Production process of antistatic nylon fabric

Abstract

The invention relates to the field of textile processing, and discloses a production process of an antistatic nylon fabric. The specific steps are: using a modified waterborne polyurethane emulsion to scrape a nylon base cloth, and then pre-baking and baking to prepare the fabric; the modified waterborne polyurethane emulsion comprises: waterborne polyurethane emulsion, hybrid composite filler, functional additive, etc.; the hybrid composite filler is prepared by modifying nano titanium dioxide with a double-bond silane coupling agent and then reacting with modified graphene; the modified graphene is prepared by reacting phenyltri(dimethylsiloxy)silane with a flame retardant additive and a double-bond silane coupling agent and then reducing graphene oxide with hydrazine hydrate; the flame retardant additive is prepared by using phenylphosphoryl dichloride, eugenol, a flame retardant primary product and sodium as raw materials; the flame retardant primary product is prepared by reacting formaldehyde with p-hydroxyphenylethylamine and then further reacting with phosphorous acid. The nylon fabric prepared by the invention not only has a conductive function, but also maintains the mechanical properties of the fabric, and has excellent flame retardant performance.

Description

Technical Field

[0001] The invention belongs to the technical field of textile processing, and in particular relates to a production process of an antistatic nylon fabric. Background Art

[0002] In recent years, with the improvement of people's living standards, functional clothing fabrics have become more and more popular. The continuous development of new varieties of functional fabrics has been the goal pursued by practitioners in the industry. Most textiles produced by existing technologies are chemical fibers plus anti-static silk. Due to their extremely poor anti-static properties, they are very easy to cause harm to the human body during wearing and use. There are problems such as poor hand feel, poor drape, poor wrinkle resistance, and easy wear and tear of silk threads during use. In addition, static electricity will cause textile fabrics to absorb floating dust during use, and clothes will stick to the body, making people feel uncomfortable. Even when a person with static electricity touches a metal object, the human body is easily stimulated by static electricity.

[0003] Nylon fabrics have excellent properties such as high strength, wear resistance, and high resilience, and are widely used in outdoor parachutes, luggage fabrics, tents and other canopy materials. In addition, nylon fabrics are required to have certain environmental adaptability and be able to meet the requirements of windproof, waterproof, and UV resistance. Therefore, polyurethane is often used to coat nylon fabrics to improve their ability to resist harsh environments. However, both nylon fabrics and polyurethane coatings are flammable polymer materials, and droplets are generated during the combustion process, causing secondary fire damage. Therefore, it is of great significance to improve the flame retardant and droplet-proof properties of polyurethane-coated nylon fabrics. Summary of the invention

[0004] In order to solve the deficiencies mentioned in the above background technology, the purpose of the present invention is to provide a production process of antistatic nylon fabric, and use hybrid composite filler to modify the water-based polyurethane emulsion to perform functional finishing on the fabric. The soft and comfortable antistatic knitwear not only has conductive function, but also maintains the mechanical properties of the fabric, and at the same time has excellent flame retardant properties.

[0005] The purpose of the present invention can be achieved by the following technical solutions:

[0006] A production process for antistatic nylon fabrics comprises the following steps: scraping and coating a nylon base fabric with a modified waterborne polyurethane emulsion, and preparing the antistatic nylon fabric after pre-baking and baking;

[0007] The modified waterborne polyurethane emulsion comprises the following raw materials in parts by weight: 50-70 parts of waterborne polyurethane emulsion, 5-10 parts of hybrid composite filler, 0.2-0.7 parts of leveling agent, 0.1-0.5 parts of defoamer, 1-2 parts of thickener, and 10-20 parts of deionized water;

[0008] The hybrid composite filler is prepared by using γ-methacryloxypropyltrimethoxysilane to modify nano titanium dioxide and then react with modified graphene to undergo a hydrosilylation reaction, wherein the modified graphene is prepared by using a modified coupling agent and hydrazine hydrate to reduce graphene oxide to undergo a condensation reaction;

[0009] The modified coupling agent is prepared by reacting phenyltri(dimethylsiloxy)silane with a flame retardant additive and vinyltriethoxysilane to undergo a silylation reaction, wherein the flame retardant additive is prepared by reacting phenylphosphoryl dichloride with solution one and solution two, solution one is prepared by mixing eugenol, sodium and a solvent, solution two is prepared by reacting formaldehyde and p-hydroxyphenylethylamine with phosphorous acid to undergo a Schiff base reaction to prepare a flame retardant primary product, and then the flame retardant primary product, sodium and a solvent are mixed to obtain the obtained product.

[0010] Preferably, the leveling agent is sodium polyacrylate; the defoaming agent is one of fatty alcohol polyoxyethylene ether or alkylphenol polyoxyethylene ether; and the thickener is polyacrylamide.

[0011] Preferably, the preparation method of the modified waterborne polyurethane emulsion comprises the following steps: taking 5 to 10 parts of hybrid composite filler and 10 to 20 parts of deionized water and stirring and mixing them uniformly to obtain a premix, then adding 50 to 70 parts of waterborne polyurethane emulsion, 0.2 to 0.7 parts of leveling agent, 0.1 to 0.5 parts of defoaming agent and 1 to 2 parts of thickener to the premix and stirring them uniformly to prepare the modified waterborne polyurethane emulsion.

[0012] Preferably, the method for preparing the hybrid composite filler comprises the following steps:

[0013] A. Ultrasonic dispersion of graphene oxide in deionized water, heating to 85-95°C, adding ammonia water and hydrazine hydrate, stirring and reacting for 10-12 hours, filtering, washing and drying after the reaction is completed to obtain reduced graphene oxide, ultrasonic dispersion of reduced graphene oxide in xylene, nitrogen gas is introduced into the reaction, heating to 120-135°C, adding a modified coupling agent, stirring and reacting for 6-9 hours, centrifuging, washing and drying after the reaction is completed to prepare modified graphene;

[0014] B. Ultrasonic dispersion of nano-titanium dioxide in a mixed solution of deionized water and anhydrous ethanol, adjusting the pH value of the system to 3-4 with hydrochloric acid, heating to 80-90°C, adding γ-methacryloxypropyltrimethoxysilane dropwise, stirring and reacting for 4-5 hours, and filtering, washing and drying after the reaction is completed to prepare modified nano-titanium dioxide;

[0015] C. Take the modified graphene and modified nano-titanium dioxide and ultrasonically disperse them in xylene. Then, introduce nitrogen into the reaction. The temperature is raised to 95-110°C. Then, add the Custer catalyst and stir the reaction for 5-8 hours. After the reaction is completed, the hybrid composite filler is prepared by suction filtration, washing and drying.

[0016] Preferably, in step C, the mass ratio of modified graphene to modified nano-titanium dioxide is 1:5-10.

[0017] Preferably, the preparation method of the modified coupling agent in step A comprises the following steps:

[0018] A1. Sodium and tetrahydrofuran are placed in a reactor, and a mixed solution of eugenol and tetrahydrofuran is added thereto. The mixture is stirred in a nitrogen atmosphere for 20 to 24 hours to obtain a solution 1.

[0019] A2, taking phosphorous acid and formaldehyde in a reactor, raising the temperature to 105-115° C., adding a mixed solution of p-hydroxyphenylethylamine and anhydrous ethanol, stirring at a constant temperature for 3-5 hours, and after the reaction is completed, rotary evaporation, washing, and drying are performed to prepare a flame retardant primary product;

[0020] A3, taking the flame retardant initial product, sodium and tetrahydrofuran into a reactor, stirring and reacting for 20-24 hours in a nitrogen atmosphere to obtain a solution 2;

[0021] A4, take phenylphosphoryl dichloride and tetrahydrofuran in a reactor, add solution 1 and solution 2, place at 55-70°C and stir to react for 20-24 hours, filter, wash and dry after the reaction to prepare a flame retardant additive;

[0022] A5. Phenyl tri(dimethylsiloxy)silane, flame retardant additive and vinyl triethoxysilane are placed in a reactor, toluene solvent is added, nitrogen is passed through the reaction, the temperature is raised to 75-90°C, Wilkinson catalyst is added, the reaction is stirred at a constant temperature for 5-8 hours, and after the reaction is completed, the solvent is removed by rotary evaporation to prepare a modified coupling agent.

[0023] Preferably, in step A2, the molar ratio of phosphorous acid, formaldehyde and hydroxyphenylethylamine is 1-1.2:1-1.2:1.

[0024] Preferably, the molar ratio of phenylphosphoryl dichloride in step A4, eugenol in solution one and the flame retardant primary product in solution two is 1:1-1.4:1-1.4.

[0025] Preferably, in step A5, the molar ratio of phenyltri(dimethylsiloxy)silane, the flame retardant additive and vinyltriethoxysilane is 1:1-1.2:1-1.2.

[0026] Preferably, the aqueous polyurethane emulsion comprises the following components in parts by weight: 25-35 parts of polytetramethylene glycol, 3-6 parts of 2,2-dihydroxymethylbutyric acid, 17-22 parts of isophorone diisocyanate, 2-7 parts of triethylamine, 1-2 parts of ethylenediamine, 0.01-0.05 parts of dibutyltin dilaurate, and 60-80 parts of deionized water;

[0027] The preparation method comprises the following steps: weighing various raw materials by weight, taking polytetrahydrofuran diol, 2,2-dihydroxymethylbutyric acid, isophorone diisocyanate and dibutyltin dilaurate in a reactor, heating to 75-85°C and stirring for reaction for 2-3 hours, then cooling to 40-50°C, adding triethylamine for reaction for 25-40 minutes, adding deionized water after the system is cooled to room temperature, emulsifying at a rotation speed of 2000-3000 r / min for 0.5-1 hour, finally adding ethylenediamine for chain extension reaction, continuing stirring for 5-10 minutes, and rotary evaporating to obtain waterborne polyurethane emulsion.

[0028] Beneficial effects of the present invention:

[0029] The invention reduces graphene oxide by hydrazine hydrate, and then uses the silicon hydroxyl group in the modified coupling agent structure to undergo a condensation reaction with the hydroxyl group in the reduced graphene oxide structure to prepare the modified graphene. Meanwhile, the invention uses gamma-methacryloxypropyltrimethoxysilane to modify nano titanium dioxide, so as to graft double bonds on the surface of the nano titanium dioxide, and react the double bonds with the silicon-hydrogen bonds in the modified graphene structure to undergo a silicon-hydrogen addition reaction to prepare a hybrid composite filler of graphene-loaded nano titanium dioxide. The composite conductive network formed by the graphene and the nano titanium dioxide is beneficial to improving the antistatic performance of the fabric, and the nano titanium dioxide, as an inorganic ultraviolet shielding agent, has antibacterial, mildew-proof and ultraviolet-resistant effects. The modified coupling agent uses formaldehyde and p-hydroxyphenylethylamine to undergo a Schiff base reaction to generate an N=CH group, which further undergoes an addition reaction with the PH bond in the phosphorous acid structure to prepare a flame retardant primary product containing nitrogen and phosphorus elements, and then eugenol and the phenolic hydroxyl group in the structure of the flame retardant primary product undergo a replacement reaction with sodium to obtain solution one and solution two, and then the -ONa groups in the structures of solution one and solution two react with the chlorine atoms at both ends of phenylphosphoryl dichloride to prepare a flame retardant additive containing a double bond structure, and then phenyltri(dimethylsiloxy)silane undergoes a silylation reaction with the flame retardant additive and vinyltriethoxysilane at the same time to prepare a modified coupling agent with one ungrafted silylation bond remaining in the structure. The invention utilizes chemical reaction to graft the modified coupling agent with the reduced graphene oxide, thereby combining the two through a strong chemical bond, which is beneficial to the uniform dispersion of the graphene, and then forms a hybrid conductive path with the modified nano titanium dioxide, and uses the prepared hybrid composite filler to modify the water-based polyurethane emulsion to perform functional finishing on the fabric. The soft and comfortable antistatic knitted fabric not only has the conductive function, but also maintains the mechanical properties of the fabric, and at the same time has excellent flame retardant performance. DETAILED DESCRIPTION

[0030] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0031] Example 1 A method for preparing a modified coupling agent comprises the following steps:

[0032] A1. Take 3 g of sodium and 100 mL of tetrahydrofuran in a reactor, add a mixed solution of 21.3 g of eugenol and 20 mL of tetrahydrofuran, and stir the mixture in a nitrogen atmosphere for 24 h to obtain solution 1.

[0033] A2, take 4.9g of phosphorous acid and 1.8g of formaldehyde in a reactor, heat to 110°C, add a mixed solution of 8.2g of p-hydroxyphenylethylamine and 50mL of anhydrous ethanol, stir and react at constant temperature for 4h, and after the reaction is completed, rotary evaporate, wash and dry to prepare a flame retardant primary product;

[0034] A3, 27.7 g of the flame retardant primary product (Mr = 231.2), 4.2 g of sodium and 120 mL of tetrahydrofuran were placed in a reactor, and stirred for reaction for 24 h in a nitrogen atmosphere to obtain solution 2;

[0035] A4, take 19.5g of phenylphosphoryl dichloride and 30mL of tetrahydrofuran in a reactor, add solution 1 and solution 2, place at 65°C and stir to react for 24h, filter, wash and dry after the reaction to prepare a flame retardant additive;

[0036] A5. Take 6.6g of phenyltri(dimethylsiloxy)silane, 10.4g of flame retardant additive (Mr=517.4) and 3.9g of vinyltriethoxysilane in a reactor, add 70mL of toluene solvent, pass nitrogen through the reaction, raise the temperature to 85°C, add 5mg of Wilkinson catalyst, stir and react at constant temperature for 8h, and after the reaction is completed, remove the solvent by rotary evaporation to prepare a modified coupling agent.

[0037] Example 2 A method for preparing a hybrid composite filler comprises the following steps:

[0038] A. Take 1g of graphene oxide and ultrasonically disperse it in 120mL of deionized water, heat it to 95°C, add 20g of ammonia water and 20g of hydrazine hydrate and stir to react for 12h. After the reaction is completed, filter, wash and dry to obtain reduced graphene oxide. Take 1g of reduced graphene oxide and ultrasonically disperse it in 120mL of xylene. Nitrogen is introduced into the reaction, heat it to 135°C, add 1.2g of the modified coupling agent prepared in Example 1 and stir to react for 8h. After the reaction is completed, centrifuge, wash and dry to prepare modified graphene.

[0039] B. Take 5g of nano-titanium dioxide and ultrasonically disperse it in a mixed solution of 10mL of deionized water and 90mL of anhydrous ethanol. Use hydrochloric acid to adjust the pH value of the system to 4. Heat it to 85°C, add 0.5g of γ-methacryloxypropyltrimethoxysilane and stir to react for 4h. After the reaction is completed, filter, wash and dry to prepare modified nano-titanium dioxide.

[0040] C. Take 1g of modified graphene and 5g of modified nano-titanium dioxide and ultrasonically disperse them in 200mL of xylene. Pass nitrogen into the reaction, raise the temperature to 105°C, add 0.2g of Custer catalyst, stir and react for 7h. After the reaction is completed, filter, wash and dry to prepare a hybrid composite filler.

[0041] Example 3 A water-based polyurethane emulsion comprises the following components in parts by weight: 30 parts of polytetramethylene glycol, 5 parts of 2,2-dihydroxymethylbutyric acid, 17 parts of isophorone diisocyanate, 5 parts of triethylamine, 2 parts of ethylenediamine, 0.03 parts of dibutyltin dilaurate, and 72 parts of deionized water;

[0042] The preparation method comprises the following steps: weighing various raw materials by weight, taking polytetrahydrofuran diol, 2,2-dihydroxymethylbutyric acid, isophorone diisocyanate and dibutyltin dilaurate in a reactor, heating to 80°C and stirring for reaction for 3 hours, then cooling to 45°C, adding triethylamine for reaction for 30 minutes, adding deionized water after the system is cooled to room temperature, emulsifying at a speed of 3000 r / min for 0.5 hours, finally adding ethylenediamine for chain extension reaction, continuing stirring for 10 minutes, and rotary evaporating to obtain an aqueous polyurethane emulsion.

[0043] Example 4 A modified waterborne polyurethane emulsion comprises the following raw materials in parts by weight: 55 parts of the waterborne polyurethane emulsion prepared in Example 3, 5 parts of the hybrid composite filler prepared in Example 2, 0.2 parts of sodium polyacrylate as a leveling agent, 0.1 parts of fatty alcohol polyoxyethylene ether as a defoaming agent, 1 part of polyacrylamide as a thickener, and 12 parts of deionized water;

[0044] The preparation method of the modified waterborne polyurethane emulsion comprises the following steps: weighing each raw material according to the above weight portion, taking a hybrid composite filler and deionized water and stirring and mixing them uniformly to obtain a premix, and then adding waterborne polyurethane emulsion, a leveling agent, a defoamer and a thickener to the premix and stirring them uniformly to prepare a modified waterborne polyurethane emulsion.

[0045] A production process for antistatic nylon fabrics, comprising the following steps: using a modified waterborne polyurethane emulsion to scrape a nylon 6 base fabric, pre-baking at 110°C for 3 minutes, and baking at 150°C for 3 minutes to obtain the antistatic nylon fabric, and controlling the coating mass increase to 100g / m 2 .

[0046] Example 5 A modified waterborne polyurethane emulsion comprises the following raw materials in parts by weight: 62 parts of the waterborne polyurethane emulsion prepared in Example 3, 7 parts of the hybrid composite filler prepared in Example 2, 0.4 parts of sodium polyacrylate as a leveling agent, 0.2 parts of fatty alcohol polyoxyethylene ether as a defoaming agent, 1.5 parts of polyacrylamide as a thickener, and 16 parts of deionized water;

[0047] The preparation method of the modified aqueous polyurethane emulsion and the production process of the antistatic nylon fabric are the same as those in Example 4.

[0048] Example 6 A modified waterborne polyurethane emulsion comprises the following raw materials in parts by weight: 67 parts of the waterborne polyurethane emulsion prepared in Example 3, 9 parts of the hybrid composite filler prepared in Example 2, 0.6 parts of sodium polyacrylate as a leveling agent, 0.4 parts of fatty alcohol polyoxyethylene ether as a defoaming agent, 2 parts of polyacrylamide as a thickener, and 18 parts of deionized water;

[0049] The preparation method of the modified aqueous polyurethane emulsion and the production process of the antistatic nylon fabric are the same as those in Example 4.

[0050] Comparative Example 1 A method for preparing a hybrid composite filler comprises the following steps:

[0051] A. Take 1g of graphene oxide and ultrasonically disperse it in 120mL of deionized water, heat it to 95°C, add 20g of ammonia water and 20g of hydrazine hydrate and stir to react for 12h. After the reaction is completed, filter, wash and dry to obtain reduced graphene oxide. Take 1g of reduced graphene oxide and ultrasonically disperse it in 120mL of xylene. Nitrogen is introduced into the reaction, heat it to 135°C, add 1.2g of modified coupling agent and stir to react for 8h. After the reaction is completed, centrifuge, wash and dry to prepare modified graphene.

[0052] B. Take 5g of nano-titanium dioxide and ultrasonically disperse it in a mixed solution of 10mL of deionized water and 90mL of anhydrous ethanol. Use hydrochloric acid to adjust the pH value of the system to 4. Heat it to 85°C, add 0.5g of γ-methacryloxypropyltrimethoxysilane and stir to react for 4h. After the reaction is completed, filter, wash and dry to prepare modified nano-titanium dioxide.

[0053] C. 1 g of modified graphene and 5 g of modified nano-titanium dioxide were ultrasonically dispersed in 200 mL of xylene, nitrogen was introduced into the reaction, the temperature was raised to 105° C., 0.2 g of Custer catalyst was added, and the reaction was stirred for 7 h. After the reaction was completed, the hybrid composite filler was prepared by suction filtration, washing and drying;

[0054] Wherein, the preparation method of the modified coupling agent comprises the following steps:

[0055] A1. Take 3 g of sodium and 100 mL of tetrahydrofuran in a reactor, add a mixed solution of 21.3 g of eugenol and 20 mL of tetrahydrofuran, and stir the mixture in a nitrogen atmosphere for 24 h to obtain solution 1.

[0056] A2, take 19.5g of phenylphosphoryl dichloride and 30mL of tetrahydrofuran in a reactor, add solution 1, place at 65°C and stir to react for 24h, filter, wash and dry after the reaction to prepare a flame retardant additive;

[0057] A3. Take 6.6g of phenyltri(dimethylsiloxy)silane, 6.5g of flame retardant additive and 3.8g of vinyltriethoxysilane in a reactor, add 70mL of toluene solvent, pass nitrogen through the reaction, raise the temperature to 85°C, add 5mg of Wilkinson catalyst, stir and react at constant temperature for 8h, and after the reaction is completed, remove the solvent by rotary evaporation to prepare a modified coupling agent.

[0058] Comparative Example 2 A method for preparing modified graphene comprises the following steps:

[0059] 1 g of graphene oxide was ultrasonically dispersed in 120 mL of deionized water, the temperature was raised to 95 ° C, 20 g of ammonia water and 20 g of hydrazine hydrate were added, and the mixture was stirred for 12 h. After the reaction was completed, the mixture was filtered, washed, and dried to obtain reduced graphene oxide. 1 g of reduced graphene oxide was ultrasonically dispersed in 120 mL of xylene, nitrogen was introduced into the reaction, the temperature was raised to 135 ° C, 1.2 g of the modified coupling agent prepared in Example 1 was added, and the mixture was stirred for 8 h. After the reaction was completed, the mixture was centrifuged, washed, and dried to obtain modified graphene.

[0060] Comparative Example 3 A modified waterborne polyurethane emulsion comprises the following raw materials in parts by weight: 67 parts of the waterborne polyurethane emulsion prepared in Example 3, 9 parts of the hybrid composite filler prepared in Comparative Example 1, 0.6 parts of sodium polyacrylate as a leveling agent, 0.4 parts of fatty alcohol polyoxyethylene ether as a defoaming agent, 2 parts of polyacrylamide as a thickener, and 18 parts of deionized water;

[0061] The preparation method of the modified aqueous polyurethane emulsion and the production process of the antistatic nylon fabric are the same as those in Example 4.

[0062] Comparative Example 4 A modified waterborne polyurethane emulsion comprises the following raw materials in parts by weight: 67 parts of the waterborne polyurethane emulsion prepared in Example 3, 9 parts of the modified graphene prepared in Comparative Example 2, 0.6 parts of sodium polyacrylate as a leveling agent, 0.4 parts of fatty alcohol polyoxyethylene ether as a defoaming agent, 2 parts of polyacrylamide as a thickener, and 18 parts of deionized water;

[0063] The preparation method of the modified aqueous polyurethane emulsion and the production process of the antistatic nylon fabric are the same as those in Example 4.

[0064] Comparative Example 5 A modified waterborne polyurethane emulsion comprises the following raw materials in parts by weight: 67 parts of the waterborne polyurethane emulsion prepared in Example 3, 1.5 parts of graphene oxide, 7.5 parts of nano-titanium dioxide, 0.6 parts of sodium polyacrylate as a leveling agent, 0.4 parts of fatty alcohol polyoxyethylene ether as a defoaming agent, 2 parts of polyacrylamide as a thickener, and 18 parts of deionized water;

[0065] The preparation method of the modified aqueous polyurethane emulsion and the production process of the antistatic nylon fabric are the same as those in Example 4.

[0066] Performance Testing

[0067] The nylon fabrics prepared in Examples 4-6 and Comparative Examples 3-5 were tested for performance:

[0068] (1) Bursting strength test: The test was carried out according to GB / T 19976-2005 “Determination of bursting strength of textiles - Steel ball method”. The data results are shown in Table 1.

[0069] (2) Surface resistance and induced voltage half-life test: The surface resistivity of nylon fabric was tested using the LFY-406 fabric surface resistivity tester; the induced voltage half-life time of nylon fabric was tested using the YG401 fabric induction static voltage tester. The data results are shown in Table 1.

[0070] (3) Washability test: The washability of the fabric was tested using the GB / T 8629-2001 5A standard method. The less the antistatic property decreases after washing, the better the antistatic property. The data results are shown in Table 1.

[0071] (4) Flame retardant performance test: The flame retardant performance of nylon fabric was tested using a vertical combustion tester in accordance with GB / T 5455-2014 “Determination of vertical direction damage length, smoldering and afterflaming time of textiles for combustion performance”; the limiting oxygen index of nylon fabric was tested using an FTT0080 oxygen index meter in accordance with GB / T 5454-1997 “Textile combustion performance test oxygen index method”. The data results are shown in Table 1.

[0072] Table 1 Test results of sample performance

[0073]

[0074] It can be seen from the data in Table 1 that the nylon fabrics prepared in Examples 4-6 of the present invention have high bursting strength, small surface resistivity and induced voltage half-life. After 20 times of washing, the surface resistivity and half-life both increase, but still remain within a small range, and have good water washing resistance. At the same time, they have excellent flame retardant properties. Among them, the modified coupling agent in the hybrid composite filler added in Comparative Example 3 does not contain the flame retardant primary product component, and its measured flame retardant performance is lower than that of Examples 4-6, indicating that the flame retardant primary product containing nitrogen and phosphorus elements can improve the flame retardant performance of the fabric to a certain extent. In Comparative Example 4, modified graphene is added, and the modified nano titanium dioxide component is not grafted. The measured bursting strength is lower than that of Examples 4-6, and the surface resistivity and induced voltage half-life time are increased compared with Examples 4-6, indicating that the addition of modified nano titanium dioxide can improve the mechanical properties of the fabric, and the addition of modified nano titanium dioxide can form a hybrid conductive path with modified graphene, which is beneficial to improving the antistatic performance of the fabric. In Comparative Example 5, graphene oxide and nano titanium dioxide are simply mixed, and the measured bursting strength, antistatic and flame retardant properties are lower than those of Examples 4-6. The reason is that the agglomeration phenomenon of the inorganic filler causes its mechanical properties to decrease, and the surface resistivity and induced voltage half-life time increase due to the failure to form a composite conductive network. In addition, the flame retardant performance is significantly reduced due to the lack of introduction of silicon, nitrogen and phosphorus elements.

[0075] In the description of this specification, the description with reference to the terms "one embodiment", "example", "specific example", etc. means that the specific features, structures, materials or characteristics described in conjunction with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic representation of the above terms does not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described can be combined in any one or more embodiments or examples in a suitable manner.

[0076] The above shows and describes the basic principles, main features and advantages of the present invention. Those skilled in the art should understand that the present invention is not limited to the above embodiments, and the above embodiments and descriptions are only for explaining the principles of the present invention. Without departing from the spirit and scope of the present invention, the present invention may have various changes and improvements, and these changes and improvements all fall within the scope of the present invention to be protected.

Claims

1. A production process for antistatic nylon fabric, characterized in that: The following steps are involved: The modified waterborne polyurethane emulsion is used to scrape the nylon base fabric, and the antistatic nylon fabric is obtained after pre-baking and baking. The modified waterborne polyurethane emulsion comprises the following raw materials in parts by weight: 50-70 parts of waterborne polyurethane emulsion, 5-10 parts of hybrid composite filler, 0.2-0.7 parts of leveling agent, 0.1-0.5 parts of defoamer, 1-2 parts of thickener, and 10-20 parts of deionized water; The preparation method of the hybrid composite filler comprises the following steps: A. Ultrasonic dispersion of graphene oxide in deionized water, heating to 85-95°C, adding ammonia water and hydrazine hydrate, stirring and reacting for 10-12 hours, filtering, washing and drying after the reaction is completed to obtain reduced graphene oxide, ultrasonic dispersion of reduced graphene oxide in xylene, nitrogen gas is introduced into the reaction, heating to 120-135°C, adding a modified coupling agent, stirring and reacting for 6-9 hours, centrifuging, washing and drying after the reaction is completed to prepare modified graphene; B. Ultrasonic dispersion of nano-titanium dioxide in a mixed solution of deionized water and anhydrous ethanol, adjusting the pH value of the system to 3-4 with hydrochloric acid, heating to 80-90°C, adding γ-methacryloxypropyltrimethoxysilane dropwise, stirring and reacting for 4-5 hours, and filtering, washing and drying after the reaction is completed to prepare modified nano-titanium dioxide; C. Take the modified graphene and modified nano-titanium dioxide and ultrasonically disperse them in xylene, introduce nitrogen into the reaction, raise the temperature to 95-110°C, add the Custer catalyst, stir and react for 5-8h, and after the reaction is completed, filter, wash and dry to prepare a hybrid composite filler; The modified coupling agent is prepared by reacting phenyltri(dimethylsiloxy)silane with a flame retardant additive and vinyltriethoxysilane to undergo a silylation reaction, wherein the flame retardant additive is prepared by reacting phenylphosphoryl dichloride with solution one and solution two, solution one is prepared by mixing eugenol, sodium and a solvent, solution two is prepared by reacting formaldehyde and p-hydroxyphenylethylamine with phosphorous acid to undergo a Schiff base reaction to prepare a flame retardant primary product, and then the flame retardant primary product, sodium and a solvent are mixed to obtain the obtained product.

2. The production process of the antistatic nylon fabric according to claim 1, characterized in that: The leveling agent is sodium polyacrylate; the defoaming agent is one of fatty alcohol polyoxyethylene ether or alkylphenol polyoxyethylene ether; and the thickener is polyacrylamide.

3. The production process of the antistatic nylon fabric according to claim 1, characterized in that: The preparation method of the modified waterborne polyurethane emulsion comprises the following steps: taking 5-10 parts of a hybrid composite filler and 10-20 parts of deionized water, stirring and mixing them uniformly to obtain a premix, and then adding 50-70 parts of waterborne polyurethane emulsion, 0.2-0.7 parts of a leveling agent, 0.1-0.5 parts of a defoaming agent and 1-2 parts of a thickener into the premix, stirring them uniformly to prepare the modified waterborne polyurethane emulsion.

4. The production process of the antistatic nylon fabric according to claim 1, characterized in that: In the step C, the mass ratio of the modified graphene to the modified nano-titanium dioxide is 1:5-10.

5. The production process of the antistatic nylon fabric according to claim 1, characterized in that: The preparation method of the modified coupling agent in step A comprises the following steps: A1. Sodium and tetrahydrofuran are placed in a reactor, and a mixed solution of eugenol and tetrahydrofuran is added thereto. The mixture is stirred in a nitrogen atmosphere for 20 to 24 hours to obtain a solution 1. A2, taking phosphorous acid and formaldehyde in a reactor, raising the temperature to 105-115° C., adding a mixed solution of p-hydroxyphenylethylamine and anhydrous ethanol, stirring at a constant temperature for 3-5 hours, and after the reaction is completed, rotary evaporation, washing, and drying are performed to prepare a flame retardant primary product; A3, taking the flame retardant initial product, sodium and tetrahydrofuran into a reactor, stirring and reacting for 20-24 hours in a nitrogen atmosphere to obtain a solution 2; A4, take phenylphosphoryl dichloride and tetrahydrofuran in a reactor, add solution 1 and solution 2, place at 55-70°C and stir to react for 20-24 hours, filter, wash and dry after the reaction to prepare a flame retardant additive; A5. Phenyl tri(dimethylsiloxy)silane, flame retardant additive and vinyl triethoxysilane are placed in a reactor, toluene solvent is added, nitrogen is passed through the reaction, the temperature is raised to 75-90°C, Wilkinson catalyst is added, the reaction is stirred at a constant temperature for 5-8 hours, and after the reaction is completed, the solvent is removed by rotary evaporation to prepare a modified coupling agent.

6. The production process of the antistatic nylon fabric according to claim 5, characterized in that: In the step A2, the molar ratio of phosphorous acid, formaldehyde and hydroxyphenylethylamine is 1-1.2:1-1.2:

1.

7. The production process of the antistatic nylon fabric according to claim 5, characterized in that: The molar ratio of phenylphosphoryl dichloride in step A4, eugenol in solution one and the flame retardant primary product in solution two is 1:1-1.4:1-1.

4.

8. The production process of the antistatic nylon fabric according to claim 5, characterized in that: In the step A5, the molar ratio of phenyltri(dimethylsiloxy)silane, the flame retardant additive and vinyltriethoxysilane is 1:1-1.2:1-1.

2.

9. The production process of the antistatic nylon fabric according to claim 1, characterized in that: The aqueous polyurethane emulsion comprises the following components in parts by weight: 25-35 parts of polytetramethylene glycol, 3-6 parts of 2,2-dihydroxymethylbutyric acid, 17-22 parts of isophorone diisocyanate, 2-7 parts of triethylamine, 1-2 parts of ethylenediamine, 0.01-0.05 parts of dibutyltin dilaurate, and 60-80 parts of deionized water; The preparation method comprises the following steps: weighing various raw materials by weight, taking polytetrahydrofuran diol, 2,2-dihydroxymethylbutyric acid, isophorone diisocyanate and dibutyltin dilaurate in a reactor, heating to 75-85°C and stirring for reaction for 2-3 hours, then cooling to 40-50°C, adding triethylamine for reaction for 25-40 minutes, adding deionized water after the system is cooled to room temperature, emulsifying at a rotation speed of 2000-3000 r / min for 0.5-1 hour, finally adding ethylenediamine for chain extension reaction, continuing stirring for 5-10 minutes, and rotary evaporating to obtain waterborne polyurethane emulsion.

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