Fabric with antistatic properties

Abstract

This application relates to an antistatic fabric, belonging to the textile field, comprising the following components in parts by weight: 200-300 parts of modified polyacrylic acid conductive fiber and 150-200 parts of modified silk fibroin fiber, wherein the modified polyacrylic acid conductive fiber comprises modified polyacrylic acid fiber and a toughening conductive agent. This application improves the antistatic, antibacterial, and tear resistance properties of the fabric.

Description

Technical Field

[0001] This application relates to the textile field, and in particular to a fabric with antistatic properties. Background Technology

[0002] Fabric is a fundamental material in the garment industry. As one of the three essential elements of clothing, fabric has a significant impact on the style, color, and shape of garments. With the widespread use of new raw materials and the continuous updating of textile dyeing and finishing processes, the feel and other properties of fabrics have also changed accordingly.

[0003] As people's living standards improve, the market demands anti-static properties in fabric products. Synthetic fiber clothing is prone to generating static electricity, and the static charge generated by electrical appliances can also be absorbed and accumulated by the skin and clothing. Under dry air conditions, the generated static electricity is not easily released. Therefore, clothing often exhibits static electricity, with instantaneous static voltages reaching tens of thousands of volts, causing discomfort to the human body.

[0004] Related technologies typically use antistatic finishing agents to treat fabrics and give them antistatic properties. However, the antistatic effect of such fabrics can only be maintained for a short time because the antistatic layer has poor wash fastness and is prone to peeling off after washing. This significantly affects the antistatic performance of the fabric, so improvements are needed. Summary of the Invention

[0005] In order to improve the antistatic properties of the fabric, this application provides a fabric with antistatic properties.

[0006] The antistatic fabric provided in this application adopts the following technical solution:

[0007] A fabric with antistatic properties comprises the following components in parts by weight:

[0008] 200-300 parts of modified polyacrylic acid conductive fiber

[0009] 150-200 parts of modified silk fibroin fiber

[0010] The modified polyacrylic conductive fiber includes modified polyacrylic fiber and a toughening conductive agent.

[0011] Modified polyacrylic acid fiber has the advantages of being lightweight, breathable, wear-resistant, wrinkle-resistant, and washable. It contains a large number of carboxyl groups, which can form hydrogen bonds with water, giving it good hydrophilicity. This can improve the fabric's moisture regain and conductivity, thereby enhancing the fabric's antistatic properties. Toughening and conductive agents have good conductivity, which can further enhance the fiber's tear resistance and antistatic properties. Modified silk fibroin fiber has high toughness and high breathability, is rich in various hydrophilic groups, has good biocompatibility and moisture absorption, and can improve the antistatic properties of clothing.

[0012] Preferably, the modified polyacrylic acid fiber comprises thiophene-grafted polyacrylic acid and a co-crosslinking agent.

[0013] Thiophene-grafted polyacrylic acid can improve the antistatic properties of fabrics through thiophene grafting modification; co-crosslinking agents can crosslink and polymerize with thiophene-grafted polyacrylic acid to form a crosslinked network, improving the tear resistance and conductivity of modified polyacrylic acid fibers, thereby enhancing the antistatic properties of the fabric.

[0014] Preferably, the thiophene-grafted polyacrylic acid comprises acrylic acid and 3,4-dimethoxythiophene.

[0015] Acrylic acid molecules contain a carboxyl group, which can participate in hydrogen bonding between water molecules, exhibiting good hydrophilicity and hygroscopicity. The resulting thiophene-grafted polyacrylic acid fibers have high moisture regain and good electrical conductivity. 3,4-Dimethoxythiophene is an organic compound with a methoxy group attached to the 3rd and 4th positions of its thiophene ring, exhibiting high electron affinity and electronic conductivity, which can synergistically enhance the electrical conductivity of the fabric with acrylic acid. Thiophene-grafted polyacrylic acid also possesses good antibacterial properties. The thiophene group reacts chemically with the cell wall, cell membrane, or cytoplasmic membrane of microorganisms, destroying their structure and causing them to become inactive and die.

[0016] Preferably, the co-crosslinking agent is pyrrole.

[0017] Pyrrole is a five-membered heterocyclic compound containing one nitrogen atom. It can undergo cross-linking and interpenetrating copolymerization with thiophene-grafted polyacrylic acid to improve the tear resistance of modified polyacrylic acid fibers. The resulting polypyrrole has excellent electrical conductivity and good biocompatibility. Polypyrrole can synergistically enhance the electrical conductivity of modified polyacrylic acid fibers with 3,4-dimethoxythiophene, thereby improving the antistatic properties of the fabric. Polypyrrole also has good antibacterial properties. It can induce bacteria to produce polysaccharides, destroy the bacterial cell membrane structure, and lead to bacterial death. It can synergistically work with thiophene-grafted polyacrylic acid to enhance the antibacterial properties of modified polyacrylic acid fibers, thereby improving the antibacterial properties of the fabric.

[0018] Preferably, the mass ratio of acrylic acid, 3,4-dimethoxythiophene and pyrrole is 1:1.08:(0.5-0.7).

[0019] The fabric obtained according to the above mass ratio has good antistatic properties, antibacterial properties and tear resistance.

[0020] Preferably, the modified polyacrylic acid conductive fiber is prepared using the following steps:

[0021] Thiophene-grafted polyacrylic acid, ferric chloride, and anhydrous ethanol were mixed to obtain spinning solution A. Pyrrole was dissolved in anhydrous ethanol to obtain spinning solution B. A toughening conductive agent, N,N-dimethylacetamide, and anhydrous ethanol were mixed to obtain a coagulation bath. Three-layer coaxial electrospinning was used. Spinning solution B was placed in the first layer, spinning solution A was placed in the second layer, and spinning solution B was placed in the third layer. The second layer covered the outside of the first layer, and the third layer covered the outside of the second layer. The obtained modified polyacrylic acid fiber was passed into the coagulation bath. The spun yarn in the coagulation bath was collected, washed, and dried to obtain modified polyacrylic acid conductive fiber.

[0022] Through three-layer coaxial electrospinning, pyrrole and thiophene-grafted polyacrylic acid can be fully contacted and cross-linked polymerized. The polypyrrole and thiophene-grafted polyacrylic acid form a cross-linked interpenetrating network, providing sites for the toughening and conductive agent to bind firmly. The toughening and conductive agent is dispersed in the coagulation bath and is quickly bound to the spun fiber through the polymerization of pyrrole when the spinning comes into contact with the coagulation bath, thereby improving the conductivity of the modified polyacrylic acid fiber and thus improving the antistatic properties of the fabric.

[0023] Preferably, the toughening conductive agent comprises a two-dimensional transition metal nitride and pyrrole.

[0024] Two-dimensional transition metal nitrides are a novel type of two-dimensional layered material with excellent electrical and mechanical properties. The abundant hydroxyl, oxygen, and fluorine functional groups on the surface contribute to good electrical conductivity and high hydrophilicity, which can synergistically enhance the antistatic properties of modified polyacrylic acid fibers with 3,4-dimethoxythiophene and pyrrole. Pyrrole forms polypyrrole particles on the surface of two-dimensional transition metal nitrides through monomer polymerization, improving the electrical conductivity of the two-dimensional transition metal nitrides. At the same time, it provides sites for the two-dimensional transition metal nitrides to bind with the modified polyacrylic acid fibers, improving the bonding strength between the two-dimensional transition metal nitrides and the modified polyacrylic acid fibers, and enhancing the fracture resistance and stability of the modified polyacrylic acid fibers.

[0025] Preferably, the modified silk fibroin includes silk fibroin, genipin, and tannic acid.

[0026] Silk fibroin is a natural high-molecular-weight fibrous protein extracted from silkworm silk. It contains 18 kinds of amino acids and has good flexibility, tensile strength, and breathability and moisture permeability. It also has a high moisture regain rate, which can improve the antistatic properties of clothing. Genipin is a product of geniposide hydrolysis by β-glucosidase. It is an excellent cross-linking agent. The amino groups on the silk fibroin molecular chain can react with genipin to form nitrogen-containing six-membered rings. The carboxyl end of genipin can also covalently bind with the amino groups, improving the stability of silk fibroin. Tannic acid is a phenolic compound that can combine with silk fibroin to improve the stability and breakage resistance of modified silk fibroin fibers. Tannic acid also has good hydrophilicity and antibacterial properties, which can improve the moisture regain rate of modified silk fibroin fibers. It works synergistically with pyrrole and 3,4-dimethoxythiophene to improve the antistatic and antibacterial properties of fabrics.

[0027] Preferably, the mass ratio of silk fibroin, genipin and tannic acid is 1:0.05:(0.05-0.1).

[0028] Fabrics obtained according to the above mass ratio have good antistatic properties, tear resistance, and antibacterial properties.

[0029] Preferably, the fabric with antistatic properties is prepared using the following steps:

[0030] Preparation of modified polyacrylic acid conductive fibers;

[0031] Preparation of modified silk fibroin fibers: Silk fibroin, genipin, tannic acid and deionized water are mixed and stirred to obtain a modified silk fibroin solution. The modified silk fibroin solution is freeze-dried to obtain modified silk fibroin. The modified silk fibroin is dissolved in calcium chloride formic acid solution to obtain a spinning solution. Deionized water, sodium dodecyl sulfate and ethanol are mixed and dissolved to obtain a coagulation bath. The spinning solution is wet-spun to collect fibers. The collected fibers are washed with deionized water and dried to obtain modified silk fibroin fibers.

[0032] A fabric with antistatic properties is obtained by weaving modified polyacrylic conductive fiber as warp and modified silk fibroin fiber as weft.

[0033] The fabric prepared according to the above steps has good antistatic properties, tear resistance, and antibacterial properties.

[0034] In summary, this application includes at least one of the following beneficial technical effects:

[0035] 1. Modified polyacrylic acid fiber has the advantages of being lightweight, breathable, wear-resistant, wrinkle-resistant, and washable. It has good hydrophilicity, which can improve the moisture regain of the fabric and increase its conductivity. Toughening and conductive agents have good conductivity, which can further enhance the fiber's tear resistance and antistatic properties. Modified silk fibroin fiber has high toughness and high breathability, is rich in a variety of hydrophilic groups, has good biocompatibility and moisture absorption, and can improve the antistatic properties of clothing. Fabrics woven using the above fibers have good antistatic properties.

[0036] 2. Pyrrole can crosslink with thiophene-grafted polyacrylic acid to form a crosslinked interpenetrating copolymer, thereby improving the tear resistance of modified polyacrylic acid fibers; two-dimensional transition metal nitrides are bonded to modified polyacrylic acid conductive fibers through the polymerization of pyrrole, and the two-dimensional transition metal nitrides and polypyrrole synergistically improve the tear resistance of the fabric.

[0037] 3. Polypyrrole, thiophene-grafted polyacrylic acid and tannic acid can disrupt the cell structure of bacteria, induce bacterial death, and synergistically enhance the antibacterial properties of the fabric. Detailed Implementation

[0038] This application discloses a fabric with antistatic properties. The following detailed description, in conjunction with embodiments, further illustrates this application:

[0039] Example

[0040] Example 1

[0041] Fabrics with antistatic properties

[0042] Preparation of thiophene-grafted polyacrylic acid

[0043] Under a nitrogen atmosphere, 167.5 g of 3,4-dimethoxythiophene (CAS No.: 51792-34-8), 370 g of 3-chloro-1,2-propanediol (CAS No.: 96-24-2), and 22.65 g of p-toluenesulfonic acid (CAS No.: 104-15-4) were dissolved in 4 L of toluene. The mixture was heated in a water bath to 90 °C and stirred at 200 rpm for 8 h. After the reaction was completed, the mixture was cooled to 30 °C, and the resulting solution was filtered through a Buchner funnel containing diatomaceous earth to obtain a filter cake. The filter cake was washed with toluene to obtain an organic phase. The organic phase was concentrated using a rotary evaporator to obtain a crude product. The crude product was separated by silica gel column chromatography and eluted with petroleum ether to obtain the thiophene graft precursor.

[0044] Thiophene graft precursor, 450 mL of dimethyl sulfoxide (CAS No.: 67-68-5), and 155 g of acrylic acid (CAS No.: 79-10-7) were dissolved in a three-necked flask. 145 g of potassium carbonate and 1.9 g of potassium iodide were added to the three-necked flask. The oil bath temperature of the three-necked flask was raised to 120 °C, and the mixture was stirred at 300 r / min for 4 h under nitrogen protection. After the reaction was completed, the solution was cooled to 30 °C, poured into deionized water, and extracted with dichloromethane. The extracted product solution was collected and washed with deionized water. The washed product solution was dried with anhydrous magnesium sulfate. The dried product solution was concentrated using a rotary evaporator and separated by silica gel column chromatography. The product was washed with petroleum ether and ethyl acetate in a volume ratio of 2:1 to obtain thiophene-grafted acrylic acid.

[0045] The thiophene-grafted acrylic acid prepared in the above steps was mixed with 15g of azobisisobutyronitrile (CAS No.: 78-67-1) and 1L of tetrahydrofuran to obtain a mixed solution. The mixture was stirred in a water bath at 60℃ for 8 hours under nitrogen protection. After the reaction was completed, the mixed solution was added dropwise to methanol to obtain a pale yellow precipitate. The pale yellow precipitate was dissolved in tetrahydrofuran and then precipitated with methanol. The precipitate was dried in an oven at 50℃ to obtain thiophene-grafted polyacrylic acid.

[0046] Preparation of toughened conductive agent

[0047] 10g of lithium fluoride (CAS No.: 7789-24-4), 50mL of hydrochloric acid and 50mL of deionized water were mixed and stirred at 200r / min for 15min in a 35℃ water bath to obtain an etching solution. 15g of aluminum titanium nitride (CAS No.: 60317-94-4) was added to the etching solution and stirred at 200r / min in a 35℃ water bath for 24h to obtain an etched phase dispersion solution. The etched phase dispersion solution was centrifuged to remove the supernatant and obtain a precipitate. The precipitate was washed five times with deionized water for 5min each time. The washed precipitate was dried at 80℃ to obtain a two-dimensional transition metal nitride.

[0048] 2g of pyrrole (CAS No.: 109-97-7) was added to deionized water and sonicated for 30min to obtain a pyrrole aqueous solution. The two-dimensional transition metal nitride dispersion and the pyrrole aqueous solution were stirred on a magnetic stirrer at 200r / min for 30min to obtain a mixed solution. 40mL of 0.3mol / L ferric chloride (CAS No.: 10025-77-1) aqueous solution was added dropwise to the mixed solution at 30 drops / min during stirring. The reaction was carried out under ice bath conditions for 6h. The solution after reaction was centrifuged to obtain a precipitate. The precipitate was washed with deionized water and then placed in a vacuum drying oven and dried at 70℃ for 12h to obtain a toughening conductive agent.

[0049] Preparation of modified polyacrylic acid conductive fibers

[0050] Spinning solution A was prepared by mixing 322.5g of thiophene-grafted polyacrylic acid, 100g of ferric chloride, and 1L of anhydrous ethanol. Spinning solution B was prepared by dissolving 77.5g of pyrrole in 2L of anhydrous ethanol. Coagulation bath was prepared by mixing 10g of toughening conductive agent, 500g of N,N-dimethylacetamide, and 1L of anhydrous ethanol. Three-layer coaxial electrospinning was used, with spinning solution B placed in the first layer, spinning solution A placed in the second layer, and spinning solution B placed in the third layer. The second layer covered the outside of the first layer, and the third layer covered the outside of the second layer. The obtained modified polyacrylic acid fiber was passed into the coagulation bath, and the spun yarn in the coagulation bath was collected. After washing with deionized water, it was dried in an oven at 50°C for 4 hours to obtain modified polyacrylic acid conductive fiber.

[0051] Preparation of modified silk fibroin fibers

[0052] 272.7g of silk fibroin (CAS No.: 96690-41-4) and 13.65g of genipin (CAS No.: 6902-77-8) were mixed and stirred in 500mL of deionized water for 30min at a stirring speed of 200r / min to obtain a preliminary modified solution. 13.65g of tannic acid (CAS No.: 1401-55-4) was dissolved in 500mL of deionized water to obtain a tannic acid aqueous solution. The tannic acid aqueous solution was added dropwise to the preliminary modified solution at a rate of 30 drops / min and stirred at a speed of 500r / min for 30min to obtain a modified silk fibroin solution. The modified silk fibroin solution was freeze-dried at -20℃ to obtain modified silk fibroin.

[0053] Modified silk fibroin was dissolved in a 5% (w / w) calcium chloride formic acid solution to obtain a spinning solution. 250 mL of deionized water, 50 g of sodium dodecyl sulfate, and 750 mL of ethanol were mixed and dissolved to obtain a coagulation bath. The spinning solution was poured into a medical syringe and allowed to stand to defoam. The spinning solution was then wet-spun at a rate of 12 mL / h. The spinning solution in the syringe was extruded parallel into the coagulation bath using a syringe pump. The inner diameter of the spinning needle was 0.85 mm, and the speed of the winding roller collecting the fibroin was 7.85 cm / s. The collected fibers were washed with deionized water and then dried in a 30°C oven to obtain modified silk fibroin fibers.

[0054] Using 200g of modified polyacrylic conductive fiber as warp and 150g of modified silk fibroin fiber as weft, an antistatic fabric is obtained through weaving, with a setting temperature of 120℃.

[0055] Example 2

[0056] Fabrics with antistatic properties

[0057] Preparation of thiophene-grafted polyacrylic acid

[0058] Under a nitrogen atmosphere, 155.4 g of 3,4-dimethoxythiophene (CAS No.: 51792-34-8), 370 g of 3-chloro-1,2-propanediol (CAS No.: 96-24-2), and 22.65 g of p-toluenesulfonic acid (CAS No.: 104-15-4) were dissolved in 4 L of toluene. The mixture was heated in a water bath to 90 °C and stirred at 200 rpm for 8 h. After the reaction was completed, the mixture was cooled to 30 °C, and the resulting solution was filtered through a Buchner funnel containing diatomaceous earth to obtain a filter cake. The filter cake was washed with toluene to obtain an organic phase. The organic phase was concentrated using a rotary evaporator to obtain a crude product. The crude product was separated by silica gel column chromatography and eluted with petroleum ether to obtain the thiophene graft precursor.

[0059] Thiophene graft precursor, 450 mL of dimethyl sulfoxide (CAS No.: 67-68-5), and 143.9 g of acrylic acid (CAS No.: 79-10-7) were dissolved in a three-necked flask. 145 g of potassium carbonate and 1.9 g of potassium iodide were added to the three-necked flask. The oil bath temperature of the three-necked flask was raised to 120 °C, and the mixture was stirred at 300 r / min for 4 h under nitrogen protection. After the reaction was completed, the solution was cooled to 30 °C, poured into deionized water, and extracted with dichloromethane. The extracted product solution was collected and washed with deionized water. The washed product solution was dried with anhydrous magnesium sulfate. The dried product solution was concentrated using a rotary evaporator and separated by silica gel column chromatography. The product was washed with petroleum ether and ethyl acetate in a volume ratio of 2:1 to obtain thiophene-grafted acrylic acid.

[0060] The thiophene-grafted acrylic acid prepared in the above steps was mixed with 15g of azobisisobutyronitrile (CAS No.: 78-67-1) and 1L of tetrahydrofuran to obtain a mixed solution. The mixture was stirred in a water bath at 60℃ for 8 hours under nitrogen protection. After the reaction was completed, the mixed solution was added dropwise to methanol to obtain a pale yellow precipitate. The pale yellow precipitate was dissolved in tetrahydrofuran and then precipitated with methanol. The precipitate was dried in an oven at 50℃ to obtain thiophene-grafted polyacrylic acid.

[0061] Preparation of toughened conductive agent

[0062] 10g of lithium fluoride (CAS No.: 7789-24-4), 50mL of hydrochloric acid and 50mL of deionized water were mixed and stirred at 200r / min for 15min in a 35℃ water bath to obtain an etching solution. 15g of aluminum titanium nitride (CAS No.: 60317-94-4) was added to the etching solution and stirred at 200r / min in a 35℃ water bath for 24h to obtain an etched phase dispersion solution. The etched phase dispersion solution was centrifuged to remove the supernatant and obtain a precipitate. The precipitate was washed five times with deionized water for 5min each time. The washed precipitate was dried at 80℃ to obtain a two-dimensional transition metal nitride.

[0063] 2g of pyrrole (CAS No.: 109-97-7) was added to deionized water and sonicated for 30min to obtain a pyrrole aqueous solution. The two-dimensional transition metal nitride dispersion and the pyrrole aqueous solution were stirred on a magnetic stirrer at 200r / min for 30min to obtain a mixed solution. 40mL of 0.3mol / L ferric chloride (CAS No.: 10025-77-1) aqueous solution was added dropwise to the mixed solution at 30 drops / min during stirring. The reaction was carried out under ice bath conditions for 6h. The solution after reaction was centrifuged to obtain a precipitate. The precipitate was washed with deionized water and then placed in a vacuum drying oven and dried at 70℃ for 12h to obtain a toughening conductive agent.

[0064] Preparation of modified polyacrylic acid conductive fibers

[0065] Spinning solution A was prepared by mixing 299.3g of thiophene-grafted polyacrylic acid, 100g of ferric chloride, and 1L of anhydrous ethanol. Spinning solution B was prepared by dissolving 100.7g of pyrrole in 2L of anhydrous ethanol. Coagulation bath was prepared by mixing 10g of toughening conductive agent, 500g of N,N-dimethylacetamide, and 1L of anhydrous ethanol. Three-layer coaxial electrospinning was used, with spinning solution B placed in the first layer, spinning solution A placed in the second layer, and spinning solution B placed in the third layer. The second layer covered the outside of the first layer, and the third layer covered the outside of the second layer. The obtained modified polyacrylic acid fiber was passed into the coagulation bath, and the spun yarn in the coagulation bath was collected. After washing with deionized water, it was dried in an oven at 50°C for 4 hours to obtain modified polyacrylic acid conductive fiber.

[0066] Preparation of modified silk fibroin fibers

[0067] 261g of silk fibroin (CAS No.: 96690-41-4) and 13g of genipin (CAS No.: 6902-77-8) were mixed and stirred in 500mL of deionized water for 30min at a stirring speed of 200r / min to obtain a preliminary modified solution. 26g of tannic acid (CAS No.: 1401-55-4) was dissolved in 500mL of deionized water to obtain a tannic acid aqueous solution. The tannic acid aqueous solution was added dropwise to the preliminary modified solution at a rate of 30 drops / min and stirred at a speed of 500r / min for 30min to obtain a modified silk fibroin solution. The modified silk fibroin solution was freeze-dried at -20℃ to obtain modified silk fibroin.

[0068] 300g of modified silk fibroin was dissolved in a 5% (w / w) calcium chloride formic acid solution to obtain a spinning solution. 250mL of deionized water, 50g of sodium dodecyl sulfate, and 750mL of ethanol were mixed and dissolved to obtain a coagulation bath. The spinning solution was poured into a medical syringe and allowed to stand to defoam. The spinning solution was then wet-spun at a rate of 12mL / h. The spinning solution in the syringe was extruded parallel into the coagulation bath using a syringe pump. The inner diameter of the spinning needle was 0.85mm, and the speed of the winding roller collecting the spinning fibers was 7.85cm / s. The collected fibers were washed with deionized water and then dried in a 30℃ oven to obtain modified silk fibroin fibers.

[0069] A fabric with antistatic properties is obtained by weaving modified polyacrylic conductive fiber as warp and 200g modified silk fibroin fiber as weft, with a setting temperature of 120℃.

[0070] Example 3

[0071] Fabrics with antistatic properties

[0072] Preparation of thiophene-grafted polyacrylic acid

[0073] Under a nitrogen atmosphere, 161.2 g of 3,4-dimethoxythiophene (CAS No.: 51792-34-8), 370 g of 3-chloro-1,2-propanediol (CAS No.: 96-24-2), and 22.65 g of p-toluenesulfonic acid (CAS No.: 104-15-4) were dissolved in 4 L of toluene. The mixture was heated in a water bath to 90 °C and stirred at 200 rpm for 8 h. After the reaction was completed, the mixture was cooled to 30 °C, and the resulting solution was filtered through a Buchner funnel containing diatomaceous earth to obtain a filter cake. The filter cake was washed with toluene to obtain an organic phase. The organic phase was concentrated using a rotary evaporator to obtain a crude product. The crude product was separated by silica gel column chromatography and eluted with petroleum ether to obtain the thiophene graft precursor.

[0074] Thiophene graft precursor, 450 mL of dimethyl sulfoxide (CAS No.: 67-68-5), and 149.3 g of acrylic acid (CAS No.: 79-10-7) were dissolved in a three-necked flask. 145 g of potassium carbonate and 1.9 g of potassium iodide were added to the three-necked flask. The oil bath temperature of the three-necked flask was raised to 120 °C, and the mixture was stirred at 300 r / min for 4 h under nitrogen protection. After the reaction was completed, the solution was cooled to 30 °C, poured into deionized water, and extracted with dichloromethane. The extracted product solution was collected and washed with deionized water. The washed product solution was dried with anhydrous magnesium sulfate. The dried product solution was concentrated using a rotary evaporator and separated by silica gel column chromatography. The product was washed with petroleum ether and ethyl acetate in a volume ratio of 2:1 to obtain thiophene-grafted acrylic acid.

[0075] The thiophene-grafted acrylic acid prepared in the above steps was mixed with 15g of azobisisobutyronitrile (CAS No.: 78-67-1) and 1L of tetrahydrofuran to obtain a mixed solution. The mixture was stirred in a water bath at 60℃ for 8 hours under nitrogen protection. After the reaction was completed, the mixed solution was added dropwise to methanol to obtain a pale yellow precipitate. The pale yellow precipitate was dissolved in tetrahydrofuran and then precipitated with methanol. The precipitate was dried in an oven at 50℃ to obtain thiophene-grafted polyacrylic acid.

[0076] Preparation of toughened conductive agent

[0077] 10g of lithium fluoride (CAS No.: 7789-24-4), 50mL of hydrochloric acid and 50mL of deionized water were mixed and stirred at 200r / min for 15min in a 35℃ water bath to obtain an etching solution. 15g of aluminum titanium nitride (CAS No.: 60317-94-4) was added to the etching solution and stirred at 200r / min in a 35℃ water bath for 24h to obtain an etched phase dispersion solution. The etched phase dispersion solution was centrifuged to remove the supernatant and obtain a precipitate. The precipitate was washed five times with deionized water for 5min each time. The washed precipitate was dried at 80℃ to obtain a two-dimensional transition metal nitride.

[0078] 2g of pyrrole (CAS No.: 109-97-7) was added to deionized water and sonicated for 30min to obtain a pyrrole aqueous solution. The two-dimensional transition metal nitride dispersion and the pyrrole aqueous solution were stirred on a magnetic stirrer at 200r / min for 30min to obtain a mixed solution. 40mL of 0.3mol / L ferric chloride (CAS No.: 10025-77-1) aqueous solution was added dropwise to the mixed solution at 30 drops / min during stirring. The reaction was carried out under ice bath conditions for 6h. The solution after reaction was centrifuged to obtain a precipitate. The precipitate was washed with deionized water and then placed in a vacuum drying oven and dried at 70℃ for 12h to obtain a toughening conductive agent.

[0079] Preparation of modified polyacrylic acid conductive fibers

[0080] Spinning solution A was prepared by mixing 310.5g of thiophene-grafted polyacrylic acid, 100g of ferric chloride, and 1L of anhydrous ethanol. Spinning solution B was prepared by dissolving 89.5g of pyrrole in 2L of anhydrous ethanol. Coagulation bath was prepared by mixing 10g of toughening conductive agent, 500g of N,N-dimethylacetamide, and 1L of anhydrous ethanol. Three-layer coaxial electrospinning was used, with spinning solution B placed in the first layer, spinning solution A placed in the second layer, and spinning solution B placed in the third layer. The second layer covered the outside of the first layer, and the third layer covered the outside of the second layer. The obtained modified polyacrylic acid fiber was passed into the coagulation bath, and the spun yarn in the coagulation bath was collected. After washing with deionized water, it was dried in an oven at 50°C for 4 hours to obtain modified polyacrylic acid conductive fiber.

[0081] Preparation of modified silk fibroin fibers

[0082] 266.7g of silk fibroin (CAS No.: 96690-41-4) and 13.3g of genipin (CAS No.: 6902-77-8) were mixed and stirred in 500mL of deionized water for 30min at a stirring speed of 200r / min to obtain a preliminary modified solution. 20g of tannic acid (CAS No.: 1401-55-4) was dissolved in 500mL of deionized water to obtain a tannic acid aqueous solution. The tannic acid aqueous solution was added dropwise to the preliminary modified solution at a rate of 30 drops / min and stirred at 500r / min for 30min to obtain a modified silk fibroin solution. The modified silk fibroin solution was freeze-dried at -20℃ to obtain modified silk fibroin.

[0083] Modified silk fibroin was dissolved in a 5% (w / w) calcium chloride formic acid solution to obtain a spinning solution. 250 mL of deionized water, 50 g of sodium dodecyl sulfate, and 750 mL of ethanol were mixed and dissolved to obtain a coagulation bath. The spinning solution was poured into a medical syringe and allowed to stand to defoam. The spinning solution was then wet-spun at a rate of 12 mL / h. The spinning solution in the syringe was extruded parallel into the coagulation bath using a syringe pump. The inner diameter of the spinning needle was 0.85 mm, and the speed of the winding roller collecting the fibroin was 7.85 cm / s. The collected fibers were washed with deionized water and then dried in a 30°C oven to obtain modified silk fibroin fibers.

[0084] A fabric with antistatic properties is obtained by weaving 250g of modified polyacrylic conductive fiber as warp and 175g of modified silk fibroin fiber as weft, with a setting temperature of 120℃.

[0085] Example 4

[0086] Example 4 is based on Example 3. The only difference between Example 4 and Example 3 is that in Example 4, the amount of acrylic acid is 168g, the amount of 3,4-dimethoxythiophene is 181.5g, and the amount of pyrrole is 50.5g.

[0087] Example 5

[0088] Example 5 is based on Example 3. The only difference between Example 5 and Example 3 is that in Example 5, the amount of acrylic acid is 134.2g, the amount of 3,4-dimethoxythiophene is 145g, and the amount of pyrrole is 120.8g.

[0089] Example 6

[0090] Example 6 is based on Example 3. The only difference between Example 6 and Example 3 is that in Example 6, the amount of silk fibroin is 280.4g, the amount of genipin is 14g, and the amount of tannic acid is 5.6g.

[0091] Example 7

[0092] Example 7 is based on Example 3. The only difference between Example 7 and Example 3 is that in Example 7, the amount of silk fibroin is 250g, the amount of genipin is 12.5g, and the amount of tannic acid is 37.5g.

[0093] Example 8

[0094] Example 8 is based on Example 3. The only difference between Example 8 and Example 3 is that in Example 8, the thiophene-grafted polyacrylic acid in the step of preparing modified polyacrylic acid conductive fiber is replaced with polyacrylic acid.

[0095] Example 9

[0096] Example 9 is based on Example 3. The only difference between Example 9 and Example 3 is that the toughening conductive agent is replaced with a two-dimensional transition metal nitride in Example 9.

[0097] Example 10

[0098] Example 10 is based on Example 3. The only difference between Example 10 and Example 3 is that tannic acid is not added in Example 10.

[0099] Example 11

[0100] Example 11 is based on Example 3. The only difference between Example 11 and Example 3 is that Example 11 does not add genipin.

[0101] Comparative Example 1

[0102] Comparative Example 1 is based on Example 3. The only difference between Comparative Example 1 and Example 3 is that no toughening conductive agent is added in Comparative Example 1.

[0103] Comparative Example 2

[0104] Comparative Example 2 is based on Example 3. The only difference between Comparative Example 2 and Example 3 is that the modified silk fibroin fiber is replaced with silk fibroin fiber in Comparative Example 2.

[0105] Performance testing

[0106] (1) The standard GB / T12703-1991 Electrostatic Test Method for Textiles was selected. The C-method charge surface density method was used for testing. Two samples were randomly selected from the warp and weft directions, and the charge surface density was calculated. Each sample was tested three times, and the average of the three tests was the measured value of the sample. The average value of the measured values ​​of the four samples was taken, and the results were recorded in Table 1.

[0107] (2) Select GB / T20944.2-2007 Evaluation of antimicrobial properties of textiles - Part 2: Absorption method as the standard, cut 6 samples of 0.4g each, conduct antimicrobial performance tests, incubate and wash off, calculate the antimicrobial rate and fill in the measurement results in Table 2.

[0108] (3) Select GB / T3923.1-2013 Fabric Properties Part 1 Determination of Breaking Strength and Elongation at Break as the standard, cut 5 samples with an effective width of 50 mm, and test the breaking strength and elongation. After measurement, take the average value and record the results in Table 1.

[0109] Table 1. Test results of antistatic, antibacterial, and tear resistance properties of the fabric.

[0110]

[0111] As shown in Table 1, the surface charge density of Examples 1-3 is less than 1.2 μC / m. 2 The fabric exhibits a high inhibition rate of 98.2% against Escherichia coli, 98.1% against Staphylococcus aureus, and 98.3% against Candida albicans. It also demonstrates a tensile strength greater than 389 N and an elongation at break greater than 77%, indicating that the fabric prepared in this application possesses excellent antistatic, antibacterial, and anti-tear properties.

[0112] As shown in Table 1, the only difference between Example 4 and Example 3 is that the mass ratio in Example 4 is 1:1.08:0.3, while the mass ratio in Example 3 is 1:1.08:0.6, and the surface charge density in Example 4 is 1.5 μC / m³. 2 The inhibition rate of *Escherichia coli* was 96.7%, the inhibition rate of *Staphylococcus aureus* was 96.3%, and the inhibition rate of *Candida albicans* was 96.1%. The tensile strength was 356 N, the elongation at break was 71%, and the surface charge density in Example 3 was 0.8 μC / m². 2 The antibacterial rate of Escherichia coli was 99.3%, the antibacterial rate of Staphylococcus aureus was 99.5%, and the antibacterial rate of Candida albicans was 99.7%. The tensile strength was 412 N, and the elongation at break was 83%. Compared with Example 3, the antistatic, antibacterial, and tensile properties of Example 4 were all reduced. This is because the amount of pyrrole was reduced, the cross-linking polymerization of pyrrole and thiophene-grafted polyacrylic acid was reduced, the synergistic effect of polypyrrole and thiophene-grafted polyacrylic acid was weakened, and the stability of the polymer network was reduced. Therefore, the antistatic, antibacterial, and tensile properties of the fabric were all reduced.

[0113] As shown in Table 1, the only difference between Example 5 and Example 3 is that the mass ratio in Example 5 is 1:1.08:0.9, and the surface charge density in Example 5 is 1.4 μC / m³. 2The antibacterial rate of Escherichia coli was 97.1%, the antibacterial rate of Staphylococcus aureus was 97.5%, and the antibacterial rate of Candida albicans was 96.9%. The tensile strength was 367 N, and the elongation at break was 73%. Compared with Example 3, the antistatic, antibacterial, and tensile properties of Example 5 were all reduced. This is because the amount of pyrrole was increased, and the excessive pyrrole further coated the thiophene-grafted polyacrylic acid on the basis of cross-linking polymerization. The synergistic effect of polypyrrole and thiophene-grafted polyacrylic acid was weakened, and the conductive toughening agent could only adhere to the surface of polypyrrole, resulting in a decrease in the toughening effect. Therefore, the antistatic, antibacterial, and tensile properties of the fabric were all reduced.

[0114] As shown in Table 1, the only difference between Example 6 and Example 3 is that the mass ratio in Example 6 is 1:0.05:0.02, while the mass ratio in Example 3 is 1:0.05:0.075, and the surface charge density in Example 6 is 1.7 μC / m². 2 The antibacterial rate of Escherichia coli was 95.8%, the antibacterial rate of Staphylococcus aureus was 96.1%, and the antibacterial rate of Candida albicans was 95.4%. The breaking strength was 351N, and the breaking elongation was 68%. Compared with Example 3, the antistatic, antibacterial, and breaking properties of Example 6 were all reduced. This is because the amount of tannic acid used was reduced, the structure of the modified silk fibroin fiber tended to be disordered, and the stability of the modified silk fibroin fiber was reduced. Therefore, the antistatic, antibacterial, and breaking properties of the fabric were all reduced.

[0115] As shown in Table 1, the only difference between Example 7 and Example 3 is that the mass ratio in Example 7 is 1:0.05:0.15, and the surface charge density in Example 7 is 1.6 μC / m³. 2 The antibacterial rate of Escherichia coli was 97.5%, the antibacterial rate of Staphylococcus aureus was 97.2%, and the antibacterial rate of Candida albicans was 97.9%. The breaking strength was 354 N, and the breaking elongation was 72%. Compared with Example 3, the antistatic, antibacterial, and breaking properties of Example 7 were all reduced. This is because the amount of tannic acid was increased. Excessive tannic acid will change the ordered structure of the modified silk fibroin, affecting the stability of the modified silk fibroin fiber, thus reducing the antistatic, antibacterial, and breaking properties of the fabric.

[0116] As shown in Table 1, the only difference between Example 8 and Example 3 is that in Example 8, the thiophene-grafted polyacrylic acid in the step of preparing modified polyacrylic acid conductive fibers is replaced with polyacrylic acid, and the charge surface density in Example 8 is 4.2 μC / m. 2The inhibition rate of Escherichia coli was 92.1%, the inhibition rate of Staphylococcus aureus was 92.5%, and the inhibition rate of Candida albicans was 91.9%. The breaking strength was 295N and the breaking elongation was 55%. Compared with Example 3, the antistatic properties, antibacterial properties and breaking resistance of Example 8 were all reduced. This is because the acrylic acid lacked thiophene modification, the synergistic effect of modified polyacrylic acid fiber, toughening conductive agent and modified silk fibroin fiber was weakened, and the stability of the fabric decreased. Therefore, the antistatic properties, antibacterial properties and breaking resistance of the fabric were all reduced.

[0117] As shown in Table 1, the only difference between Example 9 and Example 3 is that the toughening conductive agent in Example 9 is replaced with a two-dimensional transition metal nitride, and the charge surface density in Example 9 is 4.6 μC / m. 2 The antibacterial rate of Escherichia coli was 89.7%, the antibacterial rate of Staphylococcus aureus was 89.3%, and the antibacterial rate of Candida albicans was 89.1%. The tensile strength was 287 N, and the elongation at break was 49%. Compared with Example 3, the antistatic properties, antibacterial properties, and tensile strength of Example 9 were all reduced. This is because the two-dimensional transition metal nitride lacked pyrrole modification treatment, and there were no sites on the surface of the two-dimensional transition metal nitride that were conducive to adhesion to the surface of the modified polyacrylic acid fiber. The bonding force between the two-dimensional transition metal nitride and the modified polyacrylic acid fiber decreased, and the stability of the modified polyacrylic acid conductive fiber decreased. Therefore, the antistatic properties, antibacterial properties, and tensile strength of the fabric were all reduced.

[0118] As shown in Table 1, the only difference between Example 10 and Example 3 is that: no tannic acid was added in Example 10, and the surface charge density in Example 10 was 3.5 μC / m. 2 The antibacterial rate of Escherichia coli was 85.3%, the antibacterial rate of Staphylococcus aureus was 84.9%, and the antibacterial rate of Candida albicans was 84.7%. The breaking strength was 262 N, and the breaking elongation was 43%. Compared with Example 3, the antistatic properties, antibacterial properties, and breaking resistance of Example 10 were all reduced. This is because the lack of tannic acid modification treatment reduced the stability of the modified silk fibroin fiber and weakened the synergistic effect of the modified silk fibroin fiber and the modified polyacrylic acid conductive fiber. Therefore, the antistatic properties, antibacterial properties, and breaking resistance of the fabric were all reduced.

[0119] As shown in Table 1, the only difference between Example 11 and Example 3 is that Example 11 does not contain genipin, and the surface charge density in Example 11 is 3.7 μC / m². 2The antibacterial rate of Escherichia coli was 92.9%, the antibacterial rate of Staphylococcus aureus was 92.1%, and the antibacterial rate of Candida albicans was 92.5%. The breaking strength was 277 N, and the breaking elongation was 37%. Compared with Example 3, the antistatic properties, antibacterial properties, and breaking resistance of Example 11 were all reduced. This is because the lack of genipin modification treatment reduced the cross-linking between silk fibroin proteins, and the reduction of the network structure led to a decrease in the stability of silk fibroin proteins. Therefore, the antistatic properties, antibacterial properties, and breaking resistance of the fabric were all reduced.

[0120] As shown in Table 1, the only difference between Comparative Example 1 and Example 3 is that no toughening conductive agent was added in Comparative Example 1, and the surface charge density in Comparative Example 1 was 6.1 μC / m. 2 The antibacterial rate of Escherichia coli was 87.2%, the antibacterial rate of Staphylococcus aureus was 86.8%, and the antibacterial rate of Candida albicans was 86.7%. The tensile strength was 177 N, and the elongation at break was 29%. Compared with Comparative Example 1 and Example 3, the antistatic properties, antibacterial properties, and tensile properties of the fabric were significantly reduced. This is because the lack of modification treatment with toughening conductive agent reduced the toughness of the fabric and weakened the synergistic effect of modified polyacrylic acid conductive fiber and modified silk fibroin fiber. Therefore, the antistatic properties, antibacterial properties, and tensile properties of the fabric were significantly reduced.

[0121] As shown in Table 1, the only difference between Comparative Example 2 and Example 3 is that the modified silk fibroin fiber was replaced with silk fibroin fiber in Comparative Example 2, and the surface charge density in Comparative Example 2 was 4.9 μC / m. 2 The antibacterial rate of Escherichia coli was 81.2%, the antibacterial rate of Staphylococcus aureus was 80.5%, and the antibacterial rate of Candida albicans was 81.6%. The breaking strength was 183 N, and the breaking elongation was 25%. Compared with Comparative Example 2 and Example 3, the antistatic properties, antibacterial properties, and breaking resistance of the fabric were significantly reduced. This is because the silk fibroin lacked modification treatment, the stability of the silk fibroin fiber decreased, and the synergistic effect of the modified polyacrylic acid conductive fiber and the silk fibroin fiber was weakened. Therefore, the antistatic properties, antibacterial properties, and breaking resistance of the fabric were significantly reduced.

[0122] This specific embodiment is merely an explanation of this application and is not intended to limit it. Based on the above description, those skilled in the art can make various changes and modifications without departing from the technical concept of this application. The technical scope of this application is not limited to the contents of the specification but must be determined according to the scope of the claims.

Claims

1. A fabric having antistatic properties, characterized in that: The components include the following parts by mass: 200-300 parts of modified polyacrylic acid conductive fiber 150-200 parts of modified silk fibroin fiber The modified polyacrylic conductive fiber includes modified polyacrylic fiber and a toughening conductive agent; The modified polyacrylic acid fiber comprises thiophene-grafted polyacrylic acid and a co-crosslinking agent; The thiophene-grafted polyacrylic acid comprises acrylic acid and 3,4-dimethoxythiophene; The co-crosslinking agent is pyrrole; The mass ratio of acrylic acid, 3,4-dimethoxythiophene, and pyrrole is 1:1.08:(0.5-0.7). The modified polyacrylic acid conductive fiber is prepared using the following steps: Thiophene-grafted polyacrylic acid, ferric chloride, and anhydrous ethanol were mixed to obtain spinning solution A. Pyrrole was dissolved in anhydrous ethanol to obtain spinning solution B. Toughening conductive agent, N,N-dimethylacetamide, and anhydrous ethanol were mixed to obtain a coagulation bath. Three-layer coaxial electrospinning was used. Spinning solution B was placed in the first layer, spinning solution A was placed in the second layer, and spinning solution B was placed in the third layer. The second layer covered the outside of the first layer, and the third layer covered the outside of the second layer. The obtained modified polyacrylic acid fiber was passed into the coagulation bath. The spun yarn in the coagulation bath was collected, washed, and dried to obtain modified polyacrylic acid conductive fiber. The toughening conductive agent comprises a two-dimensional transition metal nitride and pyrrole; The modified silk fibroin includes silk fibroin, genipin, and tannic acid.

2. The fabric with anti-static property according to claim 1, characterized in that: The mass ratio of silk fibroin, genipin and tannic acid is 1:0.05:(0.05-0.1).

3. The fabric with anti-static property according to claim 2, characterized in that: The fabric with antistatic properties is prepared using the following steps: Preparation of modified polyacrylic acid conductive fibers; Preparation of modified silk fibroin fibers: Silk fibroin, genipin, tannic acid and deionized water are mixed and stirred to obtain a modified silk fibroin solution. The modified silk fibroin solution is freeze-dried to obtain modified silk fibroin. The modified silk fibroin is dissolved in calcium chloride formic acid solution to obtain a spinning solution. Deionized water, sodium dodecyl sulfate and ethanol are mixed and dissolved to obtain a coagulation bath. The spinning solution is wet-spun to collect fibers. The collected fibers are washed with deionized water and dried to obtain modified silk fibroin fibers. A fabric with antistatic properties is obtained by weaving modified polyacrylic conductive fiber as warp and modified silk fibroin fiber as weft.

Images