WO2023221235A1 - Preparation method for antistatic carbon-nanotube-modified wool fibers - Google Patents

Abstract

The present invention relates to a preparation method for antistatic carbon-nanotube-modified wool fibers, and belongs to the technical field of conductive fiber preparation. The preparation method of the present invention comprises the following steps: (1) pretreating wool fibers; (2) modifying the pretreated wool fibers with dopamine (a dopamine-like substance) or a derivative thereof; and (3) dipping the wool fibers, which have been modified with the dopamine (a dopamine-like substance) or the derivative thereof, in a dispersion of carbon nanotubes or a derivative thereof, and drying, washing, and drying same to obtain carbon-nanotube-modified wool fibers. Due to the addition of dopamine (a dopamine-like substance) or a derivative thereof, the problems of poor dispersity and easy agglomeration of the carbon nanotubes are solved, the problem of bonding firmness between a conductive filler and a matrix in the wool fibers is solved; in addition, a continuous conductive path is formed in a wool fiber matrix, such that the antistatic property and water-washing of the wool fibers are greatly improved.

Description

A kind of preparation method of antistatic carbon nanotube modified wool fiber Technical field

The invention belongs to the technical field of conductive fiber preparation, and specifically relates to a preparation method of antistatic carbon nanotube-modified wool fiber.

Background technique

Textile materials are electrical insulator materials with generally high resistance, especially fibers with good elasticity, strong hygroscopicity, and good warmth retention properties such as wool, low polyester, acrylic, and chlorine fiber. They are widely used in textile raw materials and in textile processing. It plays an increasingly important role in the textile industry. The fabrics made of it have the characteristics of plump texture, smooth and waxy feel, good drape, noble, light and comfortable wear, and have always been favored by consumers. However, during textile processing, due to the close contact and friction between fibers and fibers or between fibers and machine parts. Causes the transfer of charge on the surface of the object, resulting in static electricity. Fibers with the same charge repel each other, and fibers with different charges are attracted to machine parts, resulting in hairy slivers, increased fiber hairiness, poor package formation, fiber sticking to machine parts, increased yarn breakage, and Dispersed streaks, etc. are formed on the cloth surface. After the fibers are charged, they absorb a large amount of dust and are prone to contamination. In addition, the fibers can also become entangled with the human body or between fibers or generate sparks. Therefore, electrostatic interference affects the smooth progress of fiber processing, thereby affecting its wearing performance. When the static electricity phenomenon is severe, the static voltage can reach several thousand volts, which can cause sparks due to discharge and cause fires with serious consequences. Therefore, effectively reducing or removing static electricity in fiber materials is a technical problem that currently needs to be solved.

In recent years, with the increasing attention at home and abroad to the hazards of static electricity. People have done a lot of research and experiments on fiber antistatic and achieved remarkable results, especially in the field of antistatic wool fiber preparation technology. There are currently three main methods for preparing antistatic wool fibers: First, spraying or impregnating antistatic agents (such as nano-MgO) on the surface of wool fibers can form a layer of antistatic agents on the surface of wool fibers, but the antistatic performance is temporary. The antistatic agent falls off from the fiber surface after washing, affecting the durability of its antistatic effect; second, during the processing of wool fiber products, conductive fibers with good electrical conductivity are added through blending or inlay weaving, which can make the fibers more durable. The volume specific resistance is greatly reduced, which can effectively prevent the generation of static electricity. Patent CN112239905A mentions a preparation process for blended wool conductive fibers. This patent successfully prepares blended wool conductive fibers by blending Belltron organic conductive fibers and wool fibers. This process can not only improve fiber processing operations, but also produce Wool fiber blend with excellent antistatic properties. However, the embedding of Belltron organic conductive fiber in the above patent will greatly reduce the original excellent characteristics of cashmere fiber due to its fineness and flexibility, limiting its application to a certain range; third, with the help of nano fillers (such as carbon Nanotubes) are bonded to wool fiber macromolecules using physical or chemical modification methods to achieve the purpose of durable antistatic function. Liu Rangping used in-situ polymerization of dopamine to cover the surface of wool fibers with a discontinuous hydrophilic film of dopamine to reduce the hydrophobicity of the fiber surface. At the same time, dopamine was used to load carbon nanotubes with its super strong adhesion, and the conductivity of carbon nanotubes was used to make It achieves antistatic effect. However, the article does not mention the adhesion effect between conductive materials and wool fiber matrix (composite antistatic finishing of wool fabrics with dopamine-carbon nanotubes [J]. Knitting Industry, 2020(04):41-44.) .

The bonding force between the conductive filler (such as carbon nanotubes) and the matrix in the antistatic wool fiber prepared by the current method is poor, and the bonding degree between the conductive layer and the wool fiber matrix is not high, resulting in changes in the external environment (such as high temperature and humidity, The conductive layer will fall off due to the action of air and concentrated alkali, etc.), thus affecting its antistatic durability and water washing resistance.

Contents of the invention

The technical problem to be solved by the present invention is to provide a method for preparing antistatic carbon nanotube-modified wool fiber, which solves the problem of bonding firmness between the wool fiber conductive filler and the matrix, and at the same time forms a continuous conductive path in the wool fiber matrix. , which greatly improves the antistatic properties and washability of wool fibers.

In order to solve the above technical problems, a technical solution adopted by the present invention is: the preparation method of the antistatic carbon nanotube modified wool fiber, which includes the following steps:

(1) Perform ammonia/salt pretreatment on wool fibers to obtain ammonia/salt pretreated wool fibers;

(2) Use (like) dopamine or its derivatives to modify the wool fiber after the ammonia/salt pretreatment in step (1) to obtain wool fibers modified by (like) dopamine or its derivatives;

(3) Dip the wool fiber modified by dopamine (like) or its derivatives obtained in step (2) in a dispersion of carbon nanotubes or its derivatives, dry, wash, and dry to obtain carbon nanotube-modified fibers. Wool fibers.

Further, the ammonia/salt pretreatment described in step (1) is to immerse the wool fiber in a solution containing 0.5-5.5g/L ammonia and 5-60g/L salt, and immerse it at a constant temperature of 50°C for 40-90 minutes. Then take it out, wash it with water, dry it, weigh it and set it aside. The liquor ratio is 1:50.

Further, the salt described in step (1) is one of sodium chloride, calcium chloride, sodium sulfate, etc.

Further, the (analogue) dopamine or derivatives thereof described in step (2) include gallic acid, dopamine hydrochloride, polydopamine analog (DATA), N-3,4-dihydroxyphenylethyl acrylamide (DAA), MOA one or more of them.

Further, the modification described in step (2) is to immerse the ammonia/salt pretreated wool fiber in a mixed solution containing dopamine or its derivatives and tris buffer. The pH of the solution is 8-10, washed with water, and dried. Obtained; wherein the concentration of dopamine (like) or its derivatives in the mixed solution is 0.5-6.5mg/mL; the concentration of the tris buffer is 0.5-4.5M.

Further, during the modification process in step (2), the impregnation is performed at room temperature of 20-30°C and magnetic stirring at 60-100 rpm for 24-48 hours.

Further, the concentration of the carbon nanotubes and their derivatives in step (3) is 5-45mM.

Further, the impregnation temperature in step (3) is 65-85°C and the time is 30-90 minutes.

Further, the pH of the dispersion of carbon nanotubes or derivatives thereof in step (3) is 3.5-6.5.

Further, the carbon nanotubes and their derivatives described in step (3) include aminated carbon nanotubes, acidified carbon nanotubes, acrylamidated carbon nanotubes (AM-CNTs), 2,2-dihydroxymethylpropionated carbon nanotubes. One or more types of carbon nanotubes (DMPA-CNTs).

The advantages of the present invention are as follows:

(1) The antistatic carbon nanotube-modified wool fiber of the present invention is based on the antistatic carbon nanotube-modified wool fiber functionally modified by dopamine or its derivatives, and uses alternating intercalation on the surface of the matrix. Antistatic carbon nanotube-modified wool fiber is prepared by assembly composite technology; the modification of dopamine (like) or its derivatives means that the amine group, imine group, and phenolic hydroxyl group in (like) dopamine or its derivatives can be prepared by formulating Position interaction, hydrogen bond association, electrostatic interaction, hydrophobic interaction and even covalent reaction are mutually bonded with the carboxyl, amino and hydroxyl groups in the wool fiber and firmly adhere to its surface; the alternating intercalation assembly composite technology is A process in which highly oriented and continuous conductive pathways are obtained through alternating intercalation through the bonding driving force between two different substances. Such alternating intercalation effect not only increases the contact area between carbon nanotubes or their derivatives and the matrix, but also enhances Adhesion effect of carbon nanotubes or their derivatives to the matrix.

(2) The antistatic carbon nanotube-modified wool fiber of the present invention has an interface dynamic synergistic bonding mode: the amine groups, imine groups, phenolic hydroxyl groups, etc. in the polydopamine on the surface of the matrix and the conductive fillers deposited on the matrix The oxygen-containing groups in form covalent bonds and non-covalent bonds to bond cooperatively.

(3) The method of rapid deposition of dopamine used in the present invention not only solves the problem of dispersion and re-agglomeration of conductive nanofillers, but also enhances the adhesion between the conductive filler layer and wool fibers without the need for a large amount of chemical adhesion reagents, which is in line with the current situation. Compared with some chemical methods, the process method of the present invention is green, environmentally friendly, simple to operate and low in cost.

(4) The antistatic carbon nanotube-modified wool fiber prepared by the alternate intercalation assembly composite technology of the present invention not only enhances the adhesion between the conductive layer and the matrix, but also improves the poor dispersion and ease of carbon nanotubes or their derivatives. The problem of agglomeration enables the conductive fillers to be evenly dispersed, providing new ideas for the development of antistatic fibers. This preparation method has the advantages of wide applicability, strong flexibility, and high efficiency. It is an excellent way to prepare high-performance antistatic wool fibers in an efficient and controllable manner, and is convenient for industrial production.

(5) The volume specific resistance of the antistatic carbon nanotube-modified wool fiber prepared by the method of the present invention is below 21.4Ω·cm. After 500 times of rubbing, the volume specific resistance is below 68.5Ω·cm; after 150 times of water washing , the volume specific resistance is 56.7Ω·cm; indicating that the modified wool fiber has good washing resistance and antistatic properties, and is suitable for the preparation of antistatic fabrics.

Description of the drawings

Figure 1 is a schematic diagram of the preparation process of acidified carbon nanotube-modified wool fibers in Example 1 of the present invention.

Figure 2 is a scanning electron microscope image of the acidified carbon nanotube-modified wool fiber in Example 1; where a-b, c-d, and e-f are wool fiber, dopamine-modified wool fiber, and acidified carbon nanotube-modified wool fiber at 100 μm, respectively. and 50μm electron micrograph.

Figure 3 shows the infrared spectra of wool fiber before and after modification, where a, b, and c are wool fiber, dopamine-modified wool fiber, and acidified carbon nanotube-modified wool fiber, respectively.

Figure 4 shows the XRD patterns of wool fibers before and after modification, where a, b, and c are wool fibers, dopamine-modified wool fibers, and acidified carbon nanotube-modified wool fibers, respectively.

Figure 5 shows the preparation process of acidified carbon nanotube-modified wool fiber 1 in Example 1; where a and b are the preparation process of acidified carbon nanotube-modified wool fiber, acidified carbon nanotube and dopamine 2-modified wool fiber 3, respectively. synthesis mechanism.

Figure 6 shows the synthesis mechanism of acidified carbon nanotubes and polydopamine modified wool fibers in Example 1; 2 is polydopamine; 4 is hydrogen bonding; 3 is wool fiber; 1 is acidified carbon nanotubes; 5 and 7 are π -π conjugation, 8 is a chemical bond (esterification reaction).

Figure 7 is a schematic diagram of the preparation process of acidified carbon nanotube-modified wool fibers in Example 2 of the present invention.

Figure 8 is a scanning electron microscope image of the acidified carbon nanotube-modified wool fiber in Example 2; where a-b, c-d, and e-f are respectively wool fiber, gallic acid and hexamethylenediamine-modified wool fiber, acidified carbon nanotube-modified wool fiber, and acidified carbon nanotube-modified wool fiber. Electron micrographs of wool fibers at 100μm and 50μm.

Figure 9 shows the infrared spectra of wool fiber before and after modification, where a, b, and c are wool fiber, wool fiber modified by gallic acid and hexamethylenediamine, and wool fiber modified by acidified carbon nanotubes, respectively.

Figure 10 shows the XRD patterns of wool fiber before and after modification, where a, b, and c are wool fiber, wool fiber modified by gallic acid and hexamethylenediamine, and wool fiber modified by acidified carbon nanotubes, respectively.

Figure 11 is the preparation process of acidified carbon nanotube-modified wool fiber 1 in Example 2; where a and b are respectively the preparation process of acidified carbon nanotube-modified wool fiber, acidified carbon nanotubes and gallic acid 2 in collaboration with hexamethylenediamine 3 Synthesis mechanism of modified wool fiber 4.

Figure 12 shows the synthesis mechanism of acidified carbon nanotubes and polydopamine-modified wool fibers in Example 2; 2 is hexamethylenediamine; 5 is hydrogen bonding; 4 is wool fiber; 1 is acidified carbon nanotubes; 9 is amidation. Function, 8 is hydroxyl amination, 3 is hexamethylenediamine, and 6 is esterification.

Figure 13 is a scanning electron microscope image of the acidified carbon nanotube-modified wool fiber of Comparative Example 3; a-b, c-d are the electron microscopy images of wool fiber and acidified carbon nanotube-modified wool fiber at 100 μm and 50 μm, respectively.

Figure 14 shows the infrared spectrum of wool fiber before and after modification, where a and b are wool fiber and acidified carbon nanotube modified wool fiber respectively.

Figure 15 shows the XRD pattern of wool fiber before and after modification, where a and b are wool fiber and acidified carbon nanotube modified wool fiber respectively.

Detailed ways

In order to make the above objects, features and advantages of the present invention more obvious and easy to understand, the specific embodiments of the present invention will be further described below with reference to the specific drawings.

Many specific details are set forth in the following description in order to fully understand the present invention. However, the present invention can also be implemented in other ways different from those described here. Those skilled in the art can implement the invention without departing from the connotation of the present invention. Similar generalizations are made, and therefore the present invention is not limited to the specific embodiments disclosed below.

The wool fiber used in the examples was purchased from Snow Lotus Cashmere Co., Ltd., and the carbon nanotube dispersion used sodium dodecyl benzene sulfonate as the solvent, in which the carbon nanotubes were purchased from Nanjing Xianfeng Nano Materials Technology Co., Ltd.; others are not specified. The solution uses water as the solvent.

The preparation method of acidified carbon nanotubes is as follows: stir and mix carbon nanotubes and concentrated nitric acid with a mass concentration of 75% according to a mass volume ratio of 1g:90mL, react at 135°C for 12 hours, and filter and wash the obtained product until it is neutral. properties and vacuum drying to obtain acidified carbon nanotubes.

Test Methods:

Friction resistance test: Test according to the national standard GB/T21196.

Test of specific resistance: Use a fiber specific resistance meter to measure the specific resistance value of the modified fiber. Weigh 15g of fiber and fill it evenly into the fiber test box. Place the fiber sample to be tested at room temperature and a relative humidity of 65% ± 10 % environment and then tested after equilibration for 4 hours.

Determination of water washing durability: Refer to the literature (Cheng Wenqing. Preparation and performance of conductive cashmere fiber [D]. Beijing Institute of Fashion Technology 2014) to conduct the water washing durability test.

Embodiment 1: A method for preparing antistatic carbon nanotube modified wool fibers, including the following steps, as shown in Figure 1:

(1) Dip the wool fiber into a solution containing ammonia (2g/L) and salt (10g/L), soak at a constant temperature of 50°C for 60 minutes, take it out, wash, dry, and weigh for later use. The bath ratio is 1 :50, to obtain ammonia/salt pretreated wool fiber;

(2) Dip the ammonia/salt pretreated wool fiber obtained in step (1) into a mixed solution containing dopamine hydrochloride (2mg/mL) and tris buffer (1M). The pH of the solution is 8.5; then incubate at room temperature 25 Stir magnetically at 80 rpm for 24 hours at ℃;

(3) Dip the polydopamine-modified wool fiber obtained in step (2) into 35mM acidified carbon nanotube dispersion. The pH of the solution is 4, the immersion temperature is 80°C, the immersion time is 60min, and then dried at 60°C for 30min. , and then repeat the dipping-drying operation three times; the acidified carbon nanotube modified wool fiber is obtained, and the scanning electron microscope picture is shown in Figure 2.

The obtained acidified carbon nanotube modified wool fiber was subjected to performance testing and structural characterization. The test results are as follows:

Figure 3 shows the infrared spectrum of wool fiber before and after modification. Through comparison, it was found that the NH-based stretching vibration (νN-H) of the three wool fibers was 3273.5cm ^-1 , the NH-based bending vibration (δN-H) was 1514.30, and the C=O-based stretching vibration (νC=O) was 1630.5cm The characteristic absorption peak position of ^-1 does not change. It shows that the modification treatment of acidified carbon nanotubes will not destroy the structure of the wool fiber itself. At the same time, the acidified carbon nanotube modified fiber has a characteristic peak of the C=O group stretching vibration of acidified carbon nanotubes at 1712cm ^-1 , indicating acidification. Carbon nanotubes successfully adhered to wool fibers. In addition, from the XRD test results in Figure 4, it is found that the modification of dopamine and acidified carbon nanotubes on the surface of wool fibers does not affect its structural properties.

Figure 5 shows the synthesis mechanism and chemical structure of dopamine and acidified carbon nanotubes and wool fiber respectively; Figure 5(a) and Figure 5(b) respectively show the preparation process and acidified carbon modified wool fiber 1 Synthesis mechanism of wool fiber modified with nanotubes and dopamine 2. It can be seen from Figure 5 that the prepared acidified carbon nanotube-modified wool fiber has a cooperative bonding mode of covalent bonds and non-covalent bonds and a mesh-like conductive network structure.

It can be seen from Figure 6 that acidified carbon nanotubes 1 can be intercalated in the matrix of modified wool fiber 3 coated with polydopamine 2 to act as a nanospace barrier, further inhibiting the stacking of acidified carbon nanotubes, and acidified carbon The oxygen-containing groups of the nanotubes and the amine groups, imine groups, phenolic hydroxyl groups, etc. in polydopamine 2 are also embedded in the matrix in a cooperative manner with chemical bonds 8 and hydrogen bonds 4.

This method promotes the acidified carbon nanotubes to adhere evenly and tightly to the dopamine-modified wool fiber matrix, which enhances the adhesion between the interfaces and also improves its stability and durability. In addition, regarding the construction of a mesh conductive network structure: on the one hand, the amine groups, imine groups, phenolic hydroxyl groups, etc. in the polydopamine 1 on the surface of the substrate form chemical bonds 8 and hydrogen bonds with the hydroxyl groups, amine groups, carboxyl groups, etc. on the wool fiber. 4 Interface dynamic collaborative bonding; on the other hand, the bonding driving force between acidified carbon nanotubes and polydopamine is alternately intercalated on the wool fiber, thereby obtaining a highly oriented and continuously conductive mesh-like conductive network structure.

Table 1 and Table 2 show the test results of the friction resistance and water washing resistance of the acidified carbon nanotube-modified wool fiber. From Table 1 and Table 2, it can be seen that after 600 times of rubbing, the volume ratio of the acidified carbon nanotube-modified wool fiber The resistance is only 84.50Ω·cm; after 150 times of washing, the volume specific resistance is only 56.7Ω·cm, indicating that the modified wool fiber has good washing resistance and antistatic properties and is suitable for the preparation of antistatic fabrics.

Table 1 Test results of friction resistance of acidified carbon nanotube modified wool fiber

Friction resistance times/times	Specific resistance/(Ω·cm)
0	21.4
50	22.8
100	27.9
150	32.2
200	39.4
250	43.3
300	52.2
350	58.4
400	63.2
450	65.7
500	68.5

Table 2 Test results of washing resistance of acidified carbon nanotube modified wool fiber

Washing times/times	Specific resistance/(Ω·cm)
0	21.4
10	23.7
30	28.2
60	30.5
90	32.8
120	42.8
150	56.7

Embodiment 2: A method for preparing antistatic carbon nanotube modified wool fibers, as shown in Figure 7, including the following steps:

(1) Dip the wool fiber into a solution containing 2g/L ammonia and 10g/L salt, soak at a constant temperature of 50°C for 60 minutes, take it out, wash, dry, and weigh for later use. The liquor ratio is 1:50 to obtain Ammonia/salt pretreated wool fibers;

(2) Dip the ammonia/salt pretreated wool fiber obtained in step (1) into a mixed solution containing 2 mg/mL gallic acid, 1 mg/mL hexamethylenediamine and 1 M tris buffer. The pH of the solution is 8.5; then Stir magnetically at 80 rpm at room temperature 25°C for 24 hours;

(3) Dip the polydopamine-modified wool fiber obtained in step (2) into 35mM acidified carbon nanotube dispersion. The pH of the solution is 4, the immersion temperature is 80°C, the immersion time is 60min, and then dried at 60°C for 30min. , and then repeat the dipping-drying operation three times; the acidified carbon nanotube modified wool fiber is obtained, and the scanning electron microscope picture is shown in Figure 8.

The obtained acidified carbon nanotube modified wool fiber was subjected to performance testing and structural characterization. The test results are as follows:

Figure 9 shows the infrared spectrum of wool fiber before and after modification. Through comparison, it was found that the NH-based stretching vibration (νN-H) of the three wool fibers was 3273.5cm ^-1 , the NH-based bending vibration (δN-H) was 1514.30, and the C=O-based stretching vibration (νC=O) was 1630.5cm The characteristic absorption peak position of ^-1 does not change. It shows that the modification treatment of acidified carbon nanotubes will not destroy the structure of the wool fiber itself. At the same time, the acidified carbon nanotube modified fiber has a characteristic peak of the C=O group stretching vibration of acidified carbon nanotubes at 1712cm ^-1 , indicating acidification. Carbon nanotubes successfully adhered to wool fibers. In addition, from the XRD test results in Figure 10, it is found that the modification of gallic acid and acidified carbon nanotubes on the surface of wool fiber does not affect its structural properties.

Figure 11 shows the synthesis mechanism and chemical structure of gallic acid synergistic hexamethylenediamine and acidified carbon nanotubes with wool fiber respectively; Figure 11(a) and Figure 11(b) respectively show the preparation of acidified carbon nanotube modified wool fiber 1 Process and synthesis mechanism of wool fiber 4 modified by acidified carbon nanotubes and gallic acid 2 in collaboration with hexamethylene diamine 3. It can be seen from Figure 11 that the prepared acidified carbon nanotube-modified wool fiber has a cooperative bonding mode of covalent bonds and non-covalent bonds and a mesh-like conductive network structure.

As can be seen from Figure 12, acidified carbon nanotubes 1 can be intercalated in the matrix of wool fiber 4 coated with gallic acid 3 to synergistically modify it and act as a nanospace barrier, further inhibiting the stacking of acidified carbon nanotubes, and acidifying The oxygen-containing groups of carbon nanotubes and the carboxyl groups and phenolic hydroxyl groups in gallic acid 3 are also embedded in the matrix in a cooperative manner with chemical bonds and hydrogen bonds 5 . This method promotes the acidified carbon nanotubes to adhere evenly and tightly to the gallic acid and hexamethylenediamine-modified wool fiber matrix, which enhances the interfacial adhesion and also improves its stability and durability. In addition, regarding the construction of the mesh conductive network structure: on the one hand, the carboxyl and phenolic hydroxyl groups in the gallic acid 3 on the surface of the matrix form chemical bonds 8, 6, 9 and hydrogen bond 5 interfaces with the hydroxyl, amine, carboxyl and other groups on the wool fiber. Dynamic cooperative bonding; on the other hand, through the bonding driving force between acidified carbon nanotubes and gallic acid, they are alternately intercalated on the wool fiber, thereby obtaining a highly oriented and continuously conductive mesh-like conductive network structure.

Table 3 and Table 4 show the test results of the friction resistance and water washing resistance of the acidified carbon nanotube-modified wool fiber. From Table 3 and Table 4, it can be seen that after 600 times of rubbing, the volume ratio of the acidified carbon nanotube-modified wool fiber The resistance is only 55.4Ω·cm; after washing 150 times, the volume specific resistance is only 42.3Ω·cm, indicating that the modified wool fiber has good washing resistance and antistatic properties and is suitable for the preparation of antistatic fabrics.

Table 3 Test results of friction resistance of acidified carbon nanotube modified wool fiber

Friction resistance times/times	Specific resistance/(Ω·cm)
0	20.5
50	21.3
100	28.4
150	31.7
200	38.2
250	40.1
300	45.2
350	48.4
400	50.2
450	52.3
500	55.4

Table 4 Test results of washing resistance of acidified carbon nanotube modified wool fibers

Washing times/times	Specific resistance/(Ω·cm)
0	20.5
10	21.8
30	24.3
60	28.9
90	30.8
120	35.2
150	42.3

Comparative example 3:

Step (2) is omitted, and the rest is the same as in Examples 1 and 2 to obtain acidified carbon nanotube-modified wool fiber. The scanning electron microscope picture is shown in Figure 13.

The obtained acidified carbon nanotube modified wool fiber was subjected to performance testing and structural characterization. The test results are as follows:

Figures 14 and 15 show the infrared spectra of wool fibers before and after modification. Through comparison, it was found that the NH-based stretching vibration (νN-H) of the two wool fibers was 3273.5cm ^-1 , the NH-based bending vibration (δN-H) was 1514.30, and the C=O-based stretching vibration (νC=O was 1630.5cm ^- The position of the characteristic absorption peak of ¹ has not changed. This shows that the modification treatment of acidified carbon nanotubes will not destroy the structure of the wool fiber itself. At the same time, the acidified carbon nanotube-modified fiber has the C=O of acidified carbon nanotubes at 1712cm ^-1 The characteristic peak of basic tensile vibration indicates that the acidified carbon nanotubes are successfully attached to the wool fiber. In addition, from the XRD test results in Figure 15, it is found that the modification of the acidified carbon nanotubes on the surface of the wool fiber does not affect its structural properties. .

Table 5 and Table 6 show the test results of the friction resistance and water washing resistance of the acidified carbon nanotube modified wool fiber. From Table 5 and Table 6, it can be seen that after 600 times of rubbing, the volume ratio of the acidified carbon nanotube modified wool fiber The resistance is 1545.8Ω·cm; after washing 150 times, the volume specific resistance is 1348.6Ω·cm, indicating that the wool fiber has poor washing resistance and friction resistance.

Table 5 Test results of friction resistance of acidified carbon nanotube modified wool fiber

Friction resistance times/times	Specific resistance/(Ω·cm)
0	984.2
50	1023.4
100	1087.9
150	1125.6
200	1156.8
250	1203.2
300	1245.3
350	1305.3
400	1404.5
450	1505.6
500	1545.8

Table 6 Test results of washing resistance of acidified carbon nanotube modified wool fibers

Washing times/times	Specific resistance/(Ω·cm)
0	984.2
10	1034.6
30	1087.2
60	1135.9
90	1164.3
120	1235.6
150	1348.6

Based on the low-temperature green impregnation process of dynamic synergistic bonding of the interface, the present invention proposes a method for preparing antistatic carbon nanotube-modified wool fiber using alternating intercalation assembly composite technology, which solves the problem of the bond between the conductive filler and the matrix in the wool fiber. It solves the problem of bonding fastness and forms a continuous conductive path in the wool fiber matrix, which greatly improves the antistatic performance and water washing resistance of wool fiber.

The above is a detailed introduction to the preparation method of an antistatic carbon nanotube-modified wool fiber provided by this application. Specific examples are used in this article to illustrate the principles and implementation methods of this application. The description of the above examples is only for use. To help understand the methods and core ideas of this application; at the same time, for those of ordinary skill in the field, there will be changes in the specific implementation methods and application scope based on the ideas of this application. In summary, this specification The contents should not be construed as limitations on this application.

Claims (10)

1. A method for preparing antistatic carbon nanotube-modified wool fiber, which is characterized by including the following steps:

   (1) Perform ammonia/salt pretreatment on wool fibers to obtain ammonia/salt pretreated wool fibers;

   (2) Use (like) dopamine or its derivatives to modify the wool fiber after the ammonia/salt pretreatment in step (1) to obtain wool fibers modified by (like) dopamine or its derivatives;

   (3) Dip the wool fiber modified by dopamine (like) or its derivatives obtained in step (2) in a dispersion of carbon nanotubes or its derivatives, dry, wash, and dry to obtain carbon nanotube-modified fibers. Wool fiber.
2. The preparation method of antistatic carbon nanotube-modified wool fiber according to claim 1, characterized in that: the ammonia/salt pretreatment in step (1) is to immerse the wool fiber in water containing 0.5-5.5g/L ammonia , salt solution of 5-60g/L, soak at a constant temperature of 50°C for 40-90 minutes, then take it out, wash with water, dry, weigh and set aside, with a liquor ratio of 1:50.
3. The method for preparing antistatic carbon nanotube modified wool fiber according to claim 1, characterized in that: the salt in step (1) is one of sodium chloride, calcium chloride, sodium sulfate, etc.
4. The preparation method of antistatic carbon nanotube-modified wool fiber according to claim 1, characterized in that: the (like) dopamine or derivatives thereof in step (2) include gallic acid, dopamine hydrochloride, polydopamine-like ( DATA), N-3,4-dihydroxyphenylethyl acrylamide (DAA), or one or more of MOA.
5. The preparation method of antistatic carbon nanotube modified wool fiber according to claim 1, characterized in that: the modification in step (2) is to impregnate the ammonia/salt pretreated wool fiber in a solution containing dopamine or its In the mixed solution of the derivative and tris buffer, the pH of the solution is 8-10, washed and dried; the concentration of dopamine (like) or its derivatives in the mixed solution is 0.5-6.5mg/mL; the concentration of tris buffer is 0.5-4.5M.
6. The preparation method of antistatic carbon nanotube modified wool fiber according to claim 1, characterized in that: the impregnation in the modification process of step (2) is at room temperature 20-30°C with magnetic stirring at 60-100 rpm for 24 -48h.
7. The method for preparing antistatic carbon nanotube-modified wool fiber according to claim 1, characterized in that: the concentration of carbon nanotubes and their derivatives in step (3) is 5-45mM.
8. The method for preparing antistatic carbon nanotube modified wool fiber according to claim 1, characterized in that: the impregnation temperature in step (3) is 65-85°C and the time is 30-90 minutes.
9. The method for preparing antistatic carbon nanotube-modified wool fiber according to claim 1, characterized in that: the pH of the dispersion of carbon nanotubes or derivatives thereof in step (3) is 3.5-6.5.
10. The preparation method of antistatic carbon nanotube modified wool fiber according to claim 1, characterized in that: the carbon nanotubes and their derivatives in step (3) include aminated carbon nanotubes, acidified carbon nanotubes, propylene One or more of amidated carbon nanotubes (AM-CNTs) and 2,2-dimethylolpropionated carbon nanotubes (DMPA-CNTs).

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