Warm-keeping antistatic chinlon knitted fabric as well as preparation method and application thereof

Abstract

The invention relates to the technical field of functional fabrics, in particular to a warm-keeping antistatic chinlon knitted fabric and a preparation method and application thereof. According to the warm-keeping anti-static chinlon knitted fabric, the PA66 resin is subjected to melt spinning and blended with the polyester fibers to form the composite yarn, the composite yarn is spun into the fabric through the knitting technology, and by adding the betaine organic anti-static agent, the anti-static performance of the chinlon fabric can be effectively improved; the thermal insulation performance of the nylon fabric can be effectively improved by adding the inorganic composite nano material with photothermal conversion performance, molecules of the betaine organic antistatic agent contain alkenyl, the betaine organic antistatic agent can be connected to a PA66 molecular chain under the action of an initiator and is good in dispersion uniformity in PA66 resin, the inorganic composite nano material is subjected to modification treatment, and the thermal insulation performance of the nylon fabric is improved. The introduced epoxy group is bonded with the betaine organic antistatic agent and is connected to a PA66 molecular chain, so that the dispersion uniformity of the antistatic agent in the PA66 resin can be improved.

Description

Technical Field

[0001] This invention relates to the field of functional fabric technology, specifically to a warm and antistatic nylon knitted fabric, its preparation method, and its application. Background Technology

[0002] Nylon (a polyamide fiber) is widely used in the fabric industry due to its excellent abrasion resistance and moisture absorption. With technological advancements, people have increasingly higher demands for clothing fabrics, such as improved warmth retention. Adding inorganic composite nanomaterials with photothermal conversion properties can effectively improve the warmth retention of nylon fabrics. However, inorganic nanomaterials are prone to agglomeration and have poor dispersion uniformity in the resin matrix, thus affecting their light absorption and heat generation properties. Furthermore, nylon fabrics have poor antistatic properties, requiring modification treatment to improve them.

[0003] Chinese patent CN114737271B discloses a method for treating antistatic nylon fabric. By adding graphene to reduce the resistivity of nylon fibers, the antistatic properties of the fabric are improved. Graphene, as a carbon-based material, can also give the fabric light-absorbing and heat-generating properties. However, the dispersion and refinement of graphene are only achieved through physical modification with sodium lauryl sulfate, which has limited improvement on its dispersibility in nylon chips. Therefore, the antistatic and heat-retaining properties need further improvement. Summary of the Invention

[0004] To address the shortcomings of existing technologies, this invention provides a warm and antistatic nylon knitted fabric to solve the problem that the antistatic and warmth retention properties of nylon fabrics in existing technologies need to be improved.

[0005] To achieve the above objectives, the technical solution adopted by the present invention is as follows: Step 1: Disperse 2-amino-4-pentenoic acid in dimethyl sulfoxide, preheat, add potassium hydroxide, and then add N,N-dimethyl-1,3-propanediamine dropwise. After the addition is complete, raise the temperature to the set temperature and react. After the reaction is complete, rotary evaporate to obtain the amidated product. Step 2: Add the amidation product to an aqueous solution of sodium chloroacetate and react. After the reaction is complete, rotary evaporate to obtain betaine containing an alkenyl group. Step 3: Dissolve alkenyl betaine in deionized water, add PA66 resin powder and initiator H2O2 / ascorbic acid, react, filter, wash and dry to obtain modified PA66; Step 4: PA66 (polyamide 66) resin, modified PA66, and epoxy-modified inorganic composite nanomaterials are mixed and melted. The melt is then extruded through a spinneret to form fiber filaments. The fibers are cooled by side blowing, stretched, and chopped to obtain modified nylon 66 fibers. Step 5: Blend modified nylon 66 fiber with polyester fiber to obtain composite yarn. Spin the composite yarn into fabric through knitting process to obtain warm and antistatic nylon knitted fabric.

[0006] Preferably, in step one, the molar ratio of 2-amino-4-pentenoic acid to N,N-dimethyl-1,3-propanediamine is 1:(1.1-1.2), the amount of potassium hydroxide added is 0.4%-0.6% of the mass of 2-amino-4-pentenoic acid, the dropping time of N,N-dimethyl-1,3-propanediamine is 35-45 min, and the reaction conditions are stirring at a set temperature for 6-8 h. The set temperature is 150-160℃.

[0007] Preferably, a water separator is installed during the above reaction process.

[0008] Preferably, the amount of dimethyl sulfoxide used is 8-12 times the mass of 2-amino-4-pentenoic acid.

[0009] Preferably, in step two, the molar ratio of the amidation product to sodium chloroacetate in the sodium chloroacetate aqueous solution is 1:(1.05-1.1), and the reaction conditions are stirring at 75-85℃ for 6-10 hours.

[0010] Preferably, the sodium chloroacetate aqueous solution is a 20wt%-30wt% sodium chloroacetate aqueous solution.

[0011] Preferably, in step three, the mass ratio of PA66 resin powder, deionized water, initiator H2O2 / ascorbic acid, and alkenyl-containing betaine is 10:(200-300):(0.5-1):(0.4-0.8), and the reaction is carried out under the condition of stirring at 65-75℃ for 50-70 minutes.

[0012] Preferably, the initiator H2O2 / ascorbic acid is a mixed aqueous solution of H2O2 and ascorbic acid, wherein the mass percentage of H2O2 and ascorbic acid in the mixed aqueous solution is 30%, and the molar ratio of H2O2 to ascorbic acid is 1:0.6.

[0013] Preferably, in step four, the mass ratio of PA66 resin, modified PA66, and epoxy-modified inorganic composite nanomaterial is 100:(40-60):(3-5), the melting temperature is 285-295℃, the spinneret pressure is 16-20MPa, the side-blowing temperature is 15-20℃, and the draw ratio is 1.4-1.6 times.

[0014] Preferably, the epoxy-modified inorganic composite nanomaterial in step four includes epoxy-modified carbon nanotube-tungsten oxide composite nanomaterial.

[0015] Preferably, the epoxy-modified carbon nanotube-tungsten oxide composite nanomaterial is prepared by the following method: S1. Carbon nanotubes are reacted with a mixed acid of sulfuric acid and nitric acid to prepare carboxylated carbon nanotubes; S2, carboxylated carbon nanotubes react with ammonium metatungstate to prepare carbon nanotube-tungsten oxide composite nanomaterials; S3, carbon nanotube-tungsten oxide composite nanomaterials were reacted with γ-glycidyl etheroxypropyltrimethoxysilane (silane coupling agent KH560) to prepare epoxy-modified carbon nanotube-tungsten oxide composite nanomaterials.

[0016] Preferably, in step five, the mass ratio of modified nylon 66 fiber to polyester fiber is (50-70):(30-50), the yarn count of the composite yarn is 20-40S (English count), and the weight of the warm and antistatic nylon knitted fabric is 160-200 g / m². 2 .

[0017] The present invention also discloses a warm and antistatic nylon knitted fabric prepared by the above-described method for preparing warm and antistatic nylon knitted fabric.

[0018] An application of a type of warm and antistatic nylon knitted fabric, as described above, in thermal clothing.

[0019] Compared with the prior art, the beneficial effects of the present invention are as follows: The warm and antistatic nylon knitted fabric of the present invention is made by melt spinning PA66 resin and blending it with polyester fibers to form a composite yarn, which is then knitted into fabric. By adding betaine-based organic antistatic agents, the antistatic properties of the nylon fabric can be effectively improved. By adding inorganic composite nanomaterials with photothermal conversion properties, the warming properties of the nylon fabric can be effectively improved. In the present invention, during the preparation of betaine-based organic antistatic agents... 2-Amino-4-pentenoic acid reacts with N,N-dimethyl-1,3-propanediamine to prepare an amidated product, i.e., an alkenyl group is introduced onto the N,N-dimethyl-1,3-propanediamine molecule. The tertiary amine on the N,N-dimethyl-1,3-propanediamine molecule reacts with sodium chloroacetate to form alkenyl-containing betaine. Under the action of an initiator, the alkenyl group is grafted onto the PA66 molecular chain, resulting in good uniform dispersion of betaine-based organic antistatic agents in PA66 resin, which can improve the antistatic properties of nylon fabrics. The inorganic composite nanomaterial is a carbon nanotube-tungsten oxide composite nanomaterial. The synergistic effect of carbon nanotubes and tungsten oxide results in a wide light absorption range, giving nylon fabric excellent light absorption and heat generation properties, as well as good warmth retention. The carbon nanotube-tungsten oxide composite nanomaterial undergoes modification treatment, introducing epoxy groups. During the preparation of betaine-based organic antistatic agents, amino groups are introduced through 2-amino-4-pentenoic acid molecules. This allows the carbon nanotube-tungsten oxide composite nanomaterial to react with the amino groups, thereby bonding the carbon nanotube-tungsten oxide composite nanomaterial to the betaine-based organic antistatic agent and then attaching it to the PA66 molecular chain. This improves the uniformity of the dispersion of the carbon nanotube-tungsten oxide composite nanomaterial in PA66 resin, enhancing the warmth retention of the nylon fabric. Furthermore, the carbon nanotubes in the carbon nanotube-tungsten oxide composite nanomaterial can construct a conductive network in PA66 resin, achieving antistatic effects through charge leakage and dispersion, further improving the antistatic properties of the nylon fabric. Attached Figure Description

[0020] Figure 1 This is a schematic diagram illustrating the preparation of the amidated product by reacting 2-amino-4-pentenoic acid with N,N-dimethyl-1,3-propanediamine in this invention. Figure 2 This is a schematic diagram illustrating the reaction of the amidation product with sodium chloroacetate to prepare alkenyl-containing betaine in this invention. Detailed Implementation

[0021] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. All other embodiments obtained by those skilled in the art based on the embodiments of the present invention without creative effort are within the scope of protection of the present invention.

[0022] Example 1 This embodiment discloses a method for preparing epoxy-modified carbon nanotube-tungsten oxide composite nanomaterials, including the following steps: S1. Carbon nanotubes were placed in a sulfuric acid-nitric acid mixture with a mass-volume ratio of 0.1 g / 60 mL. The mixture was ultrasonically treated at 60 °C for 15 h. After ultrasonic treatment, the mixture was diluted with 1000 times the volume of deionized water, filtered under reduced pressure through a 0.22 μm filter membrane, and washed until neutral. The product was then dried in a vacuum oven at 50 °C until constant weight to obtain carboxylated carbon nanotubes. The sulfuric acid-nitric acid mixture was prepared by mixing 98 wt% sulfuric acid aqueous solution and 65 wt% nitric acid aqueous solution in a volume ratio of 3:1. S2. Carboxylated carbon nanotubes were added to a 15wt% ammonium metatungstate aqueous solution, with a mass-volume ratio of 1g / 10mL for the carboxylated carbon nanotubes and the 15wt% ammonium metatungstate aqueous solution. The mixture was heat-treated at 60℃ for 4h. After heat treatment, the mixture was filtered and dried in a vacuum chamber at 50℃ to constant weight. It was then placed in a tube furnace and calcined at 550℃ for 4h under nitrogen protection. After calcination, the mixture was naturally cooled to room temperature to obtain carbon nanotube-tungsten oxide composite nanomaterials. S3. Carbon nanotube-tungsten oxide composite nanomaterials were added to deionized water and ultrasonically dispersed at 50 kHz for 30 min to obtain a composite nanomaterial dispersion. γ-glycidyl etheroxypropyltrimethoxysilane was dissolved in 95 wt% ethanol aqueous solution to obtain a γ-glycidyl etheroxypropyltrimethoxysilane solution. The γ-glycidyl etheroxypropyltrimethoxysilane solution was added to the composite nanomaterial dispersion, and the mixture was stirred at 50 r / min for 24 h at room temperature. After the reaction was completed, the mixture was centrifuged at 4000 r / min for 5 min, the supernatant was removed, and the mixture was washed with deionized water and ethanol, centrifuged three times, and the product was dried in a 50℃ vacuum oven to constant weight to obtain epoxy-modified carbon nanotube-tungsten oxide composite nanomaterials. The mass ratio of carbon nanotube-tungsten oxide composite nanomaterials, deionized water, γ-glycidyl etheroxypropyltrimethoxysilane, and 95 wt% ethanol aqueous solution was 1:200:1:10.

[0023] Example 2 This embodiment discloses a method for preparing a warm and antistatic nylon knitted fabric, including the following steps: Step 1: 2-Amino-4-pentenoic acid is dispersed in dimethyl sulfoxide at a molar ratio of 1:1.1 to N,N-dimethyl-1,3-propanediamine. The mixture is preheated to 80°C, and potassium hydroxide is added at a stirring speed of 50 r / min. The amount of potassium hydroxide added is 0.4% of the mass of 2-amino-4-pentenoic acid. N,N-dimethyl-1,3-propanediamine is added dropwise over a period of 35 min. After the addition is complete, the temperature is raised to 150°C, and the mixture is stirred at 200 r / min for 8 h. After the reaction is complete, the solvent dimethyl sulfoxide and unreacted N,N-dimethyl-1,3-propanediamine are removed by rotary evaporation to obtain the amidated product. Step 2: Add the amidation product to a 20wt% sodium chloroacetate aqueous solution. The molar ratio of the amidation product to the sodium chloroacetate in the 20wt% sodium chloroacetate aqueous solution is 1:1.05. Stir the reaction at 75℃ and 200r / min for 10h. After the reaction is complete, remove the solvent water by rotary evaporation to obtain alkenyl-containing betaine. Step 3: Dissolve alkenyl-containing betaine in deionized water, add PA66 resin powder and initiator H2O2 / ascorbic acid. The mass ratio of PA66 resin powder, deionized water, initiator H2O2 / ascorbic acid, and alkenyl-containing betaine is 10:200:0.5:0.4. Stir the mixture at 100 r / min for 70 min at 65℃. After the reaction is complete, filter the mixture, wash it three times with deionized water, and dry it in a vacuum oven at 60℃ until constant weight to obtain modified PA66. The initiator H2O2 / ascorbic acid is a mixed aqueous solution of H2O2 and ascorbic acid. The mass percentage of H2O2 and ascorbic acid in the mixed aqueous solution is 30%, and the molar ratio of H2O2 to ascorbic acid is 1:0.6. Step 4: PA66 resin, modified PA66, and the epoxy-modified carbon nanotube-tungsten oxide composite nanomaterial prepared in Example 1 are mixed. The mass ratio of PA66 resin, modified PA66, and epoxy-modified carbon nanotube-tungsten oxide composite nanomaterial is 100:40:3. The mixture is melted at a melting temperature of 285°C. The melt is then extruded through a spinneret to form fibers at a pressure of 18 MPa. The fibers are cooled by side blowing at a temperature of 18°C. The fibers are then drawn with a draw ratio of 1.5 times and chopped to obtain modified nylon 66 fibers with a length of 38 mm. Step 5: Blend modified nylon 66 fiber with polyester fiber at a mass ratio of 50:50 to obtain a composite yarn with a yarn count of 30S. The composite yarn is then spun into fabric using a knitting process to obtain a warm and antistatic nylon knitted fabric. The weight of the warm and antistatic nylon knitted fabric is 180 g / m². 2.

[0024] Example 3 This embodiment discloses a method for preparing a warm and antistatic nylon knitted fabric, including the following steps: Step 1: 2-Amino-4-pentenoic acid is dispersed in dimethyl sulfoxide at a molar ratio of 1:1.2 to N,N-dimethyl-1,3-propanediamine. The mixture is preheated to 80°C, and potassium hydroxide is added at a stirring speed of 50 r / min. The amount of potassium hydroxide added is 0.6% of the mass of 2-amino-4-pentenoic acid. N,N-dimethyl-1,3-propanediamine is added dropwise over a period of 45 min. After the addition is complete, the temperature is raised to 160°C, and the mixture is stirred at 200 r / min for 6 h. After the reaction is complete, the solvent dimethyl sulfoxide and unreacted N,N-dimethyl-1,3-propanediamine are removed by rotary evaporation to obtain the amidated product. Step 2: Add the amidation product to a 30wt% sodium chloroacetate aqueous solution. The molar ratio of the amidation product to the sodium chloroacetate in the 30wt% sodium chloroacetate aqueous solution is 1:1.1. Stir the reaction at 85℃ and 200r / min for 6h. After the reaction is complete, remove the solvent water by rotary evaporation to obtain alkenyl-containing betaine. Step 3: Dissolve alkenyl betaine in deionized water, add PA66 resin powder and initiator H2O2 / ascorbic acid. The mass ratio of PA66 resin powder, deionized water, initiator H2O2 / ascorbic acid, and alkenyl betaine is 10:300:1:0.8. Stir the mixture at 100 r / min for 50 min at 75℃. After the reaction is complete, filter the mixture, wash it three times with deionized water, and dry it in a vacuum oven at 60℃ until constant weight to obtain modified PA66. The initiator H2O2 / ascorbic acid is a mixed aqueous solution of H2O2 and ascorbic acid. The mass percentage of H2O2 and ascorbic acid in the mixed aqueous solution is 30%, and the molar ratio of H2O2 to ascorbic acid is 1:0.6. Step 4: PA66 resin, modified PA66, and the epoxy-modified carbon nanotube-tungsten oxide composite nanomaterial prepared in Example 1 are mixed. The mass ratio of PA66 resin, modified PA66, and epoxy-modified carbon nanotube-tungsten oxide composite nanomaterial is 100:60:5. The mixture is melted at a melting temperature of 295°C. The melt is then extruded through a spinneret to form fibers at a pressure of 18 MPa. The fibers are cooled by side blowing at a temperature of 18°C. The fibers are then drawn with a draw ratio of 1.5 times and chopped to obtain modified nylon 66 fibers with a length of 38 mm. Step 5: Blend modified nylon 66 fiber with polyester fiber at a mass ratio of 70:30 to obtain a composite yarn with a yarn count of 30S. The composite yarn is then spun into fabric using a knitting process to obtain a warm and antistatic nylon knitted fabric. The weight of the warm and antistatic nylon knitted fabric is 180 g / m². 2 .

[0025] Example 4 This embodiment discloses a method for preparing a warm and antistatic nylon knitted fabric, including the following steps: Step 1: 2-Amino-4-pentenoic acid is dispersed in dimethyl sulfoxide at a molar ratio of 1:1.12 to N,N-dimethyl-1,3-propanediamine. The mixture is preheated to 80°C, and potassium hydroxide is added at a stirring speed of 50 r / min. The amount of potassium hydroxide added is 0.45% of the mass of 2-amino-4-pentenoic acid. N,N-dimethyl-1,3-propanediamine is added dropwise over a period of 40 min. After the addition is complete, the temperature is raised to 155°C, and the mixture is stirred at 200 r / min for 7 h. After the reaction is complete, the solvent dimethyl sulfoxide and unreacted N,N-dimethyl-1,3-propanediamine are removed by rotary evaporation to obtain the amidated product. Step 2: Add the amidation product to a 25 wt% sodium chloroacetate aqueous solution. The molar ratio of the amidation product to the sodium chloroacetate in the 25 wt% sodium chloroacetate aqueous solution is 1:1.06. Stir the reaction at 80°C and 200 r / min for 8 h. After the reaction is complete, remove the solvent water by rotary evaporation to obtain alkenyl-containing betaine. Step 3: Dissolve alkenyl betaine in deionized water, add PA66 resin powder and initiator H2O2 / ascorbic acid. The mass ratio of PA66 resin powder, deionized water, initiator H2O2 / ascorbic acid, and alkenyl betaine is 10:225:0.6:0.5. Stir the mixture at 100 r / min for 60 min at 70℃. After the reaction is complete, filter the mixture, wash it three times with deionized water, and dry it in a vacuum oven at 60℃ until constant weight to obtain modified PA66. The initiator H2O2 / ascorbic acid is a mixed aqueous solution of H2O2 and ascorbic acid. The mass percentage of H2O2 and ascorbic acid in the mixed aqueous solution is 30%, and the molar ratio of H2O2 to ascorbic acid is 1:0.6. Step 4: PA66 resin, modified PA66, and the epoxy-modified carbon nanotube-tungsten oxide composite nanomaterial prepared in Example 1 are mixed. The mass ratio of PA66 resin, modified PA66, and epoxy-modified carbon nanotube-tungsten oxide composite nanomaterial is 100:45:3.5. The mixture is melted at a melting temperature of 290°C. The melt is then extruded through a spinneret to form fibers at a pressure of 18 MPa. The fibers are cooled by side blowing at a temperature of 18°C. The fibers are then drawn at a draw ratio of 1.5 times and chopped to obtain modified nylon 66 fibers with a length of 38 mm. Step 5: Blend modified nylon 66 fiber with polyester fiber at a mass ratio of 55:45 to obtain a composite yarn with a yarn count of 30S. The composite yarn is then spun into fabric using a knitting process to obtain a warm and antistatic nylon knitted fabric. The weight of the warm and antistatic nylon knitted fabric is 180 g / m². 2 .

[0026] Example 5 This embodiment discloses a method for preparing a warm and antistatic nylon knitted fabric, including the following steps: Step 1: 2-Amino-4-pentenoic acid is dispersed in dimethyl sulfoxide at a molar ratio of 1:1.15 to N,N-dimethyl-1,3-propanediamine. The mixture is preheated to 80°C, and potassium hydroxide is added at a stirring speed of 50 r / min. The amount of potassium hydroxide added is 0.5% of the mass of 2-amino-4-pentenoic acid. N,N-dimethyl-1,3-propanediamine is added dropwise over a period of 40 min. After the addition is complete, the temperature is raised to 155°C, and the mixture is stirred at 200 r / min for 7 h. After the reaction is complete, the solvent dimethyl sulfoxide and unreacted N,N-dimethyl-1,3-propanediamine are removed by rotary evaporation to obtain the amidated product. Step 2: Add the amidation product to a 25wt% sodium chloroacetate aqueous solution. The molar ratio of the amidation product to the sodium chloroacetate in the 25wt% sodium chloroacetate aqueous solution is 1:1.07. Stir the reaction at 80℃ and 200r / min for 8 hours. After the reaction is complete, remove the solvent water by rotary evaporation to obtain alkenyl-containing betaine. Step 3: Dissolve alkenyl betaine in deionized water, add PA66 resin powder and initiator H2O2 / ascorbic acid. The mass ratio of PA66 resin powder, deionized water, initiator H2O2 / ascorbic acid, and alkenyl betaine is 10:250:0.75:0.6. Stir the mixture at 100 r / min for 60 min at 70℃. After the reaction is complete, filter the mixture, wash it three times with deionized water, and dry it in a vacuum oven at 60℃ until constant weight to obtain modified PA66. The initiator H2O2 / ascorbic acid is a mixed aqueous solution of H2O2 and ascorbic acid. The mass percentage of H2O2 and ascorbic acid in the mixed aqueous solution is 30%, and the molar ratio of H2O2 to ascorbic acid is 1:0.6. Step 4: PA66 resin, modified PA66, and the epoxy-modified carbon nanotube-tungsten oxide composite nanomaterial prepared in Example 1 are mixed. The mass ratio of PA66 resin, modified PA66, and epoxy-modified carbon nanotube-tungsten oxide composite nanomaterial is 100:50:4. The mixture is melted at a melting temperature of 290°C. The melt is then extruded through a spinneret to form fiber filaments at a pressure of 18 MPa. The filaments are cooled by side blowing at a temperature of 18°C. The filaments are then drawn at a draw ratio of 1.5 times and chopped to obtain modified nylon 66 fibers with a length of 38 mm. Step 5: Blend modified nylon 66 fiber with polyester fiber at a mass ratio of 60:40 to obtain a composite yarn with a yarn count of 30S. The composite yarn is then spun into fabric using a knitting process to obtain a warm and antistatic nylon knitted fabric. The weight of the warm and antistatic nylon knitted fabric is 180 g / m². 2 .

[0027] Example 6 This embodiment discloses a method for preparing a warm and antistatic nylon knitted fabric, including the following steps: Step 1: 2-Amino-4-pentenoic acid is dispersed in dimethyl sulfoxide at a molar ratio of 1:1.18 to N,N-dimethyl-1,3-propanediamine. The mixture is preheated to 80°C, and potassium hydroxide is added at a stirring speed of 50 r / min. The amount of potassium hydroxide added is 0.55% of the mass of 2-amino-4-pentenoic acid. N,N-dimethyl-1,3-propanediamine is added dropwise over a period of 40 min. After the addition is complete, the temperature is raised to 155°C, and the mixture is stirred at 200 r / min for 7 h. After the reaction is complete, the solvent dimethyl sulfoxide and unreacted N,N-dimethyl-1,3-propanediamine are removed by rotary evaporation to obtain the amidated product. Step 2: Add the amidation product to a 25wt% sodium chloroacetate aqueous solution. The molar ratio of the amidation product to the sodium chloroacetate in the 25wt% sodium chloroacetate aqueous solution is 1:1.09. Stir the reaction at 80℃ and 200r / min for 8h. After the reaction is complete, remove the solvent water by rotary evaporation to obtain alkenyl-containing betaine. Step 3: Dissolve alkenyl betaine in deionized water, add PA66 resin powder and initiator H2O2 / ascorbic acid. The mass ratio of PA66 resin powder, deionized water, initiator H2O2 / ascorbic acid, and alkenyl betaine is 10:280:0.9:0.7. Stir the mixture at 100 r / min for 60 min at 70℃. After the reaction is complete, filter the mixture, wash it three times with deionized water, and dry it in a vacuum oven at 60℃ until constant weight to obtain modified PA66. The initiator H2O2 / ascorbic acid is a mixed aqueous solution of H2O2 and ascorbic acid. The mass percentage of H2O2 and ascorbic acid in the mixed aqueous solution is 30%, and the molar ratio of H2O2 to ascorbic acid is 1:0.6. Step 4: PA66 resin, modified PA66, and the epoxy-modified carbon nanotube-tungsten oxide composite nanomaterial prepared in Example 1 are mixed. The mass ratio of PA66 resin, modified PA66, and epoxy-modified carbon nanotube-tungsten oxide composite nanomaterial is 100:55:4.5. The mixture is melted at a melting temperature of 290°C. The melt is then extruded through a spinneret to form fibers at a pressure of 18 MPa. The fibers are cooled by side blowing at a temperature of 18°C. The fibers are then drawn with a draw ratio of 1.5 times and chopped to obtain modified nylon 66 fibers with a length of 38 mm. Step 5: Blend modified nylon 66 fiber with polyester fiber at a mass ratio of 65:35 to obtain a composite yarn with a yarn count of 30S. The composite yarn is then spun into fabric using a knitting process to obtain a warm and antistatic nylon knitted fabric. The weight of the warm and antistatic nylon knitted fabric is 180 g / m². 2 .

[0028] Comparative Example 1 This comparative example discloses a method for preparing a warm and antistatic nylon knitted fabric, including the following steps: Step 1: 2-Amino-4-pentenoic acid is dispersed in dimethyl sulfoxide at a molar ratio of 1:1.1 to N,N-dimethyl-1,3-propanediamine. The mixture is preheated to 80°C, and potassium hydroxide is added at a stirring speed of 50 r / min. The amount of potassium hydroxide added is 0.4% of the mass of 2-amino-4-pentenoic acid. N,N-dimethyl-1,3-propanediamine is added dropwise over a period of 35 min. After the addition is complete, the temperature is raised to 150°C, and the mixture is stirred at 200 r / min for 8 h. After the reaction is complete, the solvent dimethyl sulfoxide and unreacted N,N-dimethyl-1,3-propanediamine are removed by rotary evaporation to obtain the amidated product. Step 2: Add the amidation product to a 20wt% sodium chloroacetate aqueous solution. The molar ratio of the amidation product to the sodium chloroacetate in the 20wt% sodium chloroacetate aqueous solution is 1:1.05. Stir the reaction at 75℃ and 200r / min for 10h. After the reaction is complete, remove the solvent water by rotary evaporation to obtain alkenyl-containing betaine. Step 3: Dissolve alkenyl-containing betaine in deionized water, add PA66 resin powder and initiator H2O2 / ascorbic acid. The mass ratio of PA66 resin powder, deionized water, initiator H2O2 / ascorbic acid, and alkenyl-containing betaine is 10:200:0.5:0.4. Stir the mixture at 100 r / min for 70 min at 65℃. After the reaction is complete, filter the mixture, wash it three times with deionized water, and dry it in a vacuum oven at 60℃ until constant weight to obtain modified PA66. The initiator H2O2 / ascorbic acid is a mixed aqueous solution of H2O2 and ascorbic acid. The mass percentage of H2O2 and ascorbic acid in the mixed aqueous solution is 30%, and the molar ratio of H2O2 to ascorbic acid is 1:0.6. Step 4: PA66 resin, modified PA66, and the carbon nanotube-tungsten oxide composite nanomaterial prepared in Example 1 are mixed. The mass ratio of PA66 resin, modified PA66, and carbon nanotube-tungsten oxide composite nanomaterial is 100:40:3. The mixture is melted at a melting temperature of 285°C. The melt is then extruded through a spinneret to form fibers at a pressure of 18 MPa. The fibers are cooled by side blowing at a temperature of 18°C. The fibers are then drawn with a draw ratio of 1.5 times and chopped to obtain modified nylon 66 fibers with a length of 38 mm. Step 5: Blend modified nylon 66 fiber with polyester fiber at a mass ratio of 50:50 to obtain a composite yarn with a yarn count of 30S. The composite yarn is then spun into fabric using a knitting process to obtain a warm and antistatic nylon knitted fabric. The weight of the warm and antistatic nylon knitted fabric is 180 g / m². 2 .

[0029] Comparative Example 2 This comparative example discloses a method for preparing a warm and antistatic nylon knitted fabric, including the following steps: Step 1: 2-Amino-4-pentenoic acid is dispersed in dimethyl sulfoxide at a molar ratio of 1:1.1 to N,N-dimethyl-1,3-propanediamine. The mixture is preheated to 80°C, and potassium hydroxide is added at a stirring speed of 50 r / min. The amount of potassium hydroxide added is 0.4% of the mass of 2-amino-4-pentenoic acid. N,N-dimethyl-1,3-propanediamine is added dropwise over a period of 35 min. After the addition is complete, the temperature is raised to 150°C, and the mixture is stirred at 200 r / min for 8 h. After the reaction is complete, the solvent dimethyl sulfoxide and unreacted N,N-dimethyl-1,3-propanediamine are removed by rotary evaporation to obtain the amidated product. Step 2: Add the amidation product to a 20wt% sodium chloroacetate aqueous solution. The molar ratio of the amidation product to the sodium chloroacetate in the 20wt% sodium chloroacetate aqueous solution is 1:1.05. Stir the reaction at 75℃ and 200r / min for 10h. After the reaction is complete, remove the solvent water by rotary evaporation to obtain alkenyl-containing betaine. Step 3: Mix PA66 resin powder with alkenyl betaine at a mass ratio of 10:0.4, melt at a melting temperature of 285℃, extrude, cool, and pelletize to obtain modified PA66. Step 4: PA66 resin, modified PA66, and the carbon nanotube-tungsten oxide composite nanomaterial prepared in Example 1 are mixed. The mass ratio of PA66 resin, modified PA66, and carbon nanotube-tungsten oxide composite nanomaterial is 100:40:3. The mixture is melted at a melting temperature of 285°C. The melt is then extruded through a spinneret to form fibers at a pressure of 18 MPa. The fibers are cooled by side blowing at a temperature of 18°C. The fibers are then drawn with a draw ratio of 1.5 times and chopped to obtain modified nylon 66 fibers with a length of 38 mm. Step 5: Blend modified nylon 66 fiber with polyester fiber at a mass ratio of 50:50 to obtain a composite yarn with a yarn count of 30S. The composite yarn is then spun into fabric using a knitting process to obtain a warm and antistatic nylon knitted fabric. The weight of the warm and antistatic nylon knitted fabric is 180 g / m². 2 .

[0030] In the above embodiments and comparative examples: the carbon nanotubes are single-walled carbon nanotubes with an inner diameter of 0.8-1.6 nm, an outer diameter of 1-2 nm, and a length of 5-30 μm; the PA66 resin used to prepare the modified PA66 is the same as that used to prepare the modified nylon 66 fiber, and the density of the PA66 resin is 1.14 g / cm³. 3 The melting temperature is 262℃. The PA66 resin powder used to prepare the modified PA66 is obtained by pulverizing PA66 resin. The particle size of the PA66 resin powder is 2000 mesh. The average length of the polyester fiber is 38mm and the specification is 20D / 1F.

[0031] Test case (1) Thermal insulation performance: The thermal insulation performance of the nylon fabric samples prepared in Examples 2-6 and Comparative Examples 1-2 was determined. The thermal insulation performance of the fabric was evaluated by comparing the temperature difference between the inner and outer sides of the fabric. The determination method was as follows: the nylon fabric sample was placed on a heat-insulating table, and the nylon fabric sample was irradiated with an infrared lamp with a power of 500W. The distance between the infrared lamp and the nylon fabric sample was 50cm, and the irradiation time was 30min. The surface temperature difference of the nylon fabric sample before and after irradiation was calculated based on the surface temperature of the nylon fabric sample before and after irradiation. The results of the temperature difference measurement are shown in Table 1.

[0032] As shown in Table 1, the present invention, in preparing nylon fabric, incorporates carbon nanotube-tungsten oxide composite nanomaterials with photothermal conversion properties. These carbon nanotube-tungsten oxide composite nanomaterials have a wide light absorption range, resulting in good light absorption and heat generation properties and excellent warmth retention of the nylon fabric. Compared to Example 1, in Comparative Examples 1 and 2, the carbon nanotube-tungsten oxide composite nanomaterials were not linked to the PA66 molecular chain, leading to decreased dispersion uniformity in the PA66 resin and reduced warmth retention.

[0033] (2) Antistatic properties: The antistatic properties of the nylon fabric samples prepared in Examples 2-6 and Comparative Examples 1-2 were determined according to the standard GB / T12703.2-2009 "Evaluation of electrostatic properties of textiles - Part 2: surface charge density". The results of the surface charge density determination are shown in Table 2.

[0034] As shown in Table 2, the nylon fabric prepared by this invention exhibits excellent antistatic properties due to the introduction of an organic antistatic agent. Furthermore, the carbon nanotubes in the carbon nanotube-tungsten oxide composite nanomaterial can construct a conductive network within the PA66 resin, achieving antistatic effects through charge leakage and dispersion, further enhancing the antistatic performance of the nylon fabric. Compared to Example 1, in Comparative Example 1, the carbon nanotube-tungsten oxide composite nanomaterial was not connected to the PA66 molecular chain, resulting in decreased dispersion uniformity in the PA66 resin and a decline in antistatic performance. Similarly, in Comparative Example 2, the betaine-based organic antistatic agent was not connected to the PA66 molecular chain, leading to decreased dispersion uniformity in the PA66 resin and a further decline in antistatic performance.

[0035] Although embodiments of the invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made to these embodiments without departing from the principles and spirit of the invention, the scope of which is defined by the appended claims and their equivalents.

Claims

1. A method for preparing a warm and antistatic nylon knitted fabric, characterized in that, Includes the following steps: Step 1: Disperse 2-amino-4-pentenoic acid in dimethyl sulfoxide, preheat, add potassium hydroxide, and then add N,N-dimethyl-1,3-propanediamine dropwise. After the addition is complete, raise the temperature to the set temperature and react. After the reaction is complete, rotary evaporate to obtain the amidated product. Step 2: Add the amidation product to an aqueous solution of sodium chloroacetate and react. After the reaction is complete, rotary evaporate to obtain betaine containing an alkenyl group. Step 3: Dissolve alkenyl betaine in deionized water, add PA66 resin powder and initiator H2O2 / ascorbic acid, react, filter, wash and dry to obtain modified PA66; Step 4: PA66 resin, modified PA66, and epoxy-modified inorganic composite nanomaterials are mixed and melted. The melt is then extruded through a spinneret to form fiber filaments. The fibers are cooled by side blowing, stretched, and chopped to obtain modified nylon 66 fibers. Step 5: Blend modified nylon 66 fiber with polyester fiber to obtain composite yarn. Spin the composite yarn into fabric through knitting process to obtain warm and antistatic nylon knitted fabric.

2. The method for preparing a warm and antistatic nylon knitted fabric according to claim 1, characterized in that, In step one, the molar ratio of 2-amino-4-pentenoic acid to N,N-dimethyl-1,3-propanediamine is 1:(1.1-1.2), the amount of potassium hydroxide added is 0.4%-0.6% of the mass of 2-amino-4-pentenoic acid, the dropping time of N,N-dimethyl-1,3-propanediamine is 40-50 min, and the reaction conditions are stirring at a set temperature for 6-10 h; the set temperature is 150-160℃.

3. The method for preparing a warm and antistatic nylon knitted fabric according to claim 1, characterized in that, In step two, the molar ratio of the amidation product to sodium chloroacetate in the sodium chloroacetate aqueous solution is 1:(1.05-1.1), and the reaction is carried out under the condition of stirring at 75-85℃ for 6-10 hours.

4. The method for preparing a warm and antistatic nylon knitted fabric according to claim 1, characterized in that, In step three, the mass ratio of PA66 resin powder, deionized water, initiator H2O2 / ascorbic acid, and alkenyl-containing betaine is 10:(200-300):(0.5-1):(0.4-0.8), and the reaction is carried out under the condition of stirring at 65-75℃ for 50-70 minutes.

5. The method for preparing a warm and antistatic nylon knitted fabric according to claim 1, characterized in that, In step four, the mass ratio of PA66 resin, modified PA66, and epoxy-modified inorganic composite nanomaterials is 100:(40-60):(3-5), the melting temperature is 285-295℃, the spinneret pressure is 16-20MPa, the side-blowing temperature is 15-20℃, and the draw ratio is 1.4-1.6 times.

6. The method for preparing a warm and antistatic nylon knitted fabric according to claim 1, characterized in that, The epoxy-modified inorganic composite nanomaterials in step four include epoxy-modified carbon nanotube-tungsten oxide composite nanomaterials.

7. The method for preparing a warm and antistatic nylon knitted fabric according to claim 6, characterized in that, The epoxy-modified carbon nanotube-tungsten oxide composite nanomaterial is prepared by the following method: S1. Carbon nanotubes are reacted with a mixed acid of sulfuric acid and nitric acid to prepare carboxylated carbon nanotubes; S2, carboxylated carbon nanotubes react with ammonium metatungstate to prepare carbon nanotube-tungsten oxide composite nanomaterials; S3, carbon nanotube-tungsten oxide composite nanomaterials were reacted with γ-glycidyl etheroxypropyltrimethoxysilane to prepare epoxy-modified carbon nanotube-tungsten oxide composite nanomaterials.

8. The method for preparing a warm and antistatic nylon knitted fabric according to claim 1, characterized in that, In step five, the mass ratio of modified nylon 66 fiber to polyester fiber is (50-70):(30-50), the yarn count of the composite yarn is 20-40S, and the weight of the warm and antistatic nylon knitted fabric is 160-200g / m². 2 .

9. A warm and antistatic nylon knitted fabric prepared by the method for preparing warm and antistatic nylon knitted fabric as described in any one of claims 1-8.

10. The application of the thermal insulation and antistatic nylon knitted fabric as described in claim 9 in thermal clothing.

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