An antistatic fabric based on modified acrylic fiber and its preparation process

Abstract

This invention provides an antistatic fabric based on modified acrylic fiber and its preparation process, belonging to the field of textile fabric technology. The process includes the following steps: first, preparing modified acrylic fiber and organosilicon quaternary ammonium salt modified CNW; then, mixing and stirring the modified acrylic fiber, DMF, and organosilicon quaternary ammonium salt modified CNW to obtain a spinning solution; mixing anhydrous ethanol and organosilicon quaternary ammonium salt modified CNW, and ultrasonically treating to obtain a dispersion; in a conjugate electrospinning device, feeding the spinning solution and dispersion into two sets of needles respectively, and electrospinning the spinning solution to form nanofibers under the action of a high-voltage electric field; feeding cotton yarn into the electric field region, causing the nanofibers to spirally wind around the surface of the cotton yarn and form a coating shell; and electrostatically spraying the dispersion to deposit the organosilicon quaternary ammonium salt modified CNW onto the surface of the coating shell; collecting and winding to obtain a fiber core-spun yarn, and weaving the fiber core-spun yarn to obtain the antistatic fabric. This invention can improve the antistatic performance of the fabric while also possessing certain antibacterial properties.

Description

Technical Field

[0001] This invention relates to the field of textile fabric technology, specifically to an antistatic fabric based on modified acrylic fibers and its preparation process. Background Technology

[0002] Acrylic fiber, primarily composed of polyacrylonitrile, is lightweight, highly resilient, and exhibits good resistance to sunlight and weathering. It is commonly used in knitwear, thermal underwear, home textiles, and functional textiles. However, with increasing demands for comfort, health protection, and durability in autumn and winter clothing and close-fitting fabrics, acrylic fabrics have revealed several common problems in practical use: First, the limited polarity of polyacrylonitrile leads to static electricity buildup during wear, resulting in dust accumulation, discomfort against the skin, and crackling discharge. Second, the surface chemical inertness of acrylic fibers means that functional additives or finishing agents bind to the fibers primarily through physical adsorption, resulting in insufficient wash and abrasion resistance, and the antistatic effect often diminishes with repeated use. Third, autumn and winter thermal fabrics are prone to bacterial growth in enclosed, humid, and warm environments, producing odors and causing skin irritation. Therefore, antibacterial durability has gradually become an important indicator for functional fabrics. However, existing antibacterial finishing methods also suffer from problems such as easy agent migration, short shelf life, weak bonding with fibers, or affecting hand feel and breathability.

[0003] To improve the antistatic properties of synthetic fibers, existing technologies generally employ two approaches: one is to apply hydrophilic antistatic finishing agents (such as surfactants, polyethers, and hydrophilic resins) to the fabric surface. This method is simple to implement but easily washed away and its effectiveness is unstable in low-humidity environments. The other approach involves introducing conductive fillers or conductive fibers (such as carbon black, metal powders, carbon nanomaterials, or conductive filaments) to reduce resistance and dissipate static electricity. However, this often suffers from problems such as difficulty in dispersion, stiffening of the hand feel, processing wear, and insufficient bonding with the fiber interface, making it particularly difficult to balance comfort and durability in soft, close-fitting fabrics. Regarding antibacterial properties, existing technologies often use inorganic antibacterial agents such as silver-based and zinc-based agents. However, inorganic antibacterial agents may migrate and discolor, and have adverse effects on softness and breathability.

[0004] Patent application CN1377995A discloses a modified polyacrylonitrile fiber and a highly absorbent fabric. The main method involves adding polyethylene glycol-based antistatic components and inorganic fillers such as zinc oxide whiskers to the polyacrylonitrile spinning system to improve antistatic properties. While this approach can improve hygroscopicity and alleviate static electricity to some extent, the hydrophilic components such as polyethylene glycol are at risk of migrating and being lost during washing, resulting in limited wash and abrasion resistance retention. Furthermore, the whisker-based inorganic filler has poor dispersibility, is prone to agglomeration, and can easily introduce fluctuations in fiber consistency.

[0005] Therefore, there is a need to provide an antistatic fabric based on modified acrylic fibers and its preparation process to solve the above-mentioned technical problems. Summary of the Invention

[0006] In view of this, the present invention provides an antistatic fabric based on modified acrylic fiber and its preparation process, which can improve the antistatic performance of the fabric while also having a certain antibacterial property.

[0007] To achieve the above objectives, the present invention provides a process for preparing an antistatic fabric based on modified acrylic fiber, comprising the following steps:

[0008] S1. Add acrylic fiber to sodium hydroxide aqueous solution, heat and stir, rinse, dry, then immerse in L-cysteine ​​aqueous solution and protein dispersion in sequence, heat and stir, separate, wash, and dry to obtain modified acrylic fiber;

[0009] S2. Cellulose nanocrystals were added to an ethanol aqueous solution and magnetically stirred. Then, dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride was added and the mixture was shaken to react. After cooling, washing, and drying, the organosilicon quaternary ammonium salt modified CNW was obtained.

[0010] S3. Modified acrylic fiber, DMF, and organosilicon quaternary ammonium salt modified CNW are mixed and stirred to obtain a spinning solution; anhydrous ethanol and organosilicon quaternary ammonium salt modified CNW are mixed and ultrasonically treated to obtain a dispersion.

[0011] S4. On a conjugate electrospinning device, the spinning solution and dispersion solution are fed into two sets of needles respectively. Under the action of a high-voltage electric field, the spinning solution is electrospun to form nanofibers. Cotton yarn is fed into the electric field area, so that the nanofibers spirally wind around the surface of the cotton yarn and form a coating shell. The dispersion solution is electrostatically sprayed to deposit the organosilicon quaternary ammonium salt modified CNW on the surface of the coating shell. The core-spun fiber yarn is collected and wound to obtain the fiber core-spun yarn. The fiber core-spun yarn is woven to obtain an antistatic fabric.

[0012] This invention first activates acrylic fibers through alkaline hydrolysis, introducing polar functional groups such as carboxyl groups onto the fiber surface and enhancing interfacial reactivity. Then, L-cysteine ​​is used as the key interfacial modification component. Its molecules possess both amino and thiol groups as interaction sites, enabling ionic and hydrogen bonding with the polar sites on the hydrolyzed fiber surface to form multi-point adsorption. This creates a stable interfacial transition layer on the acrylic fiber surface, increasing the density of polar sites and providing effective anchoring and fixation sites for protein molecules. Covalent bonds connect the acrylic fiber to the protein molecules, enriching the modified acrylic surface with hydrophilic polar groups such as -NH and -COOH. This makes it easier for the fabric to form a continuous hydration layer and ion-conducting medium under common usage humidity conditions, reducing surface resistance and promoting charge migration and release after triboelectric charging, thus reducing static electricity buildup. Simultaneously, the introduction of hydrophilic segments on the surface can regulate the triboelectric interface state, reduce charge separation intensity, and improve the stability of the antistatic effect.

[0013] Furthermore, the invention first forms an L-cysteine ​​interfacial transition layer and then grafts proteins onto the surface of this layer, thereby improving the binding strength and wash resistance of the hydrophilic protein segments on the fiber surface. Compared to directly bonding the protein onto the acrylic fiber using only physical action, this invention further improves the adhesion of the protein membrane by forming an L-cysteine ​​interfacial transition layer to achieve multi-site binding and fixation, which can reduce the probability of protein component migration and detachment under washing and friction conditions. At the same time, the hydrophilic polar groups on the fiber surface easily form a bound water layer with water molecules, producing a certain interfacial lubrication effect, reducing frictional wear caused by washing and agitation, thereby delaying the decay of hydrophilic function and making the antistatic performance more durable and stable after repeated washing.

[0014] This invention uses dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride to modify cellulose nanofibers (CNW) to obtain organosilicon quaternary ammonium salt modified CNW. Further, this invention introduces the organosilicon quaternary ammonium salt modified CNW into the spinning solution and dispersion, and uses conjugated electrospinning to form a core-shell structure with the modified acrylic nanofibers spirally wrapped around the cotton yarn surface. The quaternary ammonium salt in the organosilicon quaternary ammonium salt modified CNW carries a permanent positive charge, endowing the cotton yarn shell with antibacterial properties. Furthermore, it acts as a high-modulus nanoskeleton, forming a reinforcing support within the shell, and through hydrogen bonding / electrostatic interactions, it generates multi-point binding with the modified acrylic segments, enhancing the bonding strength and density of the shell network, thereby improving overall mechanical properties and reducing the migration and shedding of functional components during use and washing. In addition, the dispersion is electrostatically sprayed onto the surface of the coating shell by the second set of needles, which is more conducive to the enrichment of organosilicon quaternary ammonium salt modified CNW on the shell surface and improves its effective exposure. In the presence of the hydration layer, it further promotes the dissipation of ionic charge and enhances the antistatic response speed and durability of the fabric; its quaternary ammonium salt sites can also provide contact antibacterial effect.

[0015] Optionally, in step S1, the acrylic fiber is added to a 10wt% sodium hydroxide aqueous solution, stirred at 70-80℃ for 10-20 min, rinsed with deionized water 3-5 times, dried at 70℃ for 8-10 h, immersed in a 5wt% L-cysteine ​​aqueous solution, stirred at 70-80℃ for 1-2 h, then immersed in a 5wt% protein dispersion, stirred and reacted at 50-60℃ for 40-60 min, separated, washed with deionized water 3-5 times, and vacuum dried at 50℃ for 10-12 h to obtain the modified acrylic fiber; the protein in the protein dispersion is either casein or collagen.

[0016] Optionally, in step S2, cellulose nanocrystals are added to an aqueous ethanol solution with a concentration of 90-95 vol%, and magnetically stirred for 30-40 min. Then, dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride is added and the pH is adjusted to 4-5.5. The mixture is then shaken and reacted at 65-75°C and 140 rpm for 5-6 h. After cooling, the mixture is washed 2-4 times with anhydrous ethanol by centrifugation and then vacuum dried at 60-65°C for 8-10 h to obtain organosilicon quaternary ammonium salt modified CNW.

[0017] Optionally, the spinning solution is obtained by adding modified acrylic fiber to DMF, stirring at 40~45℃ for 5~6h, and then adding organosilicon quaternary ammonium salt modified CNW and stirring for another 2~3h; the dispersion is obtained by mixing anhydrous ethanol and organosilicon quaternary ammonium salt modified CNW and ultrasonically treating for 40~90min.

[0018] Optionally, during the preparation of the dispersion, 0.3-0.6 parts of an antibacterial composite material are added when mixing anhydrous ethanol and organosilicon quaternary ammonium salt modified CNW. The antibacterial composite material is prepared by adding 0.8-1 parts of cinnamaldehyde-modified chitosan to 800-1000 parts of deionized water, adjusting the pH to 2.5-3.5 with acetic acid solution, stirring at 55-65℃ for 30-50 min, adding 3-4 parts of IPTS-modified graphene oxide and ultrasonically treating for 40-50 min, magnetically stirring at 55-65℃ for 40-60 min, adding sodium hydroxide solution dropwise to adjust the pH to 9.5-10, heating at 60-65℃ for 3-5 h, washing with deionized water 2-4 times, filtering, vacuum drying at 50-60℃ for 8-10 h, and grinding.

[0019] This invention introduces an antibacterial composite material formed by IPTS-modified graphene oxide loaded with cinnamaldehyde-modified chitosan into a dispersion, which is deposited synchronously with the dispersion during electrostatic spraying and preferentially distributed on the surface of the coating layer, thereby further improving the antibacterial properties and heat retention. Compared to directly adding cinnamaldehyde-modified chitosan and IPTS-modified graphene oxide to the dispersion system, this invention loads cinnamaldehyde-modified chitosan onto the surface of IPTS-modified graphene oxide. This allows chitosan segments to form a polymeric coating layer on the graphene oxide sheet surface, inhibiting sheet aggregation and sedimentation through steric hindrance and electrostatic interactions, thereby improving its dispersion uniformity during spinning. Furthermore, after loading cinnamaldehyde-modified chitosan, the cation sites and Schiff base active sites of chitosan are more concentrated on the sheet surface, achieving higher effective exposure with the high specific surface area of ​​graphene oxide, increasing contact efficiency with bacterial cell walls / membranes, and thus enhancing the antibacterial onset speed and duration. Simultaneously, the silane functional groups introduced by IPTS modification facilitate multi-point bonding and fixation between the complex and the shell matrix, reducing the risk of migration and loss under washing and friction conditions, resulting in better retention of antibacterial properties. The sheet structure can also form certain barriers and tortuous channels, synergistically improving the shell's density and thermal insulation stability.

[0020] Optionally, the cinnamaldehyde-modified chitosan is prepared by dissolving 1-1.5 parts of chitosan in 90-100 parts of a 1 vol% aqueous acetic acid solution, adding dropwise to 100 parts of a 0.8-1 wt% cinnamaldehyde ethanol solution, stirring and reacting at 45-55°C for 6-8 hours, then adding dropwise sodium hydroxide solution to adjust the pH to 9.5-10, washing successively with deionized water and anhydrous ethanol, filtering, vacuum drying at 50-60°C for 8-10 hours, and grinding.

[0021] This method involves fully swelling and dissolving chitosan in an acetic acid medium to expose its amino sites. After dropwise introduction of cinnamaldehyde, its aldehyde groups condense with the amino groups of chitosan to form a Schiff base structure. The cationic sites in chitosan can adsorb onto negatively charged groups on the bacterial cell wall / membrane surface, perturbing membrane permeability. Simultaneously, the Schiff base structure introduced by the condensation of chitosan amino groups and cinnamaldehyde aldehyde groups possesses certain biological activity, further enhancing interference with the bacterial membrane lipid layer and bacterial protein / enzyme system, resulting in faster and more sustained antibacterial action. The structural formula of the obtained cinnamaldehyde-modified chitosan is as follows:

[0022]

[0023] Optionally, the IPTS-modified graphene oxide is prepared by adding 0.02-0.03 parts of dibutyltin dioleate dropwise to a mixture of 1-1.5 parts of ethyl acetate and 1.5-2 parts of propyltriethoxysilane isocyanate. After magnetic stirring at 35-45°C for 4-5 hours, 5-7 parts of graphene oxide, 250-280 parts of anhydrous ethanol, and 120-150 parts of deionized water are added and mixed. After ultrasonic treatment for 50-80 minutes, sodium hydroxide solution is added to adjust the pH to 9.5-10. The mixture is stirred at 600 r / min at 55-60°C for 10-12 hours. After washing with anhydrous ethanol and deionized water, the mixture is filtered and vacuum dried at 60-70°C for 8-10 hours.

[0024] This invention modifies graphene oxide by silanization with propyltriethoxysilane, introducing hydrolyzable triethoxysilane groups onto the sheet surface and improving its interfacial properties. Dibutyltin dioleate is used as a catalyst, which facilitates the reaction between isocyanate and oxygen-containing groups such as hydroxyl or carboxyl groups on the graphene oxide surface, improving grafting efficiency. An ethanol / water mixture combined with ultrasonic dispersion further exfoliates the sheets and increases the reaction contact area. Adjusting the pH to alkaline and stirring under heating promotes the hydrolysis and condensation of silane groups, forming a stable silicon-oxygen bond structure on the sheet surface, thereby reducing the tendency for sheet aggregation and improving dispersion uniformity in subsequent systems.

[0025] Optionally, in the conjugate electrospinning device, the spinning solution is injected into the first set of needles A1 and A2, and the dispersion is injected into the second set of needles B1 and B2. A voltage of 20-25kV is applied, and cotton yarn is continuously fed into the electric field region at a speed of 8-15m / min. Under the action of the high-voltage electric field, the first set of needles electrospins the spinning solution to form nanofibers. The nanofibers are deposited on the surface of the cotton yarn and spirally wound under the rotational traction of the metal flared end at 30-40r / min to form a coating shell. The second set of needles electrostatically sprays the dispersion, so that the organosilicon quaternary ammonium salt modified CNW in the dispersion is deposited on the surface of the coating shell. The dispersion is then collected and wound at a speed of 40-60r / min to obtain fiber core-spun yarn. The fiber core-spun yarn is then woven to make an antistatic fabric.

[0026] Optionally, the flow rate of the first set of needles A1 and A2 is 0.6~1.0 mL / h, and the flow rate of the second set of needles B1 and B2 is 0.1~0.3 mL / h.

[0027] This invention sets the liquid supply flow rate of the first set of needles A1 and A2 to 0.6~1.0 mL / h and the liquid supply flow rate of the second set of needles B1 and B2 to 0.1~0.3 mL / h to control the supply ratio of the main fiber-forming component (spinning solution) and the functional enrichment component (dispersion), forming a continuous, stable shell with effectively exposed functional sites. In the spinning solution, modified acrylic / organosilicon quaternary ammonium salt modified CNW serves as the main fiber-forming component, with a higher flow rate to ensure spinning stability and continuous nanofiber generation, resulting in a dense coating shell and providing some mechanical support. In the dispersion, organosilicon quaternary ammonium salt modified CNW and antibacterial composite material serve as functional enrichment components, with a lower flow rate to reduce the adverse effects of large particle accumulation on the final fiber quality and to promote the deposition of functional components mainly on the surface of the coating shell, improving the effective exposure and utilization rate of antibacterial and antistatic sites.

[0028] Preferably, the linear density of the cotton yarn is 40 to 60 count.

[0029] The present invention also provides an antistatic fabric based on modified acrylic fiber, comprising the following parts by weight of raw materials: 45-50 parts modified acrylic fiber, 250-300 parts DMF, 1.4-2.5 parts organosilicon quaternary ammonium salt modified CNW, 120-150 parts anhydrous ethanol, and 150-200 parts cotton yarn; wherein the modified acrylic fiber comprises the following parts by weight of raw materials: 50-60 parts acrylic fiber, 320-350 parts sodium hydroxide aqueous solution, 300-320 parts L-cysteine ​​aqueous solution, and 300-350 parts protein dispersion; wherein the organosilicon quaternary ammonium salt modified CNW comprises the following parts by weight of raw materials: 4-5 parts cellulose nanofibers, 200-300 parts ethanol aqueous solution, and 5-7 parts dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride.

[0030] The antistatic fabric finally obtained by the above material ratio can stabilize the spinning solution, make the shell layer continuous and dense, and firmly cover the cotton yarn to form a stable core-shell structure. The hydrophilic polar sites on the modified acrylic surface and the ionic sites of the modified CNW work together to improve the efficiency of moisture absorption and charge dissipation, and reduce static electricity accumulation. At the same time, the shell layer reinforcement and surface site enrichment reduce migration and shedding under washing friction, making the antistatic effect more durable.

[0031] The above-described technical solution of the present invention has at least the following beneficial effects:

[0032] 1. This invention introduces polar functional groups into acrylic fibers through alkaline hydrolysis activation and constructs an interfacial transition layer using L-cysteine, enabling protein molecules to be effectively anchored and fixed on the fiber surface, promoting the enrichment of hydrophilic segments / polar groups of proteins on the surface. As a result, the fabric is more likely to form a stable hydration layer and ion conduction channels under operating humidity, significantly reducing surface resistance, accelerating the release of static charge, and improving antistatic properties by adjusting the triboelectric interface to reduce charge separation intensity.

[0033] 2. This invention first forms an L-cysteine ​​interfacial transition layer on the surface of acrylic fibers, then grafts proteins for functionalization and fixation, improving the binding strength and wash resistance of the protein-related hydrophilic sites, thereby enhancing the antistatic durability. Compared to relying solely on physical adsorption, the interfacial transition layer provides multiple binding sites, inhibiting the migration and stripping of functional components caused by washing friction. During washing, the hydrophilic polar groups easily form hydrogen bonds with water molecules to create an interfacial lubrication effect, reducing washing friction wear, delaying film degradation, and making the antistatic performance more stable after repeated washing.

[0034] 3. This invention modifies CNW with dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride to obtain organosilicon quaternary ammonium salt modified CNW, which is then introduced into spinning solution and dispersion solution respectively. Conjugate electrospinning is used to construct a helical core-shell structure on the surface of cotton yarn. The permanent positive charge of the quaternary ammonium salt imparts contact-type antibacterial properties and a potential point to the shell layer. The organosilicon quaternary ammonium salt modified CNW acts as a high-modulus nanoframework, enhancing the shell layer's density and bonding strength through hydrogen bonding / electrostatic multi-point binding with modified acrylic fiber segments, improving mechanical properties and reducing washing migration and shedding. Simultaneous deposition in the dispersion solution promotes the enrichment of sites near the surface, increasing exposure. The presence of a hydration layer accelerates the dissipation of ionic charges, enhancing antistatic response and durability. Detailed Implementation

[0035] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. The described embodiments are some embodiments of the present invention, and all other embodiments obtained by those skilled in the art based on the described embodiments of the present invention are within the scope of protection of the present invention.

[0036] The cellulose nanofibers used in this embodiment of the invention were purchased from Nanjing Jicang Nanotechnology Co., Ltd., and the cotton yarn was purchased from Weifang Xinda Textile Co., Ltd.

[0037] Example 1

[0038] 50g of acrylic fiber (CAS No.: 25014-41-9) was added to 320g of 10wt% sodium hydroxide aqueous solution, stirred at 70℃ for 10min, rinsed 3 times with deionized water, dried at 70℃ for 8h, immersed in 300g of 5wt% L-cysteine ​​aqueous solution, stirred at 70℃ for 1h, and then immersed in 300g of 5wt% protein (casein, CAS No.: 9000-71-9) dispersion, stirred and reacted at 50℃ for 40min, separated, washed 3 times with deionized water, and vacuum dried at 50℃ for 10h to obtain modified acrylic fiber.

[0039] 0.02 g of dibutyltin dioleate was added dropwise to a mixture of 1.0 g ethyl acetate and 1.5 g propyltriethoxysilane isocyanate (IPTS). After magnetic stirring at 35 °C for 4 h, 5 g of graphene oxide, 250 g of anhydrous ethanol, and 120 g of deionized water were added and mixed. The mixture was ultrasonically treated for 50 min, and then sodium hydroxide solution was added to adjust the pH to 9.5. The mixture was stirred at 55 °C at 600 r / min for 10 h. After washing with anhydrous ethanol and deionized water, the mixture was filtered and vacuum dried at 60 °C for 8 h to obtain IPTS-modified graphene oxide. 1.0 g of chitosan was dissolved in 90 g of 1 vol% acetic acid aqueous solution and added dropwise to 100 g of 0.8 wt% cinnamaldehyde ethanol solution. After stirring at 5℃ for 6 hours, sodium hydroxide solution was added dropwise to adjust the pH to 9.5, causing a flocculent precipitate to form in the solution. The precipitate was washed successively with deionized water and anhydrous ethanol, filtered, and vacuum dried at 50℃ for 8 hours. The precipitate was then ground to obtain cinnamaldehyde-modified chitosan. 0.8 g of cinnamaldehyde-modified chitosan was added to 800 g of deionized water, and the pH was adjusted to 2.5 with acetic acid solution. The mixture was stirred at 55℃ for 30 minutes, and 3 g of IPTS-modified graphene oxide was added. The mixture was ultrasonically treated for 40 minutes, magnetically stirred at 55℃ for 40 minutes, and sodium hydroxide solution was added dropwise to adjust the pH to 9.5, causing a flocculent precipitate to form in the solution. The mixture was heated at 60℃ for 3 hours, washed twice with deionized water, filtered, and vacuum dried at 50℃ for 8 hours. The mixture was then ground to obtain the antibacterial composite material.

[0040] 4 g of cellulose nanofibers (CNW) were added to 200 g of 90 vol% ethanol aqueous solution and magnetically stirred for 30 min. Then, 5 g of dimethyl octadecyl [3-(trimethoxysilyl)propyl]ammonium chloride was added and the pH was adjusted to 4. The mixture was then shaken at 65 °C and 140 rpm for 5 h. After cooling, the mixture was washed twice with anhydrous ethanol by centrifugation and dried under vacuum at 60 °C for 8 h to obtain organosilicon quaternary ammonium salt modified CNW.

[0041] 45g of modified acrylic fiber was added to 250g of DMF and stirred at 40℃ for 5h. Then, 1.0g of organosilicon quaternary ammonium salt modified CNW was added and stirred for another 2h to obtain the spinning solution. 120g of anhydrous ethanol, 0.4g of organosilicon quaternary ammonium salt modified CNW and 0.3g of antibacterial composite material were mixed and ultrasonically treated for 90min to obtain the dispersion. On a conjugate electrospinning device, the spinning solution was injected into the first set of needles A1 and A2, and the dispersion was injected into the second set of needles B1 and B2, and a voltage of 20kV was applied. The flow rate of the solution for needles A1 and A2 was 0.6mL / h, and the flow rate of the solution for needles B1 and B2 was 0.1mL / h. 150g of 40-count cotton yarn is continuously fed into the electric field region at a speed of 9m / min. Under the action of a high-voltage electric field, the first set of needles electrospins the spinning solution to form nanofibers. The nanofibers are deposited on the surface of the cotton yarn and spirally wound under the continuous rotation and traction of the metal flared end at 30r / min to form a coating shell. The second set of needles electrostatically sprays the dispersion solution, causing the organosilicon quaternary ammonium salt modified CNW and antibacterial composite material in the dispersion solution to be deposited on the surface of the coating shell. Then, the yarn is collected and wound at a speed of 40r / min to obtain fiber core-spun yarn. Finally, the fiber core-spun yarn is woven into an antistatic fabric.

[0042] Example 2

[0043] 60g of acrylic fiber (CAS No.: 25014-41-9) was added to 350g of 10wt% sodium hydroxide aqueous solution, stirred at 80℃ for 20min, rinsed 5 times with deionized water, dried at 70℃ for 10h, immersed in 320g of 5wt% L-cysteine ​​aqueous solution, stirred at 80℃ for 2h, and then immersed in 350g of 5wt% protein (collagen, CAS No.: 9007-34-5) dispersion, stirred at 60℃ for 60min, separated, washed 5 times with deionized water, and vacuum dried at 50℃ for 12h to obtain modified acrylic fiber.

[0044] 0.03 g of dibutyltin dioleate was added dropwise to a mixture of 1.5 g of ethyl acetate and 2.0 g of propyltriethoxysilane isocyanate (IPTS). After magnetic stirring at 45 °C for 5 h, 7 g of graphene oxide, 280 g of anhydrous ethanol, and 150 g of deionized water were added and mixed. The mixture was ultrasonically treated for 80 min, and then sodium hydroxide solution was added to adjust the pH to 10. The mixture was stirred at 60 °C at 600 r / min for 12 h. After washing with anhydrous ethanol and deionized water, the mixture was filtered and vacuum dried at 70 °C for 10 h to obtain IPTS-modified graphene oxide. 1.5 g of chitosan was dissolved in 100 g of 1 vol% acetic acid aqueous solution and added dropwise to 100 g of 1.0 wt% cinnamaldehyde ethanol solution. The mixture was stirred at 55 °C. After stirring for 8 hours, sodium hydroxide solution was added dropwise to adjust the pH to 10, causing a flocculent precipitate to form in the solution. The precipitate was washed successively with deionized water and anhydrous ethanol, filtered, and vacuum dried at 60°C for 10 hours. The precipitate was then ground to obtain cinnamaldehyde-modified chitosan. 1.0 g of cinnamaldehyde-modified chitosan was added to 1000 g of deionized water, and the pH was adjusted to 3.5 with acetic acid solution. The mixture was stirred at 65°C for 50 minutes, and 4 g of IPTS-modified graphene oxide was added and ultrasonically treated for 50 minutes. The mixture was then magnetically stirred at 65°C for 60 minutes, and sodium hydroxide solution was added dropwise to adjust the pH to 10, causing a flocculent precipitate to form in the solution. The mixture was heated at 65°C for 5 hours, washed four times with deionized water, filtered, and vacuum dried at 60°C for 10 hours. The mixture was then ground to obtain the antibacterial composite material.

[0045] 5g of cellulose nanofibers (CNW) were added to 300g of 95vol% ethanol aqueous solution and magnetically stirred for 40min. Then, 7g of dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride was added and the pH was adjusted to 4.5. The mixture was then shaken at 75℃ and 140rpm for 6h. After cooling, the mixture was washed four times with anhydrous ethanol by centrifugation and dried under vacuum at 65℃ for 10h to obtain organosilicon quaternary ammonium salt modified CNW.

[0046] 50g of modified acrylic fiber was added to 300g of DMF and stirred at 45℃ for 6h. Then, 1.5g of organosilicon quaternary ammonium salt modified CNW was added and stirred for another 3h to obtain the spinning solution. 150g of anhydrous ethanol, 1.0g of organosilicon quaternary ammonium salt modified CNW and 0.8g of antibacterial composite material were mixed and ultrasonically treated for 50min to obtain the dispersion. On a conjugate electrospinning device, the spinning solution was injected into the first set of needles A1 and A2, and the dispersion was injected into the second set of needles B1 and B2, with a voltage of 25kV applied. The flow rate of the solution for needles A1 and A2 was 1.0mL / h, and the flow rate of the solution for needles B1 and B2 was 0.3mL / h. 200g of 60-count cotton yarn was continuously fed into the electric field region at a speed of 11m / min. Under the action of a high-voltage electric field, the first set of needles electrospun the spinning solution to form nanofibers. The nanofibers were deposited on the surface of the cotton yarn and spirally wound under the continuous rotation and traction of the metal flared end at 40r / min to form a coating shell. The second set of needles electrostatically sprayed the dispersion solution, causing the organosilicon quaternary ammonium salt modified CNW and antibacterial composite material in the dispersion solution to be deposited on the surface of the coating shell. Subsequently, the yarn was collected and wound at a speed of 60r / min to obtain fiber core-spun yarn. Finally, the fiber core-spun yarn was woven into an antistatic fabric.

[0047] Example 3

[0048] 55g of acrylic fiber (CAS No.: 25014-41-9) was added to 335g of 10wt% sodium hydroxide aqueous solution, stirred at 75℃ for 15min, rinsed 4 times with deionized water, dried at 70℃ for 9h, immersed in 310g of 5wt% L-cysteine ​​aqueous solution, stirred at 75℃ for 1.5h, and then immersed in 325g of 5wt% protein (casein, CAS No.: 9000-71-9) dispersion, stirred at 55℃ for 50min, separated, washed 4 times with deionized water, and vacuum dried at 50℃ for 11h to obtain modified acrylic fiber.

[0049] 0.025 g of dibutyltin dioleate was added dropwise to a mixture of 1.2 g of ethyl acetate and 1.7 g of propyltriethoxysilane isocyanate (IPTS). After magnetic stirring at 40 °C for 4.5 h, 6 g of graphene oxide, 265 g of anhydrous ethanol, and 135 g of deionized water were added and mixed. The mixture was ultrasonically treated for 65 min, and then sodium hydroxide solution was added to adjust the pH to 9.7. The mixture was stirred at 57 °C at 600 r / min for 11 h. After washing with anhydrous ethanol and deionized water, the mixture was filtered and vacuum dried at 65 °C for 9 h to obtain IPTS-modified graphene oxide. 1.2 g of chitosan was dissolved in 95 g of 1 vol% acetic acid aqueous solution and added dropwise to 100 g of 0.9 wt% cinnamaldehyde ethanol solution. After stirring at 0℃ for 7 h, sodium hydroxide solution was added dropwise to adjust the pH to 9.7 to form a flocculent precipitate in the solution. The precipitate was washed successively with deionized water and anhydrous ethanol, filtered, and vacuum dried at 55℃ for 9 h. The precipitate was then ground to obtain cinnamaldehyde-modified chitosan. 0.9 g of cinnamaldehyde-modified chitosan was added to 900 g of deionized water, and the pH was adjusted to 3.0 with acetic acid solution. The mixture was stirred at 60℃ for 40 min, and 3.5 g of IPTS-modified graphene oxide was added and ultrasonically treated for 45 min. The mixture was then magnetically stirred at 60℃ for 50 min, and sodium hydroxide solution was added dropwise to adjust the pH to 9.7 to form a flocculent precipitate in the solution. The mixture was heated at 62℃ for 4 h, washed three times with deionized water, filtered, and vacuum dried at 55℃ for 9 h. The precipitate was then ground to obtain the antibacterial composite material.

[0050] 4.5 g of cellulose nanocrystals (CNW) were added to 250 g of 92 vol% ethanol aqueous solution and magnetically stirred for 35 min. Then, 6 g of dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride was added and the pH was adjusted to 5.5. The mixture was then shaken at 70 °C and 140 rpm for 5.5 h. After cooling, the mixture was washed three times with anhydrous ethanol by centrifugation and dried under vacuum at 62 °C for 9 h to obtain organosilicon quaternary ammonium salt modified CNW.

[0051] 48g of modified acrylic fiber was added to 275g of DMF and stirred at 42℃ for 5.5h. Then, 1.2g of organosilicon quaternary ammonium salt modified CNW was added and stirred for another 2.5h to obtain the spinning solution. 135g of anhydrous ethanol, 0.7g of organosilicon quaternary ammonium salt modified CNW and 0.5g of antibacterial composite material were mixed and ultrasonically treated for 40min to obtain the dispersion. On a conjugate electrospinning device, the spinning solution was injected into the first set of needles A1 and A2, and the dispersion was injected into the second set of needles B1 and B2, and a voltage of 23kV was applied. The flow rate of the solution for needles A1 and A2 was 0.8mL / h, and the flow rate of the solution for needles B1 and B2 was 0.2mL / h. 180g of 50-count cotton yarn was continuously fed into the electric field region at a speed of 10m / min. Under the action of a high-voltage electric field, the first set of needles electrospun the spinning solution to form nanofibers. The nanofibers were deposited on the surface of the cotton yarn and spirally wound under the continuous rotation and traction of the metal flared end at 35r / min to form a coating shell. The second set of needles electrostatically sprayed the dispersion solution, causing the organosilicon quaternary ammonium salt modified CNW and antibacterial composite material in the dispersion solution to be deposited on the surface of the coating shell. Subsequently, the yarn was collected and wound at a speed of 50r / min to obtain fiber core-spun yarn. Finally, the fiber core-spun yarn was woven into an antistatic fabric.

[0052] Example 4

[0053] 52g of acrylic fiber (CAS No.: 25014-41-9) was added to 330g of 10wt% sodium hydroxide aqueous solution, stirred at 73℃ for 12min, rinsed 4 times with deionized water, dried at 70℃ for 9h, immersed in 305g of 5wt% L-cysteine ​​aqueous solution, stirred at 73℃ for 1.2h, and then immersed in 315g of 5wt% protein (collagen, CAS No.: 9007-34-5) dispersion, stirred at 52℃ for 45min, separated, washed 4 times with deionized water, and vacuum dried at 50℃ for 10.5h to obtain modified acrylic fiber.

[0054] 0.023 g of dibutyltin dioleate was added dropwise to a mixture of 1.1 g of ethyl acetate and 1.6 g of propyltriethoxysilane isocyanate (IPTS). After magnetic stirring at 38 °C for 4.2 h, 6 g of graphene oxide, 260 g of anhydrous ethanol, and 130 g of deionized water were added and mixed. The mixture was ultrasonically treated for 60 min, and then sodium hydroxide solution was added to adjust the pH to 9.6. The mixture was stirred at 56 °C at 600 r / min for 10.5 h. After washing with anhydrous ethanol and deionized water sequentially, the mixture was filtered and vacuum dried at 63 °C for 9 h to obtain IPTS-modified graphene oxide. 1.1 g of chitosan was dissolved in 95 g of 1 vol% acetic acid aqueous solution and added dropwise to 100 g of 0.9 wt% cinnamaldehyde ethanol solution. After stirring at 48℃ for 7 hours, sodium hydroxide solution was added dropwise to adjust the pH to 9.6, causing a flocculent precipitate to form in the solution. The precipitate was washed successively with deionized water and anhydrous ethanol, filtered, and vacuum dried at 55℃ for 9 hours. The precipitate was then ground to obtain cinnamaldehyde-modified chitosan. 0.9 g of cinnamaldehyde-modified chitosan was added to 950 g of deionized water, and the pH was adjusted to 3.2 with acetic acid solution. The mixture was stirred at 60℃ for 40 minutes, and 3.6 g of IPTS-modified graphene oxide was added and ultrasonically treated for 45 minutes. The mixture was then magnetically stirred at 60℃ for 50 minutes. Sodium hydroxide solution was added dropwise to adjust the pH to 9.6, causing a flocculent precipitate to form in the solution. The mixture was heated at 62℃ for 4 hours, washed three times with deionized water, filtered, and vacuum dried at 55℃ for 9 hours. The mixture was then ground to obtain the antibacterial composite material.

[0055] 4.2 g of cellulose nanocrystals (CNW) were added to 230 g of 92 vol% ethanol aqueous solution and magnetically stirred for 35 min. Then, 5.5 g of dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride was added and the pH was adjusted to 4.8. The mixture was then shaken at 68 °C and 140 rpm for 5.3 h. After cooling, the mixture was washed three times with anhydrous ethanol by centrifugation and dried under vacuum at 62 °C for 9 h to obtain organosilicon quaternary ammonium salt modified CNW.

[0056] 46g of modified acrylic fiber was added to 270g of DMF and stirred at 42℃ for 5.5h. Then, 1.2g of organosilicon quaternary ammonium salt modified CNW was added and stirred for another 2.5h to obtain the spinning solution. 130g of anhydrous ethanol, 0.6g of organosilicon quaternary ammonium salt modified CNW and 0.5g of antibacterial composite material were mixed and ultrasonically treated for 60min to obtain the dispersion. On a conjugate electrospinning device, the spinning solution was injected into the first set of needles A1 and A2, and the dispersion was injected into the second set of needles B1 and B2, and a voltage of 22kV was applied. The flow rate of the solution for needles A1 and A2 was 0.75mL / h, and the flow rate of the solution for needles B1 and B2 was 0.2mL / h. 190g of 50-count cotton yarn was continuously fed into the electric field region at a speed of 10.5m / min. Under the action of a high-voltage electric field, the first set of needles electrospun the spinning solution to form nanofibers. The nanofibers were deposited on the surface of the cotton yarn and spirally wound under the continuous rotation and traction of the metal flared end at 35r / min to form a coating shell. The second set of needles electrostatically sprayed the dispersion solution, causing the organosilicon quaternary ammonium salt modified CNW and antibacterial composite material in the dispersion solution to be deposited on the surface of the coating shell. Subsequently, the yarn was collected and wound at a speed of 55r / min to obtain fiber core-spun yarn. Finally, the fiber core-spun yarn was woven to produce an antistatic fabric.

[0057] Example 5

[0058] 58g of acrylic fiber (CAS No.: 25014-41-9) was added to 340g of 10wt% sodium hydroxide aqueous solution, stirred at 78℃ for 18min, rinsed 4 times with deionized water, dried at 70℃ for 9.5h, immersed in 315g of 5wt% L-cysteine ​​aqueous solution, stirred at 78℃ for 1.8h, and then immersed in 340g of 5wt% protein (casein, CAS No.: 9000-71-9) dispersion, stirred at 58℃ for 55min, separated, washed 4 times with deionized water, and vacuum dried at 50℃ for 11h to obtain modified acrylic fiber.

[0059] 0.026 g of dibutyltin dioleate was added dropwise to a mixture of 1.3 g of ethyl acetate and 1.8 g of propyltriethoxysilane isocyanate (IPTS). After magnetic stirring at 42 °C for 4.8 h, 6 g of graphene oxide, 270 g of anhydrous ethanol, and 140 g of deionized water were added and mixed. The mixture was ultrasonically treated for 70 min, and then sodium hydroxide solution was added to adjust the pH to 9.8. The mixture was stirred at 58 °C at 600 r / min for 11.5 h. After washing with anhydrous ethanol and deionized water sequentially, the mixture was filtered and vacuum dried at 66 °C for 9 h to obtain IPTS-modified graphene oxide. 1.3 g of chitosan was dissolved in 98 g of 1 vol% acetic acid aqueous solution and added dropwise to 100 g of 0.9 wt% cinnamaldehyde ethanol solution. The mixture was stirred at 52 °C for 4.8 h. After stirring at ℃ for 7.5 h, sodium hydroxide solution was added dropwise to adjust the pH to 9.8, causing a flocculent precipitate to form in the solution. The precipitate was washed successively with deionized water and anhydrous ethanol, filtered, and vacuum dried at 58℃ for 9 h. The precipitate was then ground to obtain cinnamaldehyde-modified chitosan. 0.9 g of cinnamaldehyde-modified chitosan was added to 900 g of deionized water, and the pH was adjusted to 3.0 with acetic acid solution. The mixture was stirred at 62℃ for 45 min, and 3.4 g of IPTS-modified graphene oxide was added and ultrasonically treated for 45 min. The mixture was then magnetically stirred at 62℃ for 55 min, and sodium hydroxide solution was added dropwise to adjust the pH to 9.8, causing a flocculent precipitate to form in the solution. The mixture was heated at 63℃ for 4.5 h, washed three times with deionized water, filtered, and vacuum dried at 58℃ for 9 h. The mixture was then ground to obtain the antibacterial composite material.

[0060] 4.6 g of cellulose nanocrystals (CNW) were added to 260 g of 93 vol% ethanol aqueous solution and magnetically stirred for 38 min. Then, 6.5 g of dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride was added and the pH was adjusted to 5.2. The mixture was then shaken at 72 °C and 140 rpm for 5.8 h. After cooling, the mixture was washed three times with anhydrous ethanol by centrifugation and dried under vacuum at 63 °C for 9 h to obtain organosilicon quaternary ammonium salt modified CNW.

[0061] 49g of modified acrylic fiber was added to 290g of DMF and stirred at 44℃ for 6h. Then, 1.4g of organosilicon quaternary ammonium salt modified CNW was added and stirred for another 2.5h to obtain a spinning solution. 145g of anhydrous ethanol, 0.5g of organosilicon quaternary ammonium salt modified CNW and 0.4g of antibacterial composite material were mixed and ultrasonically treated for 80min to obtain a dispersion. On a conjugate electrospinning device, the spinning solution was injected into the first set of needles A1 and A2, and the dispersion was injected into the second set of needles B1 and B2, and a voltage of 21kV was applied. The flow rate of the solution for needles A1 and A2 was 0.95mL / h, and the flow rate of the solution for needles B1 and B2 was 0.12mL / h. 165g of 40-count cotton yarn was continuously fed into the electric field region at a speed of 9.5m / min. Under the action of a high-voltage electric field, the first set of needles electrospun the spinning solution to form nanofibers. The nanofibers were deposited on the surface of the cotton yarn and spirally wound under the continuous rotation and traction of the metal flared end at 32r / min to form a coating shell. The second set of needles electrostatically sprayed the dispersion solution, causing the organosilicon quaternary ammonium salt modified CNW and antibacterial composite material in the dispersion solution to be deposited on the surface of the coating shell. Subsequently, the yarn was collected and wound at a speed of 48r / min to obtain fiber core-spun yarn. Finally, the fiber core-spun yarn was woven to produce an antistatic fabric.

[0062] Example 6

[0063] 54g of acrylic fiber (CAS No.: 25014-41-9) was added to 332g of 10wt% sodium hydroxide aqueous solution, stirred at 76℃ for 16min, rinsed 4 times with deionized water, dried at 70℃ for 9h, immersed in 308g of 5wt% L-cysteine ​​aqueous solution, stirred at 76℃ for 1.4h, and then immersed in 320g of 5wt% protein (casein, CAS No.: 9000-71-9) dispersion, stirred at 56℃ for 50min, separated, washed 4 times with deionized water, and vacuum dried at 50℃ for 11h to obtain modified acrylic fiber.

[0064] 0.025 g of dibutyltin dioleate was added dropwise to a mixture of 1.2 g of ethyl acetate and 1.7 g of propyltriethoxysilane isocyanate (IPTS). After magnetic stirring at 40 °C for 4.5 h, 6 g of graphene oxide, 268 g of anhydrous ethanol, and 138 g of deionized water were added and mixed. The mixture was ultrasonically treated for 65 min, and then sodium hydroxide solution was added to adjust the pH to 9.7. The mixture was stirred at 57 °C at 600 r / min for 11 h. After washing with anhydrous ethanol and deionized water sequentially, the mixture was filtered and vacuum dried at 65 °C for 9 h to obtain IPTS-modified graphene oxide. 1.2 g of chitosan was dissolved in 96 g of 1 vol% acetic acid aqueous solution and added dropwise to 100 g of 0.9 wt% cinnamaldehyde ethanol solution. After stirring at 0℃ for 7 h, sodium hydroxide solution was added dropwise to adjust the pH to 9.7 to form a flocculent precipitate in the solution. The precipitate was washed successively with deionized water and anhydrous ethanol, filtered, and vacuum dried at 55℃ for 9 h. The precipitate was then ground to obtain cinnamaldehyde-modified chitosan. 0.9 g of cinnamaldehyde-modified chitosan was added to 920 g of deionized water, and the pH was adjusted to 3.2 with acetic acid solution. The mixture was stirred at 60℃ for 42 min, and 3.6 g of IPTS-modified graphene oxide was added and ultrasonically treated for 45 min. The mixture was then magnetically stirred at 60℃ for 55 min, and sodium hydroxide solution was added dropwise to adjust the pH to 9.7 to form a flocculent precipitate in the solution. The mixture was heated at 62℃ for 4 h, washed three times with deionized water, filtered, and vacuum dried at 55℃ for 9 h. The mixture was then ground to obtain the antibacterial composite material.

[0065] 4.8 g of cellulose nanocrystals (CNW) were added to 270 g of 94 vol% ethanol aqueous solution and magnetically stirred for 36 min. Then, 6.8 g of dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride was added and the pH was adjusted to 4.6. The mixture was then shaken at 73 °C and 140 rpm for 5.6 h. After cooling, the mixture was washed three times with anhydrous ethanol by centrifugation and dried under vacuum at 63 °C for 9 h to obtain organosilicon quaternary ammonium salt modified CNW.

[0066] 47g of modified acrylic fiber was added to 280g of DMF and stirred at 43℃ for 5.5h. Then, 1.3g of organosilicon quaternary ammonium salt modified CNW was added and stirred for another 2.5h to obtain the spinning solution. 140g of anhydrous ethanol, 0.8g of organosilicon quaternary ammonium salt modified CNW and 0.6g of antibacterial composite material were mixed and ultrasonically treated for 70min to obtain the dispersion. On a conjugate electrospinning device, the spinning solution was injected into the first set of needles A1 and A2, and the dispersion was injected into the second set of needles B1 and B2, and a voltage of 24kV was applied. The flow rate of the solution for needles A1 and A2 was 0.7mL / h, and the flow rate of the solution for needles B1 and B2 was 0.28mL / h. 175g of 60-count cotton yarn was continuously fed into the electric field region at a speed of 10m / min. Under the action of a high-voltage electric field, the first set of needles electrospun the spinning solution to form nanofibers. The nanofibers were deposited on the surface of the cotton yarn and spirally wound under the continuous rotation and traction of the metal flared end at 38r / min to form a coating shell. The second set of needles electrostatically sprayed the dispersion solution, causing the organosilicon quaternary ammonium salt modified CNW and antibacterial composite material in the dispersion solution to be deposited on the surface of the coating shell. Subsequently, the yarn was collected and wound at a speed of 55r / min to obtain fiber core-spun yarn. Finally, the fiber core-spun yarn was woven into an antistatic fabric.

[0067] The present invention also includes comparative examples and related experiments.

[0068] Comparative Example 1

[0069] Compared with Example 3, the only difference is that acrylic fiber is used directly instead of modified acrylic fiber, while the other preparation methods and components are completely the same, and the antistatic fabric is finally obtained.

[0070] Comparative Example 2

[0071] Compared with Example 3, the only difference is that nanocellulose whiskers are used directly to replace organosilicon quaternary ammonium salt to modify CNW. The other preparation methods and components are completely consistent, and the antistatic fabric is finally obtained.

[0072] Comparative Example 3

[0073] Compared with Example 3, the only difference is that the second set of needles and the electrostatic spraying deposition of the dispersion liquid were not set. Only the first set of needles was used to electrospin the spinning solution. The other preparation methods and components were completely consistent, and the antistatic fabric was finally obtained.

[0074] Performance testing

[0075] The antistatic fabrics prepared in Examples 1-6 and Comparative Examples 1-3 were subjected to relevant performance tests. The resistivity, triboelectric voltage, and electrostatic voltage half-life were tested according to GB / T12703.4-2010 Electrostatic Properties of Textiles to evaluate the antistatic properties. The tensile strength was tested according to GB / T3923.1-2013 Tensile Properties of Textile Fabrics Part 1 to evaluate the mechanical properties. The results of the above performance tests are shown in Table 1.

[0076] Table 1

[0077]

[0078] As shown in Table 1, the surface resistivity of the antistatic fabrics obtained in Examples 1-6 is all within 10. 5 The resistivity is on the order of Ω, with a triboelectric voltage of 125~195V and a static voltage half-life of 0.4~0.8s, indicating that the antistatic fabric prepared by this invention significantly reduces static electricity accumulation after triboelectric charging. In contrast, the surface resistivity of Comparative Example 1 increased to 4.8×10⁻⁶. 8 The resistivity and voltage of the unmodified acrylic fiber reached 8500V with a half-life extended to 18.0s, indicating that the unmodified acrylic fiber easily generates and accumulates static electricity. The resistivity and voltage of Comparative Example 2 were also significantly higher than those of the Example, indicating that the organosilicon quaternary ammonium salt modification of CNW also plays a key role in antistatic effects. In addition, the tensile strength of Examples 1-6 was also better than that of Comparative Examples 1-3.

[0079] In addition, the antistatic fabrics prepared in Examples 1-6 and Comparative Examples 1-3 were tested for viable bacterial concentration according to GB / T20944.2-2007 Evaluation of antimicrobial properties of textiles - Part 2: Test method of absorption method, and the antimicrobial inhibition rate was calculated to evaluate the antimicrobial performance; the thermal resistance R was determined according to GB / T35762-2017 Test method for heat transfer properties of textiles - Plate method. ct The insulation rate was used to evaluate the thermal insulation performance; the results of the above performance tests are shown in Table 2.

[0080] Table 2

[0081]

[0082] As shown in Table 2, the inhibition rates of Examples 1-6 against Escherichia coli and Staphylococcus aureus were 97.8%-99.2% and 98.4%-99.5%, respectively, demonstrating stable broad-spectrum antibacterial effects; meanwhile, the thermal resistance Rct was 0.300-0.320m. 2The K / W ratio and the heat retention rate of 44.0%~47.5% indicate that the antistatic fabric prepared by this invention has good heat retention performance. In contrast, the antibacterial rate of Comparative Example 1 using conventional acrylic fibers decreased to 76.5%~78.2%, and the antibacterial rate of Comparative Example 2, which used nanocellulose whiskers to replace organosilicon quaternary ammonium salt to modify CNW, was significantly reduced due to the lack of organosilicon quaternary ammonium salt modification. The antibacterial performance of Comparative Example 3 was also significantly reduced even when organosilicon quaternary ammonium salt was present in the spinning solution. In addition, Comparative Example 3 had the lowest thermal resistance Rct and heat retention rate, indicating that the lack of dispersion synergistic deposition and surface enrichment affected the shell density, which also resulted in the absence of antibacterial composite material, thus limiting both antibacterial and heat retention performance.

[0083] The antistatic fabrics prepared in Examples 1-6 and Comparative Examples 1-3 were washed 20 times according to the selected household washing program in GB / T8629-2017. The resistivity, antibacterial rate and heat retention rate were re-measured to evaluate the washability and retention. The specific performance test results are shown in Table 3.

[0084] Table 3

[0085]

[0086] As shown in Table 3, after 20 washes using the household washing program specified in GB / T8629-2017, the surface resistivity of Examples 1-6 remained at 10. 5 Even with an Ω-level resistance, the antibacterial rate remained within the range of 93.5% to 97.2%, and the heat retention rate remained within the range of 42.5% to 46.0%, indicating that the antistatic fabric prepared by this invention has good wash fastness and performance retention. In Comparative Example 2, the use of nanocellulose whiskers to replace organosilicon quaternary ammonium salts to modify CNW made it difficult to form stable antibacterial sites, resulting in a significant decrease in antibacterial performance after 20 washes. Comparative Example 3 also showed a significant decrease in heat retention and antibacterial rate after washing, further illustrating that dispersion deposition and surface enrichment play an important role in maintaining functionality.

[0087] In summary, the present invention exhibits superior performance in terms of antistatic, antibacterial, and heat-retaining properties, and also demonstrates better washability and stability.

[0088] The above are preferred embodiments of the present invention. Those skilled in the art can make several improvements and modifications without departing from the principle of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. A preparation process for an antistatic fabric based on modified acrylic fiber, characterized in that, Includes the following steps: S1. Add acrylic fiber to sodium hydroxide aqueous solution, heat and stir, rinse, dry, then immerse in L-cysteine ​​aqueous solution and protein dispersion in sequence, heat and stir, separate, wash, and dry to obtain modified acrylic fiber; S2. Cellulose nanocrystals were added to an ethanol aqueous solution and magnetically stirred. Then, dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride was added and the mixture was shaken to react. After cooling, washing, and drying, the organosilicon quaternary ammonium salt modified CNW was obtained. S3. Modified acrylic fiber, DMF, and organosilicon quaternary ammonium salt modified CNW are mixed and stirred to obtain a spinning solution; Anhydrous ethanol and organosilicon quaternary ammonium salt-modified CNW were mixed and ultrasonically treated to obtain a dispersion. S4. On the conjugate electrospinning device, the spinning solution and dispersion solution are fed into two sets of needles respectively. Under the action of a high voltage electric field, the spinning solution is electrospun to form nanofibers. Cotton yarn is fed into the electric field area, so that the nanofibers spirally wind around the surface of the cotton yarn and form a coating shell. The dispersion solution is electrostatically sprayed to deposit the organosilicon quaternary ammonium salt modified CNW on the surface of the coating shell. Collect and wind the fiber core-spun yarn, and then weave the fiber core-spun yarn to obtain antistatic fabric.

2. The preparation process of an antistatic fabric based on modified acrylic fiber according to claim 1, characterized in that, In step S1, acrylic fibers are added to a 10wt% sodium hydroxide aqueous solution, stirred at 70-80℃ for 10-20 min, rinsed with deionized water 3-5 times, dried at 70℃ for 8-10 h, immersed in a 5wt% L-cysteine ​​aqueous solution, stirred at 70-80℃ for 1-2 h, then immersed in a 5wt% protein dispersion, stirred and reacted at 50-60℃ for 40-60 min, separated, washed with deionized water 3-5 times, and vacuum dried at 50℃ for 10-12 h to obtain modified acrylic fibers; The protein dispersion contains either casein or collagen.

3. The preparation process of an antistatic fabric based on modified acrylic fiber according to claim 1, characterized in that, In step S2, cellulose nanocrystals are added to an ethanol aqueous solution with a concentration of 90-95 vol%, and magnetically stirred for 30-40 min. Then, dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride is added and the pH is adjusted to 4-5.

5. The mixture is then shaken and reacted at 65-75℃ and 140 rpm for 5-6 h. After cooling, the mixture is washed 2-4 times with anhydrous ethanol by centrifugation and then vacuum dried at 60-65℃ for 8-10 h to obtain organosilicon quaternary ammonium salt modified CNW.

4. The preparation process of an antistatic fabric based on modified acrylic fiber according to claim 1, characterized in that, The spinning solution is obtained by adding modified acrylic fiber to DMF, stirring at 40~45℃ for 5~6h, and then adding organosilicon quaternary ammonium salt modified CNW and stirring for another 2~3h; the dispersion is obtained by mixing anhydrous ethanol and organosilicon quaternary ammonium salt modified CNW and ultrasonically treating for 40~90min.

5. The preparation process of an antistatic fabric based on modified acrylic fiber according to claim 4, characterized in that, The dispersion was prepared by adding 0.3-0.6 parts of an antibacterial composite material when mixing anhydrous ethanol and organosilicon quaternary ammonium salt modified CNW. The antibacterial composite material was prepared by adding 0.8-1 parts of cinnamaldehyde-modified chitosan to 800-1000 parts of deionized water, adjusting the pH to 2.5-3.5 with acetic acid solution, stirring at 55-65℃ for 30-50 min, adding 3-4 parts of IPTS-modified graphene oxide and ultrasonicating for 40-50 min, magnetically stirring at 55-65℃ for 40-60 min, adding sodium hydroxide solution dropwise to adjust the pH to 9.5-10, heating at 60-65℃ for 3-5 h, washing with deionized water 2-4 times, filtering, vacuum drying at 50-60℃ for 8-10 h, and grinding.

6. The preparation process of an antistatic fabric based on modified acrylic fiber according to claim 5, characterized in that, The cinnamaldehyde-modified chitosan was prepared by dissolving 1-1.5 parts of chitosan in 90-100 parts of a 1 vol% aqueous acetic acid solution, adding dropwise to 100 parts of a 0.8-1 wt% cinnamaldehyde ethanol solution, stirring and reacting at 45-55℃ for 6-8 hours, then adding dropwise sodium hydroxide solution to adjust the pH to 9.5-10, washing successively with deionized water and anhydrous ethanol, filtering, vacuum drying at 50-60℃ for 8-10 hours, and grinding.

7. The preparation process of an antistatic fabric based on modified acrylic fiber according to claim 5, characterized in that, The IPTS-modified graphene oxide was prepared by adding 0.02-0.03 parts of dibutyltin dioleate dropwise to a mixture of 1-1.5 parts of ethyl acetate and 1.5-2 parts of propyltriethoxysilane isocyanate. After magnetic stirring at 35-45°C for 4-5 hours, 5-7 parts of graphene oxide, 250-280 parts of anhydrous ethanol, and 120-150 parts of deionized water were added and mixed. The mixture was ultrasonically treated for 50-80 minutes, and then sodium hydroxide solution was added to adjust the pH to 9.5-10. The mixture was stirred at 600 r / min at 55-60°C for 10-12 hours. After washing with anhydrous ethanol and deionized water, the mixture was filtered and vacuum dried at 60-70°C for 8-10 hours.

8. The preparation process of an antistatic fabric based on modified acrylic fiber according to claim 1, characterized in that, In step S4, on the conjugate electrospinning device, the spinning solution is injected into the first set of needles A1 and A2 respectively, and the dispersion is injected into the second set of needles B1 and B2 respectively. A voltage of 20~25kV is applied, and the cotton yarn is continuously fed into the electric field area at a speed of 8~15m / min. Under the action of the high voltage electric field, the first set of needles electrospins the spinning solution to form nanofibers. The nanofibers are deposited on the surface of the cotton yarn and spirally wound under the rotation traction of the metal horn mouth at 30~40r / min to form a coating shell. The second set of needles electrostatically sprays the dispersion liquid, causing the organosilicon quaternary ammonium salt modified CNW in the dispersion liquid to deposit on the surface of the coating shell. The CNW is then collected and wound at a speed of 40~60 r / min to obtain fiber core-spun yarn. The fiber core-spun yarn is then woven into an antistatic fabric.

9. The preparation process of an antistatic fabric based on modified acrylic fiber according to claim 8, characterized in that, The flow rate of the first set of needles A1 and A2 is 0.6~1.0 mL / h, and the flow rate of the second set of needles B1 and B2 is 0.1~0.3 mL / h.

10. An antistatic fabric based on modified acrylic fiber, characterized in that, The fabric is prepared using the preparation process of the modified acrylic fiber-based antistatic fabric according to any one of claims 1 to 9, comprising the following raw materials in parts by weight: 45-50 parts modified acrylic fiber, 250-300 parts DMF, 1.4-2.5 parts organosilicon quaternary ammonium salt modified CNW, 120-150 parts anhydrous ethanol, and 150-200 parts cotton yarn; the modified acrylic fiber comprises the following raw materials in parts by weight: 50-60 parts acrylic fiber, 320-350 parts sodium hydroxide aqueous solution, 300-320 parts L-cysteine ​​aqueous solution, and 300-350 parts protein dispersion; the organosilicon quaternary ammonium salt modified CNW comprises the following raw materials in parts by weight: 4-5 parts cellulose nanofibers, 200-300 parts ethanol aqueous solution, and 5-7 parts dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride.

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