Highly elastic textile fiber and method for making same

Abstract

The application relates to the technical field of functional textile fibers, and discloses a high-elasticity textile fiber and a preparation method thereof, which comprises the following preparation steps: mixing isocyanate, polyhydric alcohol and an organic solvent, heating, adding a catalyst, stirring and reacting, then adding a chain extender and a composite conductive additive, stirring and reacting, obtaining a polyurethane matrix; after the polyurethane matrix is washed, dried and sliced, the polyurethane matrix is extruded and granulated, and then is subjected to melt spinning and winding, so that the high-elasticity textile fiber is obtained. In the composite conductive additive, the tubular structure with porous silicon dioxide as a core material and graphene-polyphenylamine as a shell has good tensile resistance, the liquid metal is prevented from being easily separated and precipitated under high tension, so that the conductive performance is prevented from being reduced, and the crosslinked network structure formed on the surface of the activated conductive filler can enhance the impact resistance of the fiber.

Description

Technical Field

[0001] This invention relates to the field of functional textile fiber technology, specifically to a high-elasticity textile fiber and its preparation method. Background Technology

[0002] High-elasticity textile fibers play an irreplaceable role in clothing comfort, warmth, and other aspects due to their ability to provide a good tactile feel. Therefore, they hold a stable position in the textile industry, and giving textile fabrics a certain degree of elasticity has become an inevitable development trend in apparel textiles. However, high-elasticity textile fibers themselves have high electrical resistance, making them highly susceptible to static electricity due to friction, which is difficult to eliminate. This brings many problems to the manufacturing and use of synthetic fibers and their products. For example, static electricity in clothing can accumulate on the fiber surface due to friction, causing fires, explosions, electric shocks, and electrostatic induction disasters. The prevention and control of static electricity has attracted widespread attention.

[0003] Using fiber-forming polymers as the matrix and adding inorganic conductive fillers in a composite manner, high-elasticity textile fibers are endowed with excellent electrical conductivity through composite spinning technology, while also possessing the excellent processing properties of ordinary synthetic fibers, thus becoming functional fibers with spinnability. However, inorganic conductive fillers are prone to agglomeration and uneven dispersion in high-elasticity textile fibers, affecting their electrical conductivity. Furthermore, under high tensile conditions, the conductivity of high-elasticity textile fibers drops sharply due to the separation of inorganic conductive fillers. Summary of the Invention

[0004] This invention provides a highly elastic textile fiber and its preparation method, which solves the problem of easy agglomeration and uneven dispersion of inorganic conductive fillers in highly elastic textile fibers.

[0005] The technical solution of the present invention:

[0006] A method for preparing a highly elastic textile fiber includes the following preparation steps:

[0007] S1. Mix isocyanate, polyol and organic solvent, heat to 50-60℃, add catalyst, stir and react for 2-4 hours, then add chain extender and composite conductive additive, stir and react at 50-100℃ for 1-2 hours to obtain polyurethane matrix;

[0008] S2. After washing, drying and slicing the polyurethane matrix, elastomer chips are obtained; after extrusion and granulation, the elastomer chips are melt-spun and wound to obtain highly elastic textile fibers.

[0009] The composite conductive additive is obtained by surface treatment of conductive fillers with mixed acids, followed by reaction with polystyrene-glycidyl methacrylate and organosilicon.

[0010] The conductive filler is obtained by mixing porous silica with liquid metal, and then reacting it with aminosilane, aniline, and graphene oxide nanosheets.

[0011] Furthermore, the mass ratio of isocyanate, polyol, organic solvent, catalyst, chain extender and composite conductive additive is (60-80):(70-80):(100-120):(0.3-0.5):(20-30):(8-10).

[0012] Furthermore, a twin-screw extruder is used for extrusion, with an extruder temperature of 170-210℃.

[0013] Furthermore, the melt spinning process specifically includes: spinning temperature of 240-260℃, spinning speed of 600-630m / min, drawing temperature of 75-85℃, heat setting temperature of 130-150℃, and drawing ratio of 3.5-4.5 times.

[0014] Furthermore, the isocyanate is selected from one of toluene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, and terephthalimethylene diisocyanate.

[0015] Furthermore, the polyol is selected from one of polyethylene glycol, polypropylene glycol, and polycaprolactone diol.

[0016] Furthermore, the chain extender is selected from one of butanediol, 2,2-dimethylolpropionic acid, 1,6-hexanediol, and trimethylolpropane.

[0017] Furthermore, the catalyst is dibutyltin dilaurate.

[0018] Furthermore, the organic solvent is N,N-dimethylformamide.

[0019] Furthermore, the composite conductive additive is prepared by the following steps:

[0020] A1. Add porous silica to ethanol, stir until homogeneous, add liquid metal, heat to 60-70℃, stir and mix at a rate of 1000-1500 r / min for 20-30 min, continue to heat to 80-90℃, stir until ethanol evaporates, remove the reactant, wash and dry to obtain porous silica loaded with liquid metal.

[0021] A2. Mix porous silica loaded with liquid metal, ethanol and deionized water, stir until homogeneous, add aminosilane, stir and react at 100-110℃ for 30-40 min, cool to room temperature, filter, wash and dry to obtain aminated porous silica loaded with liquid metal.

[0022] A3. Add aniline, graphene oxide nanosheets and acetic acid solution to deionized water, stir evenly, add ammonium persulfate and porous silica loaded with aminated liquid metal, stir and react at 2-5℃ for 1-3h, filter, wash and dry to obtain conductive filler;

[0023] A4. Mix concentrated sulfuric acid solution and concentrated nitric acid solution, stir evenly to obtain mixed acid, add conductive filler to mixed acid, stir and mix at 80-90℃ for 1-2 hours, cool to room temperature, filter, wash and dry to obtain activated conductive filler;

[0024] A5. Styrene and glycidyl methacrylate were added to deionized water and stirred until homogeneous. Benzoyl peroxide was added, the temperature was raised to 80-100℃, and the mixture was stirred for 4-6 hours. After filtration, washing, and drying, styrene-glycidyl methacrylate polymer was obtained.

[0025] A6. Add the styrene-glycidyl methacrylate polymer to deionized water, stir until homogeneous, add hydrochloric acid and activated conductive filler, stir and react at 70-90℃ for 10-20 min, add organosilicon, continue stirring and reacting for 10-20 min, filter, wash and dry to obtain the composite conductive additive.

[0026] Furthermore, in the above-mentioned A1 reaction process, porous silica has a large specific surface area and porous structure, and has excellent adsorption performance, which can adsorb liquid metal into the pores of porous silica, thus obtaining porous silica loaded with liquid metal.

[0027] Furthermore, during the A2 reaction described above, the silanol groups generated by the hydrolysis of aminosilane can chemically bond with the hydroxyl groups on the surface of porous silica loaded with liquid metal, thereby grafting aminosilane onto the surface of porous silica loaded with liquid metal to obtain aminated porous silica loaded with liquid metal.

[0028] Furthermore, in the A3 reaction process described above, using graphene oxide nanosheets as templates, under the action of ammonium persulfate initiator, aniline monomers react with amino groups in porous silica loaded with aminated liquid metal, forming branched and trunk-shaped polyaniline on the graphene oxide nanosheets. As polymerization continues, the branched and trunk-shaped polyaniline forms, under the action of porous silica, causes the graphene oxide nanosheets to self-roll into a tubular structure with porous silica loaded with liquid metal as the core material and graphene-polyaniline as the shell, thus obtaining a conductive filler.

[0029] Furthermore, during the A4 reaction process described above, the tubular conductive filler is surface functionalized in a mixed acid formed by concentrated sulfuric acid and concentrated nitric acid, introducing oxygen-containing functional groups carboxyl and hydroxyl groups onto the surface of the tubular conductive filler to improve its surface activity.

[0030] Furthermore, in the A5 reaction process described above, styrene and glycidyl methacrylate undergo double bond polymerization under the action of the initiator benzoyl peroxide to obtain a styrene-glycidyl methacrylate polymer.

[0031] Furthermore, during the A6 reaction process described above, the epoxy groups of the styrene-glycidyl methacrylate polymer can react with the carboxyl and hydroxyl groups on the surface of the activated conductive filler, allowing the styrene-glycidyl methacrylate polymer to be grafted onto the surface of the activated conductive filler. In addition, the silanol groups contained in the organosilicon can also be chemically bonded to the hydroxyl groups generated by ring opening on the styrene-glycidyl methacrylate polymer molecular chain, thereby forming a cross-linked network structure of the styrene-glycidyl methacrylate polymer and obtaining a composite conductive additive.

[0032] Further, in step A1, the ratio of the porous silica, ethanol and liquid metal is (5-6)g:(15-25)mL:(2.2-2.6)g.

[0033] Further, in step A2, the ratio of the porous silica loaded with liquid metal, ethanol, deionized water and aminosilane is (2-3)g:(20-30)mL:(8-12)mL:(1-2)g.

[0034] Further, in step A3, the ratio of the amount of aniline, graphene oxide nanosheets, acetic acid solution, deionized water, ammonium persulfate and ammoniated liquid metal-supported porous silica is (2-4)g:(6-8)g:(2-4)mL:(90-110)mL:(0.1-0.3)g:(4.6-5)g.

[0035] Further, in step A4, the volume ratio of the concentrated sulfuric acid solution to the concentrated nitric acid solution is (15-25):(35-45).

[0036] Further, in step A4, the ratio of the conductive filler to the mixed acid is (4-5) g:(15-25) mL.

[0037] Further, in step A5, the ratio of styrene, glycidyl methacrylate, deionized water and benzoyl peroxide is (4.2-4.4)g:(3-4)g:(85-95)mL:(0.4-0.6)g.

[0038] Further, in step A6, the ratio of the amount of styrene-glycidyl methacrylate polymer, deionized water, hydrochloric acid, activated conductive filler and organosilicon is (3-3.6)g:(45-55)mL:(4-6)mL:(5.5-5.9)g:(2.2-2.4)g.

[0039] Furthermore, the liquid metal is selected from gallium indium alloy or gallium indium tin alloy.

[0040] Furthermore, the aminosilane is γ-aminopropyltriethoxysilane.

[0041] Furthermore, the graphene oxide nanosheets are approximately 30-40 nm thick and have a sheet diameter of 8-10 μm.

[0042] Furthermore, the organosilicon is a dihydroxy-terminated polydimethylsiloxane.

[0043] The present invention has the following beneficial effects:

[0044] (1) In the technical solution of the present invention, liquid metal is adsorbed into the pores of porous silica, and the liquid metal forms a conductive path in the porous silica, giving the silica excellent conductivity. Furthermore, the porous silica, as a carrier, can carry a large amount of liquid metal and avoid the migration and precipitation of liquid metal. The aminosilane grafted on the surface of the porous silica loaded with liquid metal is beneficial for graphene and polyaniline to curl on the surface of the porous silica.

[0045] (2) In the technical solution of the present invention, graphene oxide nanosheets are used as templates. Ammoniated porous silica loaded with liquid metal and aniline monomers are polymerized on graphene oxide nanosheets, so that graphene oxide nanosheets are rolled up to form a tubular structure with porous silica loaded with liquid metal as the core material and graphene-polyaniline as the shell. On the one hand, the formed tubular structure has good tensile strength, avoiding the easy separation and precipitation of liquid metal under high tensile conditions of high elastic textile fibers, which leads to a decrease in conductivity. On the other hand, graphene oxide nanosheets and polyaniline have high carrier mobility, which can form a conductive path with liquid metal in the tubular structure, and have good conductivity, further improving the conductivity of high elastic textile fibers.

[0046] (3) In the technical solution of the present invention, the tubular conductive filler is surface functionalized in a mixed acid of concentrated sulfuric acid and concentrated nitric acid. Oxygen-containing functional groups carboxyl and hydroxyl groups are introduced on the surface of the tubular conductive filler to improve the surface activity of the tubular conductive filler. The cross-linked network structure formed by styrene-glycidyl methacrylate polymer and organosilicon on the surface of the activated conductive filler is used as a composite conductive additive. On the one hand, styrene-glycidyl methacrylate polymer itself has good impact resistance, which can enhance the impact resistance of the fiber. Moreover, the cross-linked network structure formed by styrene-glycidyl methacrylate polymer on the surface of the tubular conductive filler has excellent tensile strength, which makes the fiber exhibit high elasticity. On the other hand, the silanol contained in the cross-linked network structure can participate in the synthesis of polyurethane prepolymer. The composite conductive additive can be arranged in an orderly manner in the polyurethane matrix to form a stable conductive network, so that the composite conductive additive is uniformly dispersed in the polyurethane fiber and effectively improves the mechanical strength of the polyurethane fiber. Detailed Implementation

[0047] 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. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0048] The raw materials used in the embodiments of this invention are shown below, and all reagents used are analytical grade.

[0049] The isocyanate is toluene diisocyanate, the polyol is polyethylene glycol 2000, the chain extender is butanediol, the catalyst is dibutyltin dilaurate, and the organic solvent is N,N-dimethylformamide.

[0050] The porous silica is model SYLOID-244FP, manufactured by Beijing Fengli Jingqiu Pharmaceutical Co., Ltd.

[0051] The spherical silica has the product code JL-SiO2-W3 and is manufactured by Ningbo Jinlei Nanomaterials Technology Co., Ltd.

[0052] The liquid metal is a gallium-indium alloy with a purity of 99.99%, manufactured by Sichuan High Purity Materials Technology Co., Ltd.

[0053] The aminosilane is γ-aminopropyltriethoxysilane.

[0054] The graphene oxide nanosheets are approximately 35 nm thick and have a sheet diameter of 9 μm.

[0055] The organosilicon is a dihydroxy-terminated polydimethylsiloxane. Example

[0056] A method for preparing a highly elastic textile fiber includes the following preparation steps:

[0057] S1. Mix toluene diisocyanate, polyethylene glycol 2000 and N,N-dimethylformamide, heat to 50°C, add dibutyltin dilaurate, stir and react for 2 hours, then add butanediol and composite conductive additive, stir and react at 50°C for 1 hour to obtain polyurethane matrix;

[0058] S2. The polyurethane matrix is ​​washed, dried at 100°C, and then sliced ​​to obtain elastomer slices; the elastomer slices are extruded, granulated, melt-spun, and wound to obtain highly elastic textile fibers.

[0059] The mass ratio of isocyanate, polyethylene glycol 2000, N,N-dimethylformamide, dibutyltin dilaurate, butanediol and composite conductive additive is 30:70:100:0.3:20:8.

[0060] The extrusion process uses a twin-screw extruder with an extrusion temperature of 170℃.

[0061] The melt spinning process is as follows: spinning temperature 240℃, spinning speed 600m / min, drawing temperature 75℃, heat setting temperature 130℃, and drawing ratio 3.5 times.

[0062] The composite conductive additive is prepared by the following steps:

[0063] A1. Add 5g of porous silica to 15mL of ethanol and stir until homogeneous. Add 2.2g of gallium-indium alloy, heat to 60℃, stir and mix at 1000r / min for 20min, continue to heat to 80℃, stir until ethanol evaporates, remove the reactant, wash 3 times with deionized water, and dry in a 70℃ oven for 10min to obtain porous silica loaded with liquid metal.

[0064] A2. Mix 2g of porous silica loaded with liquid metal, 20mL of ethanol and 8mL of deionized water, stir well, add 1g of γ-aminopropyltriethoxysilane, stir and react at 100℃ for 30min, cool to room temperature, filter, wash 3 times with ethanol and 3 times with deionized water, and dry in an oven at 80℃ for 10min to obtain aminated porous silica loaded with liquid metal.

[0065] A3. Add 2g aniline, 6g graphene oxide nanosheets and 2mL of 10% acetic acid solution to 90mL of deionized water, stir well, add 0.1g ammonium persulfate and 4.6g amination-supported liquid metal porous silica, stir and react at 2℃ for 1h, filter, wash 3 times with deionized water, and dry in an oven at 70℃ for 15min to obtain conductive filler;

[0066] A4. Mix 15 mL of 98% concentrated sulfuric acid solution and 35 mL of 68% concentrated nitric acid solution, stir well to obtain a mixed acid, add 4 g of conductive filler to 15 mL of mixed acid, stir and mix at 80℃ for 1 h, cool to room temperature, filter, wash with deionized water until the washing solution is neutral, dry in an oven at 90℃ for 12 min to obtain activated conductive filler;

[0067] A5. Add 4.2g styrene and 3g glycidyl methacrylate to 85mL of deionized water, stir well, add 0.4g benzoyl peroxide, heat to 80℃, stir and react for 4h, filter, wash with deionized water, and dry in an oven at 70℃ for 10min to obtain styrene-glycidyl methacrylate polymer.

[0068] A6. Add 3g of styrene-glycidyl methacrylate polymer to 45mL of deionized water, stir well, add 4mL of 20% hydrochloric acid and 5.5g of activated conductive filler, stir and react at 70℃ for 10min, add 2.2g of dihydroxy-terminated polydimethylsiloxane, continue stirring and reacting for 10min, filter, wash with deionized water, and dry in an oven at 70℃ for 10min to obtain the composite conductive additive. Example

[0069] A method for preparing a highly elastic textile fiber includes the following preparation steps:

[0070] S1. Mix toluene diisocyanate, polyethylene glycol 2000 and N,N-dimethylformamide, heat to 55°C, add dibutyltin dilaurate, stir and react for 3 hours, then add butanediol and composite conductive additive, stir and react at 85°C for 1.5 hours to obtain polyurethane matrix;

[0071] S2. The polyurethane matrix is ​​washed, dried at 100°C, and then sliced ​​to obtain elastomer slices; the elastomer slices are extruded, granulated, melt-spun, and wound to obtain highly elastic textile fibers.

[0072] The mass ratio of isocyanate, polyethylene glycol 2000, N,N-dimethylformamide, dibutyltin dilaurate, butanediol, and composite conductive additive is 70:75:110:0.4:25:9.

[0073] Extrusion is performed using a twin-screw extruder with an extrusion temperature of 170-210℃.

[0074] The melt spinning process is as follows: spinning temperature 250℃, spinning speed 620m / min, drawing temperature 80℃, heat setting temperature 140℃, and drawing ratio 4 times.

[0075] The composite conductive additive is prepared by the following steps:

[0076] A1. Add 5.6g of porous silica to 20mL of ethanol and stir until homogeneous. Add 2.4g of gallium-indium alloy, heat to 65℃, stir and mix at 1300r / min for 25min, continue to heat to 85℃, stir until ethanol evaporates, remove the reactant, wash 3 times with deionized water, and dry in a 70℃ oven for 10min to obtain porous silica loaded with liquid metal.

[0077] A2. Mix 2.5g of porous silica loaded with liquid metal, 25mL of ethanol and 10mL of deionized water, stir well, add 1.5g of γ-aminopropyltriethoxysilane, stir and react at 105℃ for 35min, cool to room temperature, filter, wash 3 times with ethanol and 3 times with deionized water, and dry in an oven at 80℃ for 10min to obtain aminated porous silica loaded with liquid metal.

[0078] A3. Add 3g aniline, 7g graphene oxide nanosheets and 3mL of 10% acetic acid solution to 100mL of deionized water, stir well, add 0.2g ammonium persulfate and 4.8g amination-supported liquid metal porous silica, stir and react at 3℃ for 2h, filter, wash 3 times with deionized water, and dry in an oven at 70℃ for 15min to obtain conductive filler;

[0079] A4. Mix 20 mL of 98% concentrated sulfuric acid solution and 40 mL of 68% concentrated nitric acid solution, stir well to obtain a mixed acid, add 4.5 g of conductive filler to 20 mL of mixed acid, stir and mix at 85℃ for 1.5 h, cool to room temperature, filter, wash with deionized water until the washing solution is neutral, dry in an oven at 90℃ for 12 min to obtain activated conductive filler;

[0080] A5. Add 4.3g styrene and 3.5g glycidyl methacrylate to 90mL of deionized water, stir well, add 0.5g benzoyl peroxide, heat to 90℃, stir and react for 5h, filter, wash with deionized water, and dry in an oven at 70℃ for 10min to obtain styrene-glycidyl methacrylate polymer.

[0081] A6. Add 3.3g of styrene-glycidyl methacrylate polymer to 50mL of deionized water, stir well, add 5mL of 20% hydrochloric acid and 5.7g of activated conductive filler, stir and react at 80℃ for 15min, add 2.3g of dihydroxy-terminated polydimethylsiloxane, continue stirring and reacting for 20min, filter, wash with deionized water, and dry in an oven at 70℃ for 10min to obtain the composite conductive additive. Example

[0082] A method for preparing a highly elastic textile fiber includes the following preparation steps:

[0083] S1. Mix toluene diisocyanate, polyethylene glycol 2000 and N,N-dimethylformamide, heat to 60°C, add dibutyltin dilaurate, stir and react for 4 hours, then add butanediol and composite conductive additive, stir and react at 100°C for 2 hours to obtain polyurethane matrix;

[0084] S2. The polyurethane matrix is ​​washed, dried at 100°C, and then sliced ​​to obtain elastomer slices; the elastomer slices are extruded, granulated, melt-spun, and wound to obtain highly elastic textile fibers.

[0085] The mass ratio of isocyanate, polyethylene glycol 2000, N,N-dimethylformamide, dibutyltin dilaurate, butanediol and composite conductive additive is 80:80:120:0.5:80:10.

[0086] A twin-screw extruder was used for extrusion, with an extruder temperature of 210℃.

[0087] The melt spinning process is as follows: spinning temperature 260℃, spinning speed 630m / min, drawing temperature 85℃, heat setting temperature 150℃, and drawing ratio 4.5 times.

[0088] The composite conductive additive is prepared by the following steps:

[0089] A1. Add 6g of porous silica to 25mL of ethanol and stir until homogeneous. Add 2.6g of gallium-indium alloy, heat to 70℃, stir and mix at 1500r / min for 30min, continue to heat to 90℃, stir until ethanol evaporates, remove the reactant, wash 3 times with deionized water, and dry in a 70℃ oven for 10min to obtain porous silica loaded with liquid metal.

[0090] A2. Mix 3g of porous silica loaded with liquid metal, 30mL of ethanol and 12mL of deionized water, stir well, add 2g of γ-aminopropyltriethoxysilane, stir and react at 110℃ for 40min, cool to room temperature, filter, wash 3 times with ethanol and 3 times with deionized water, and dry in an oven at 80℃ for 10min to obtain aminated porous silica loaded with liquid metal.

[0091] A3. Add 4g aniline, 8g graphene oxide nanosheets and 4mL of 10% acetic acid solution to 110mL of deionized water, stir well, add 0.3g ammonium persulfate and 5g ammoniated loaded liquid metal porous silica, stir and react at 5℃ for 3h, filter, wash 3 times with deionized water, and dry in an oven at 70℃ for 15min to obtain conductive filler;

[0092] A4. Mix 25 mL of 98% concentrated sulfuric acid solution and 45 mL of 68% concentrated nitric acid solution, stir well to obtain a mixed acid, add 5 g of conductive filler to 25 mL of mixed acid, stir and mix at 90℃ for 2 h, cool to room temperature, filter, wash with deionized water until the washing solution is neutral, dry in an oven at 90℃ for 12 min to obtain activated conductive filler;

[0093] A5. Add 4.4g styrene and 4g glycidyl methacrylate to 95mL of deionized water, stir well, add 0.6g benzoyl peroxide, heat to 100℃, stir and react for 6h, filter, wash with deionized water, and dry in an oven at 70℃ for 10min to obtain styrene-glycidyl methacrylate polymer.

[0094] A6. Add 3.6g of styrene-glycidyl methacrylate polymer to 55mL of deionized water, stir well, add 6mL of 20% hydrochloric acid and 5.9g of activated conductive filler, stir and react at 90℃ for 20min, add 2.4g of dihydroxy-terminated polydimethylsiloxane, continue stirring and reacting for 20min, filter, wash with deionized water, and dry in an oven at 70℃ for 10min to obtain the composite conductive additive.

[0095] Comparative Example 1

[0096] A method for preparing a highly elastic textile fiber includes the following preparation steps:

[0097] S1. Mix toluene diisocyanate, polyethylene glycol 2000 and N,N-dimethylformamide, heat to 60°C, add dibutyltin dilaurate, stir and react for 4 hours, then add butanediol and composite conductive additive, stir and react at 100°C for 2 hours to obtain polyurethane matrix;

[0098] S2. The polyurethane matrix is ​​washed, dried at 100°C, and then sliced ​​to obtain elastomer slices; the elastomer slices are extruded, granulated, melt-spun, and wound to obtain highly elastic textile fibers.

[0099] The mass ratio of isocyanate, polyethylene glycol 2000, N,N-dimethylformamide, dibutyltin dilaurate, butanediol and composite conductive additive is 80:80:120:0.5:80:10.

[0100] A twin-screw extruder was used for extrusion, with an extruder temperature of 210℃.

[0101] The melt spinning process is as follows: spinning temperature 260℃, spinning speed 630m / min, drawing temperature 85℃, heat setting temperature 150℃, and drawing ratio 4.5 times.

[0102] The composite conductive additive is prepared by the following steps:

[0103] A1. Add 6g of spherical silica to 25mL of ethanol and stir until homogeneous. Add 2.6g of gallium-indium alloy, heat to 70℃, stir and mix at 1500r / min for 30min, continue to heat to 90℃, stir until ethanol evaporates, remove the reactant, wash 3 times with deionized water, and dry in a 70℃ oven for 10min to obtain the mixture.

[0104] A2. Add 4g aniline, 8g graphene oxide nanosheets and 4mL of 10% acetic acid solution to 110mL of deionized water, stir well, add 0.3g ammonium persulfate and 5g of the mixture, stir and react at 5℃ for 3h, filter, wash 3 times with deionized water, and dry in an oven at 70℃ for 15min to obtain conductive filler.

[0105] A3. Mix 25 mL of 98% concentrated sulfuric acid solution and 45 mL of 68% concentrated nitric acid solution, stir well to obtain a mixed acid, add 5 g of conductive filler to 25 mL of mixed acid, stir and mix at 90℃ for 2 h, cool to room temperature, filter, wash with deionized water until the washing solution is neutral, dry in an oven at 90℃ for 12 min to obtain activated conductive filler;

[0106] A4. Add 4.4g styrene and 4g glycidyl methacrylate to 95mL of deionized water, stir well, add 0.6g benzoyl peroxide, heat to 100℃, stir and react for 6h, filter, wash with deionized water, and dry in an oven at 70℃ for 10min to obtain styrene-glycidyl methacrylate polymer.

[0107] A5. Add 3.6g of styrene-glycidyl methacrylate polymer to 55mL of deionized water, stir well, add 6mL of 20% hydrochloric acid and 5.9g of activated conductive filler, stir and react at 90℃ for 20min, add 2.4g of dihydroxy-terminated polydimethylsiloxane, continue stirring and reacting for 20min, filter, wash with deionized water, and dry in an oven at 70℃ for 10min to obtain the composite conductive additive.

[0108] Comparative Example 2

[0109] A method for preparing a highly elastic textile fiber includes the following preparation steps:

[0110] S1. Mix toluene diisocyanate, polyethylene glycol 2000 and N,N-dimethylformamide, heat to 60°C, add dibutyltin dilaurate, stir and react for 4 hours, then add butanediol and composite conductive additive, stir and react at 100°C for 2 hours to obtain polyurethane matrix;

[0111] S2. The polyurethane matrix is ​​washed, dried at 100°C, and then sliced ​​to obtain elastomer slices; the elastomer slices are extruded, granulated, melt-spun, and wound to obtain highly elastic textile fibers.

[0112] The mass ratio of isocyanate, polyethylene glycol 2000, N,N-dimethylformamide, dibutyltin dilaurate, butanediol and composite conductive additive is 80:80:120:0.5:80:10.

[0113] A twin-screw extruder was used for extrusion, with an extruder temperature of 210℃.

[0114] The melt spinning process is as follows: spinning temperature 260℃, spinning speed 630m / min, drawing temperature 85℃, heat setting temperature 150℃, and drawing ratio 4.5 times.

[0115] The composite conductive additive is prepared by the following steps:

[0116] A1. Add 6g of porous silica to 25mL of ethanol and stir until homogeneous. Add 2.6g of gallium-indium alloy, heat to 70℃, stir and mix at 1500r / min for 30min, continue to heat to 90℃, stir until ethanol evaporates, remove the reactant, wash 3 times with deionized water, and dry in a 70℃ oven for 10min to obtain porous silica loaded with liquid metal.

[0117] A2. Mix 3g of porous silica loaded with liquid metal, 30mL of ethanol and 12mL of deionized water, stir well, add 2g of γ-aminopropyltriethoxysilane, stir and react at 110℃ for 40min, cool to room temperature, filter, wash 3 times with ethanol and 3 times with deionized water, and dry in an oven at 80℃ for 10min to obtain aminated porous silica loaded with liquid metal.

[0118] A3. Add 4.4g styrene and 4g glycidyl methacrylate to 95mL of deionized water, stir well, add 0.6g benzoyl peroxide, heat to 100℃, stir and react for 6h, filter, wash with deionized water, and dry in an oven at 70℃ for 10min to obtain styrene-glycidyl methacrylate polymer.

[0119] A4. Add 3.6g of styrene-glycidyl methacrylate polymer to 55mL of deionized water, stir well, add 6mL of 20% hydrochloric acid and 5.9g of aminated liquid metal-loaded porous silica, stir and react at 90℃ for 20min, add 2.4g of dihydroxy-terminated polydimethylsiloxane, continue stirring and reacting for 20min, filter, wash with deionized water, and dry in an oven at 70℃ for 10min to obtain the composite conductive additive.

[0120] Comparative Example 3

[0121] A method for preparing a highly elastic textile fiber includes the following preparation steps:

[0122] S1. Mix toluene diisocyanate, polyethylene glycol 2000 and N,N-dimethylformamide, heat to 60°C, add dibutyltin dilaurate, stir and react for 4 hours, then add butanediol and composite conductive additive, stir and react at 100°C for 2 hours to obtain polyurethane matrix;

[0123] S2. The polyurethane matrix is ​​washed, dried at 100°C, and then sliced ​​to obtain elastomer slices; the elastomer slices are extruded, granulated, melt-spun, and wound to obtain highly elastic textile fibers.

[0124] The mass ratio of isocyanate, polyethylene glycol 2000, N,N-dimethylformamide, dibutyltin dilaurate, butanediol and composite conductive additive is 80:80:120:0.5:80:10.

[0125] A twin-screw extruder was used for extrusion, with an extruder temperature of 210℃.

[0126] The melt spinning process is as follows: spinning temperature 260℃, spinning speed 630m / min, drawing temperature 85℃, heat setting temperature 150℃, and drawing ratio 4.5 times.

[0127] The composite conductive additive is prepared by the following steps:

[0128] A1. Add 6g of porous silica to 25mL of ethanol and stir until homogeneous. Add 2.6g of gallium-indium alloy, heat to 70℃, stir and mix at 1500r / min for 30min, continue to heat to 90℃, stir until ethanol evaporates, remove the reactant, wash 3 times with deionized water, and dry in a 70℃ oven for 10min to obtain porous silica loaded with liquid metal.

[0129] A2. Mix 3g of porous silica loaded with liquid metal, 30mL of ethanol and 12mL of deionized water, stir well, add 2g of γ-aminopropyltriethoxysilane, stir and react at 110℃ for 40min, cool to room temperature, filter, wash 3 times with ethanol and 3 times with deionized water, and dry in an oven at 80℃ for 10min to obtain aminated porous silica loaded with liquid metal.

[0130] A3. Add 4g aniline, 8g graphene oxide nanosheets and 4mL of 10% acetic acid solution to 110mL of deionized water, stir well, add 0.3g ammonium persulfate and 5g ammoniated loaded liquid metal porous silica, stir and react at 5℃ for 3h, filter, wash 3 times with deionized water, and dry in an oven at 70℃ for 15min to obtain conductive filler;

[0131] A4. Add 4.4g styrene and 4g glycidyl methacrylate to 95mL of deionized water, stir well, add 0.6g benzoyl peroxide, heat to 100℃, stir and react for 6h, filter, wash with deionized water, and dry in an oven at 70℃ for 10min to obtain styrene-glycidyl methacrylate polymer.

[0132] A5. Add 3.6g of styrene-glycidyl methacrylate polymer to 55mL of deionized water, stir well, add 6mL of 20% hydrochloric acid and 5.9g of conductive filler, stir and react at 90℃ for 20min, add 2.4g of dihydroxy-terminated polydimethylsiloxane, continue stirring and reacting for 20min, filter, wash with deionized water, and dry in an oven at 70℃ for 10min to obtain the composite conductive additive.

[0133] Comparative Example 4

[0134] A method for preparing a highly elastic textile fiber includes the following preparation steps:

[0135] S1. Mix toluene diisocyanate, polyethylene glycol 2000 and N,N-dimethylformamide, heat to 60°C, add dibutyltin dilaurate, stir and react for 4 hours, then add butanediol and composite conductive additive, stir and react at 100°C for 2 hours to obtain polyurethane matrix;

[0136] S2. The polyurethane matrix is ​​washed, dried at 100°C, and then sliced ​​to obtain elastomer slices; the elastomer slices are extruded, granulated, melt-spun, and wound to obtain highly elastic textile fibers.

[0137] The mass ratio of isocyanate, polyethylene glycol 2000, N,N-dimethylformamide, dibutyltin dilaurate, butanediol and composite conductive additive is 80:80:120:0.5:80:10.

[0138] A twin-screw extruder was used for extrusion, with an extruder temperature of 210℃.

[0139] The melt spinning process is as follows: spinning temperature 260℃, spinning speed 630m / min, drawing temperature 85℃, heat setting temperature 150℃, and drawing ratio 4.5 times.

[0140] The composite conductive additive is prepared by the following steps:

[0141] A1. Add 6g of porous silica to 25mL of ethanol and stir until homogeneous. Add 2.6g of gallium-indium alloy, heat to 70℃, stir and mix at 1500r / min for 30min, continue to heat to 90℃, stir until ethanol evaporates, remove the reactant, wash 3 times with deionized water, and dry in a 70℃ oven for 10min to obtain porous silica loaded with liquid metal.

[0142] A2. Mix 3g of porous silica loaded with liquid metal, 30mL of ethanol and 12mL of deionized water, stir well, add 2g of γ-aminopropyltriethoxysilane, stir and react at 110℃ for 40min, cool to room temperature, filter, wash 3 times with ethanol and 3 times with deionized water, and dry in an oven at 80℃ for 10min to obtain aminated porous silica loaded with liquid metal.

[0143] A3. Add 4g aniline, 8g graphene oxide nanosheets and 4mL of 10% acetic acid solution to 110mL of deionized water, stir well, add 0.3g ammonium persulfate and 5g ammoniated loaded liquid metal porous silica, stir and react at 5℃ for 3h, filter, wash 3 times with deionized water, and dry in an oven at 70℃ for 15min to obtain conductive filler;

[0144] A4. Mix 25 mL of 98% concentrated sulfuric acid solution and 45 mL of 68% concentrated nitric acid solution, stir well to obtain a mixed acid, add 5 g of conductive filler to 25 mL of mixed acid, stir and mix at 90℃ for 2 h, cool to room temperature, filter, wash with deionized water until the washing solution is neutral, dry in an oven at 90℃ for 12 min to obtain activated conductive filler;

[0145] A5. Mix 55 mL of deionized water, 6 mL of 20% hydrochloric acid and 5.9 g of activated conductive filler, stir and react at 90 °C for 20 min, add 2.4 g of dihydroxy-terminated polydimethylsiloxane, continue stirring and reacting for 20 min, filter, wash with deionized water, and dry in an oven at 70 °C for 10 min to obtain the composite conductive additive.

[0146] Comparative Example 5

[0147] A method for preparing a highly elastic textile fiber includes the following preparation steps:

[0148] S1. Mix toluene diisocyanate, polyethylene glycol 2000 and N,N-dimethylformamide, heat to 60°C, add dibutyltin dilaurate, stir and react for 4 hours, then add butanediol and composite conductive additive, stir and react at 100°C for 2 hours to obtain polyurethane matrix;

[0149] S2. The polyurethane matrix is ​​washed, dried at 100°C, and then sliced ​​to obtain elastomer slices; the elastomer slices are extruded, granulated, melt-spun, and wound to obtain highly elastic textile fibers.

[0150] The mass ratio of isocyanate, polyethylene glycol 2000, N,N-dimethylformamide, dibutyltin dilaurate, butanediol and composite conductive additive is 80:80:120:0.5:80:10.

[0151] A twin-screw extruder was used for extrusion, with an extruder temperature of 210℃.

[0152] The melt spinning process is as follows: spinning temperature 260℃, spinning speed 630m / min, drawing temperature 85℃, heat setting temperature 150℃, and drawing ratio 4.5 times.

[0153] The composite conductive additive is prepared by the following steps:

[0154] A1. Add 6g of porous silica to 25mL of ethanol and stir until homogeneous. Add 2.6g of gallium-indium alloy, heat to 70℃, stir and mix at 1500r / min for 30min, continue to heat to 90℃, stir until ethanol evaporates, remove the reactant, wash 3 times with deionized water, and dry in a 70℃ oven for 10min to obtain porous silica loaded with liquid metal.

[0155] A2. Mix 3g of porous silica loaded with liquid metal, 30mL of ethanol and 12mL of deionized water, stir well, add 2g of γ-aminopropyltriethoxysilane, stir and react at 110℃ for 40min, cool to room temperature, filter, wash 3 times with ethanol and 3 times with deionized water, and dry in an oven at 80℃ for 10min to obtain aminated porous silica loaded with liquid metal.

[0156] A3. Add 4g aniline, 8g graphene oxide nanosheets and 4mL of 10% acetic acid solution to 110mL of deionized water, stir well, add 0.3g ammonium persulfate and 5g ammoniated loaded liquid metal porous silica, stir and react at 5℃ for 3h, filter, wash 3 times with deionized water, and dry in an oven at 70℃ for 15min to obtain conductive filler;

[0157] A4. Mix 25 mL of 98% concentrated sulfuric acid solution and 45 mL of 68% concentrated nitric acid solution, stir well to obtain a mixed acid, add 5 g of conductive filler to 25 mL of mixed acid, stir and mix at 90℃ for 2 h, cool to room temperature, filter, wash with deionized water until the washing solution is neutral, dry in an oven at 90℃ for 12 min to obtain activated conductive filler;

[0158] A5. Add 4.4g styrene and 4g glycidyl methacrylate to 95mL of deionized water, stir well, add 0.6g benzoyl peroxide, heat to 100℃, stir and react for 6h, filter, wash with deionized water, and dry in an oven at 70℃ for 10min to obtain styrene-glycidyl methacrylate polymer.

[0159] A6. Add 3.6g of styrene-glycidyl methacrylate polymer to 55mL of deionized water, stir well, add 6mL of 20% hydrochloric acid and 5.9g of activated conductive filler, stir and react at 90℃ for 20min, filter, wash with deionized water, and dry in an oven at 70℃ for 10min to obtain the composite conductive additive.

[0160] The performance of the highly elastic textile fibers prepared in Examples 1-3 and Comparative Examples 1-5 was then tested.

[0161] Antistatic performance testing: In accordance with the standard GB / T24249-2009, the conductivity of the fiber is calculated by measuring the resistance and judging the performance. The higher the conductivity, the better the antistatic performance.

[0162] Elasticity performance test: The elasticity performance was tested using a 5843 universal tensile testing machine. The fiber elongation was set to 10%, the clamping distance was 100mm, and the stretching speed was 500mm / min. Elastic recovery rate = (fiber elongation value - L1) / fiber elongation value × 100%, where L1 is the elongation value corresponding to the fiber when it is stretched again to the pre-applied tension after relaxation recovery.

[0163] Elastic modulus testing: The elastic modulus of the high elastic textile fibers prepared above was tested in accordance with GB / T 32376-2015 standard.

[0164] Tensile strength test: The tensile strength of the high elastic textile fiber prepared above was tested in accordance with GB / T14344-2022 standard, with a clamping distance of 250 mm and a tensile speed of 200 mm / min.

[0165] As shown in Table 1 below.

[0166] Table 1. Performance testing of the high-elasticity textile fibers prepared in Examples 1-3 and Comparative Examples 1-5

[0167] project Conductivity S / cm Elastic recovery rate / % Fracture strength cN / dtex Elastic modulus cN / dtex Example 1 <![CDATA[5.6×10 6 ]]> 99.6 16.3 396 Example 2 <![CDATA[5.8×10 6 ]]> 99.7 17.8 399 Example 3 <![CDATA[5.5×10 6 ]]> 99.5 15.6 392 Comparative Example 1 <![CDATA[4.3×10 4 ]]> 85.3 8.6 352 Comparative Example 2 <![CDATA[4.8×10 4 ]]> 72.3 7.5 323 Comparative Example 3 <![CDATA[4.6×10 6 ]]> 70.1 6.3 311 Comparative Example 4 <![CDATA[4.9×10 6 ]]> 71.6 6.8 317 Comparative Example 5 <![CDATA[6.9×10 4 ]]> 77.9 8.7 349

[0168] As can be seen from the data in Table 1, the high-elasticity textile fibers prepared in Examples 1-3 have high mechanical strength and electrical conductivity.

[0169] In Comparative Example 1, when porous silica was replaced with spherical silica to prepare a composite conductive additive, the conductivity and mechanical properties of the high-elasticity textile fiber decreased. This demonstrates that the liquid metal is adsorbed into the pores of porous silica, preventing the liquid metal from migrating and precipitating. Furthermore, under the action of porous silica, the graphene oxide nanosheets self-roll to form a tubular structure with porous silica loaded with liquid metal as the core material and graphene-polyaniline as the shell, which has good tensile strength.

[0170] In Comparative Example 2, when the conductive filler was replaced with porous silica loaded with aminated liquid metal, the composite conductive additive was added to the highly elastic textile fiber. The conductivity and mechanical properties of the fiber decreased, demonstrating that the tubular structure formed by porous silica loaded with liquid metal as the core material and graphene-polyaniline as the shell has good tensile strength. Furthermore, the graphene oxide nanosheets and polyaniline have high carrier mobility and can form conductive pathways with the liquid metal in the tubular structure, resulting in good conductivity.

[0171] In Comparative Example 3, when the activated conductive filler was replaced with a composite conductive additive prepared by the conductive filler and added to the high-elasticity textile fiber, its mechanical properties decreased. This proves that introducing oxygen-containing functional groups carboxyl and hydroxyl groups on the surface of the tubular conductive filler improves the surface activity of the tubular conductive filler, which is beneficial to the cross-linked network structure formed on the surface of the activated conductive filler, thereby enhancing the fiber's impact resistance and tensile strength.

[0172] In Comparative Example 4, the composite conductive additive prepared without the addition of styrene-glycidyl methacrylate polymer was added to the high-elasticity textile fiber, which resulted in a decrease in its mechanical properties. This demonstrates that the styrene-glycidyl methacrylate polymer has good impact resistance and can enhance the impact resistance of the fiber. Furthermore, the styrene-glycidyl methacrylate polymer forms a cross-linked network structure on the surface of the tubular conductive filler, exhibiting excellent tensile properties, which makes the fiber exhibit high elasticity.

[0173] In Comparative Example 5, the composite conductive additive prepared without the addition of dihydroxy-terminated polydimethylsiloxane was added to highly elastic textile fibers, resulting in a decrease in their mechanical and mechanical properties. This demonstrates that the styrene-glycidyl methacrylate polymer can improve the fiber's elasticity through the cross-linked network structure formed by dihydroxy-terminated polydimethylsiloxane on the surface of the activated conductive filler. Furthermore, the dihydroxy-terminated polydimethylsiloxane can participate in the synthesis of polyurethane prepolymers, allowing the composite conductive additive to arrange itself in an orderly manner within the polyurethane matrix, forming a stable conductive network and improving conductivity.

[0174] In the description of this specification, the references to terms such as "an embodiment," "example," "specific example," etc., indicate that a specific feature, structure, material, or characteristic described in connection with that embodiment or example is included in at least one embodiment or example of the present invention. In this specification, the illustrative expressions of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in one or more embodiments or examples.

[0175] The above description is merely an example and illustration of the present invention. Those skilled in the art can make various modifications or additions to the specific embodiments described, or use similar methods to replace them, as long as they do not deviate from the invention or exceed the scope defined in the claims, all of which should fall within the protection scope of the present invention.

Claims

1. A method for preparing a highly elastic textile fiber, characterized in that, The preparation steps include the following: S1. Mix isocyanate, polyol and organic solvent, heat to 50-60℃, add catalyst, stir and react for 2-4 hours, then add chain extender and composite conductive additive, stir and react at 50-100℃ for 1-2 hours to obtain polyurethane matrix; S2. After washing, drying and slicing the polyurethane matrix, elastomer chips are obtained; after extrusion and granulation, the elastomer chips are melt-spun and wound to obtain highly elastic textile fibers. The composite conductive additive is prepared by the following steps: A1. Add porous silica to ethanol, stir until homogeneous, add liquid metal, heat to 60-70℃, stir and mix at a rate of 1000-1500 r / min for 20-30 min, stir until homogeneous at 80-90℃, remove the reactant, wash and dry to obtain porous silica loaded with liquid metal. A2. Mix porous silica loaded with liquid metal, ethanol and deionized water, stir until homogeneous, add aminosilane, stir and react at 100-110℃ for 30-40 min, cool to room temperature, filter, wash and dry to obtain aminated porous silica loaded with liquid metal. A3. Add aniline, graphene oxide nanosheets and acetic acid solution to deionized water, stir evenly, add ammonium persulfate and ammoniated liquid metal-supported porous silica, stir and react at 2-5℃ for 1-3h, filter, wash and dry to obtain conductive filler; A4. Mix concentrated sulfuric acid solution and concentrated nitric acid solution, stir evenly to obtain mixed acid, add conductive filler to mixed acid, stir and mix at 80-90℃ for 1-2 hours, cool to room temperature, filter, wash and dry to obtain activated conductive filler; A5. Add styrene and glycidyl methacrylate to deionized water, stir until homogeneous, add benzoyl peroxide, heat to 80-100℃, stir and react for 4-6 hours, filter, wash and dry to obtain styrene-glycidyl methacrylate polymer. A6. Add the styrene-glycidyl methacrylate polymer to deionized water, stir until homogeneous, add hydrochloric acid and activated conductive filler, stir and react at 70-90℃ for 10-20 min, add organosilicon, continue stirring and reacting for 10-20 min, filter, wash and dry to obtain the composite conductive additive.

2. The method for preparing a high-elasticity textile fiber according to claim 1, characterized in that, In step A1, the ratio of porous silica, ethanol and liquid metal is (5-6)g:(15-25)mL:(2.2-2.6)g.

3. The method for preparing a high-elasticity textile fiber according to claim 1, characterized in that, In step A2, the ratio of the porous silica loaded with liquid metal, ethanol, deionized water and aminosilane is (2-3)g:(20-30)mL:(8-12)mL:(1-2)g.

4. The method for preparing a high-elasticity textile fiber according to claim 1, characterized in that, In step A3, the ratio of aniline, graphene oxide nanosheets, acetic acid solution, deionized water, ammonium persulfate, and ammoniated liquid metal-supported porous silica is (2-4)g:(6-8)g:(2-4)mL:(90-110)mL:(0.1-0.3)g:(4.6-5)g.

5. The method for preparing a high-elasticity textile fiber according to claim 1, characterized in that, In step A4, the volume ratio of the concentrated sulfuric acid solution to the concentrated nitric acid solution is (15-25):(35-45); The ratio of the conductive filler to the mixed acid is (4-5)g:(15-25)mL.

6. The method for preparing a high-elasticity textile fiber according to claim 1, characterized in that, In step A5, the ratio of styrene, glycidyl methacrylate, deionized water and benzoyl peroxide is (4.2-4.4)g:(3-4)g:(85-95)mL:(0.4-0.6)g.

7. The method for preparing a high-elasticity textile fiber according to claim 1, characterized in that, In step A6, the ratio of the amount of styrene-glycidyl methacrylate polymer, deionized water, hydrochloric acid, activated conductive filler and organosilicon is (3-3.6)g:(45-55)mL:(4-6)mL:(5.5-5.9)g:(2.2-2.4)g.

8. A high-elasticity textile fiber prepared by the method of any one of claims 1-7.