for knittable fibriform supercapacitor | |
| CN114277574A (en) | Preparation method of multi-walled carbon nanotube functional fiber textile and product thereof | |
| JP2011058153A (en) | Method of preparing paper, textile and leather containing carbon-based nano structure and product therefrom | |
| Perumalraj | Electrical surface resistivity of polyaniline coated woven fabrics | |
| CN1258027C (en) | Electrostatic preventive sol and gel finishing liquid and its use for preparing electrostatic preventive Dacron |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |