A magnetic therapy fabric containing heat-generating polyamide fiber, its preparation method and application

Abstract

The present invention relates to the technical field of fabrics, and particularly relates to a magnetic therapy fabric containing heat-generating polyamide fibers, a preparation method thereof, and an application thereof. The magnetic therapy fabric containing heat-generating polyamide fibers in the present invention includes an inner fabric layer and an outer fabric layer. The air layer formed by the gap between the two fabric layers improves the heat preservation performance of the fabric. The fabric is made of polyamide fibers and has good wear resistance. By adding additives, the components of the additives include far-infrared heat-generating material graphene oxide, magnetic material iron tetroxide, and alkyl quaternary ammonium salt, which can achieve its far-infrared heat-generating performance and magnetic therapy performance. At the same time, it can improve its antistatic performance and antibacterial performance; the polyamide fabric is subjected to finishing and modification treatment, which can further enhance the antibacterial performance, antistatic performance, and moisture absorption performance of the polyamide fabric. The prepared magnetic therapy fabric containing heat-generating polyamide fibers in the present invention has a wide application in the field of textiles such as health care clothing.

Description

Technical Field

[0001] The present invention relates to the technical field of fabrics, and particularly to a magnetic therapy fabric containing heat-generating polyamide fibers, and a preparation method and application thereof. Background Art

[0002] Polyamide, commonly known as nylon, has excellent wear resistance and hygroscopicity, and is widely used in the field of fabrics. With the development of technology, people's requirements for clothing are getting higher and higher, such as far-infrared heat generation performance. By adding far-infrared substances, it can absorb far-infrared rays in sunlight, convert them into its own heat energy, increase the skin surface temperature, and has good heat preservation effect. In addition, textiles with magnetic therapy functions have gradually received attention.

[0003] Chinese Patent CN111778581B discloses a far-infrared heat-generating and weather-resistant graphene polyamide filament, which is prepared by melt spinning of polyamide fiber and graphene fiber. The addition of graphene fiber can achieve the far-infrared heat generation of the polyamide filament. However, the polyamide fiber and the graphene fiber are physically blended, resulting in uneven dispersion, and the far-infrared heat generation performance needs to be improved. Chinese Patent Application CN108385190A discloses a polyamide fiber with magnetic therapy and health care functions, which is prepared by melt spinning of a magnetic stone physiotherapy masterbatch and polyamide 6 chips. The magnetic stone physiotherapy masterbatch and polyamide 6 are physically blended, resulting in uneven dispersion, and the magnetic therapy function needs to be improved. In addition, polyamide is prone to generating static electricity, and the antistatic performance of polyamide fibers needs to be improved. Summary of the Invention

[0004] Aiming at the deficiencies of the prior art, the present invention provides a magnetic therapy fabric containing heat-generating polyamide fibers to solve the problems that the heat generation, magnetic therapy and antistatic performances of heat-generating and magnetic therapy polyamide fibers in the prior art need to be improved.

[0005] To achieve the above object, the technical solution adopted by the present invention is as follows: A preparation method of a magnetic therapy fabric containing heat-generating polyamide fibers, comprising the following steps:

[0006] Step 1: Drop N,N-dimethyl-1,3-propanediamine into oleic acid (cis-9-octadecenoic acid). After the dropping is completed, react. After the reaction is completed, purify to obtain oleamide propyl-N,N-dimethyl tertiary amine;

[0007] Step 2: Dissolve oleamide propyl-N,N-dimethyl tertiary amine in isopropanol-deionized water, add a quaternization reagent, react. After the reaction is completed, purify to obtain oleamide propyl-N,N-dimethyl quaternary ammonium salt;

[0008] Step 3: Dissolve γ-methacryloxypropyltrimethoxysilane (silane coupling agent KH-570) in an ethanol aqueous solution, adjust the pH value to 4-5, add the graphene oxide-ferroferric oxide composite material, perform ultrasonic dispersion, then react. After the reaction is completed, filter, wash, and dry to obtain an alkenyl-modified graphene oxide-ferroferric oxide composite material; Immerse nylon 66 powder in an initiator solution, and perform a pre-initiation reaction under microwave radiation. After the reaction is completed, filter to obtain pre-initiated nylon 66 powder; Add oleic acid amide propyl-N,N-dimethyl quaternary ammonium salt, alkenyl-modified graphene oxide-ferroferric oxide composite material, and an emulsifier to deionized water, perform ultrasonic dispersion, then add the pre-initiated nylon 66 powder, and perform a grafting reaction under microwave radiation. After the reaction is completed, filter, wash, and dry to obtain an auxiliary agent;

[0009] Step 4: Blend and melt the auxiliary agent with nylon 66 resin. The melt is extruded through a spinneret to form fiber filaments, which are cooled by side blowing, drawn, and cut short to obtain heat-generating polyamide fibers; Spin the heat-generating polyamide fibers into yarns to obtain heat-generating polyamide yarns, spin the heat-generating polyamide yarns into fabrics to obtain polyamide fabrics; Immerse the polyamide fabrics in a finishing solution for impregnation treatment. After the impregnation is completed, perform photocuring treatment, wash, and dry to obtain modified polyamide fabrics; Use the modified polyamide fabrics as the outer fabric and the inner fabric respectively, sew the outer fabric and the inner fabric with equal areas, and the gap between the outer fabric and the inner fabric forms an air layer to obtain a magnetic therapy fabric containing heat-generating polyamide fibers.

[0010] Preferably, in the said Step 1, the molar ratio of oleic acid to N,N-dimethyl-1,3-propanediamine is 1:(1.5-2.5), the dropping rate of N,N-dimethyl-1,3-propanediamine is 1-2 mL / min, and the reaction conditions are to react under nitrogen protection and at a temperature of 130-150 °C for 8-10 h in a closed system.

[0011] Preferably, in the said Step 2, the molar ratio of oleic acid amide propyl-N,N-dimethyl tertiary amine to the quaternization reagent is 1:(1.1-1.3), the dosage of isopropanol-deionized water is 3-5 times the mass of oleic acid amide propyl-N,N-dimethyl tertiary amine, and the reaction conditions are to react at a temperature of 80-90 °C for 4-6 h.

[0012] Preferably, the said quaternization reagent includes n-butyl bromide.

[0013] Preferably, the said isopropanol-deionized water is a mixture of isopropanol and deionized water in a mass ratio of 1:2.

[0014] Preferably, in the third step, when preparing the alkenyl-modified graphene oxide-ferroferric oxide composite material, the mass ratio of the graphene oxide-ferroferric oxide composite material, γ-methacryloxypropyltrimethoxysilane, and the ethanol aqueous solution is 0.2:(0.8 - 1.2):(60 - 100), and the reaction conditions are to react at a temperature of 50 - 70°C for 6 - 8 h.

[0015] Preferably, the ethanol aqueous solution includes a 75 wt% ethanol aqueous solution.

[0016] Preferably, the graphene oxide-ferroferric oxide composite material is prepared by the following steps: adding amino-modified nano-ferroferric oxide and nano-graphene oxide into deionized water, after ultrasonic dispersion, adding 1-ethyl-(3-dimethylaminopropyl)carbodiimide, reacting, after the reaction ends, filtering, washing, and drying to obtain the graphene oxide-ferroferric oxide composite material.

[0017] Preferably, the mass ratio of the amino-modified nano-ferroferric oxide, nano-graphene oxide, deionized water, and 1-ethyl-(3-dimethylaminopropyl)carbodiimide is (15 - 25):(75 - 85):(800 - 1200):(15 - 25), and the reaction conditions are to stir and react at a temperature of 75 - 85°C for 20 - 30 h.

[0018] Preferably, the amino-modified nano-ferroferric oxide is prepared by the following steps: adding nano-ferroferric oxide into the ethanol aqueous solution, after ultrasonic dispersion, adding 3-aminopropyltrimethoxysilane (silane coupling agent KH-540), reacting, after the reaction ends, filtering, washing, and drying to obtain the amino-modified nano-ferroferric oxide.

[0019] Preferably, the mass ratio of nano-ferroferric oxide, 3-aminopropyltrimethoxysilane, and the ethanol aqueous solution is 0.1:(0.5 - 1.5):(50 - 70), and the reaction conditions are to react at a temperature of 40 - 50°C for 6 - 10 h.

[0020] Preferably, the ethanol aqueous solution includes a 75 wt% ethanol aqueous solution.

[0021] Preferably, in the third step, when preparing the pre-initiated nylon 66 powder, the mass ratio of the nylon 66 powder to the initiator solution is 1:(20 - 30), the microwave power is 350 - 450 W, the temperature of the pre-initiation reaction is 60 - 80°C, and the time of the pre-initiation reaction is 20 - 40 min; the initiator solution includes an aqueous solution of potassium persulfate; the mass percentage content of potassium persulfate in the aqueous solution of potassium persulfate is 0.2 wt% - 0.4 wt%.

[0022] Preferably, in the third step, when preparing the auxiliary agent, the mass ratio of oleamide propyl-N,N-dimethyl quaternary ammonium salt, alkenyl modified graphene oxide-ferroferric oxide composite material, emulsifier, deionized water, and pre-initiated nylon 66 powder is (2-4):(4-8):(3-5):(600-800):100, the microwave power is 350-450 W, the temperature of the grafting reaction is 60-80 °C, and the time of the grafting reaction is 45-75 min; the emulsifier includes Span (sorbitan laurate).

[0023] Preferably, in the fourth step, the mass ratio of the auxiliary agent to the nylon 66 resin is (18-24):100, the melting temperature is 285-295 °C, the pressure of the spinneret is 16-20 MPa, the temperature of the side air blowing is 15-20 °C, and the draw ratio is 1.3-1.5 times.

[0024] Preferably, in the fourth step, the yarn count of the heat-generating polyamide yarn is 20-30 S (English count), and the gram weight of the polyamide fabric is 200-220 g / m 2 .

[0025] Preferably, in the fourth step, the mass ratio of the polyamide fabric to the finishing solution is 1:(15-25), the impregnation treatment is carried out at room temperature, two-dip two-roll, and the liquor pickup rate is 90%.

[0026] Preferably, the finishing solution is prepared by the following steps: adding dimethyldiallylammonium chloride, acrylamide, 2-hydroxyethyl methacrylate, and photoinitiator into deionized water, and ultrasonic dispersing to obtain the finishing solution; wherein, the mass ratio of dimethyldiallylammonium chloride, acrylamide, 2-hydroxyethyl methacrylate, photoinitiator, and deionized water is (16-20):(7-10):(13-18):(3.5-6):(300-500); the photoinitiator includes lithium phenyl(2,4,6-trimethylbenzoyl)phosphate.

[0027] The present invention also provides a magnetic therapy fabric containing heat-generating polyamide fibers prepared by using the preparation method of the magnetic therapy fabric containing heat-generating polyamide fibers as described above.

[0028] An application of a magnetic therapy fabric containing heat-generating polyamide fibers as described above in textiles.

[0029] Compared with the prior art, the beneficial effects of the present invention are as follows: In the present invention, the magnetic therapy fabric containing heat-generating polyamide fibers includes an inner fabric layer and an outer fabric layer. The air layer formed by the gap between the two fabric layers improves the heat preservation performance of the fabric. The fabric is made of polyamide fibers and has good abrasion resistance. By adding additives, since the additives are made of far-infrared heat-generating material graphene oxide and magnetic material iron tetroxide, the far-infrared heat-generating performance and magnetic therapy performance of the polyamide fabric can be achieved. At the same time, the additives also contain alkyl quaternary ammonium salts, which can improve the antibacterial and antistatic properties of the polyamide fabric. In addition, the polyamide fabric is subjected to finishing and modification treatment. The raw materials in the finishing solution include dimethyldiallylammonium chloride, acrylamide, and 2-hydroxyethyl methacrylate. Under the action of a photoinitiator, a film is polymerized on the surface of the polyamide fabric and between the pores of the fabric under light irradiation conditions. The introduction of quaternary ammonium salt dimethyldiallylammonium chloride can further enhance the antibacterial and antistatic properties of the polyamide fabric, and the introduction of acrylamide and 2-hydroxyethyl methacrylate can improve the hydrophilicity of the polyamide and further enhance the moisture absorption performance of the polyamide fabric. In the present invention, when preparing the additives, oleic acid is used as the raw material for the alkyl chain. Oleic acid reacts with N,N-dimethyl-1,3-propanediamine to obtain oleic acid amide propyl-N,N-dimethyl tertiary amine. Oleic acid amide propyl-N,N-dimethyl tertiary amine reacts with a quaternizing reagent to obtain oleic acid amide propyl-N,N-dimethyl quaternary ammonium salt. The graphene oxide-iron tetroxide composite material reacts with γ-methacryloxypropyltrimethoxysilane to obtain an alkenyl-modified graphene oxide-iron tetroxide composite material. Nylon 66 powder undergoes a pre-initiation reaction under microwave irradiation conditions under the action of an initiator, which can initiate active free radicals on the surface of nylon 66. Oleic acid amide propyl-N,N-dimethyl quaternary ammonium salt and the alkenyl-modified graphene oxide-iron tetroxide composite material react with the pre-initiated nylon 66 through the alkenyl groups on the molecules and graft onto the nylon 66 molecules, improving the dispersion uniformity among the quaternary ammonium salt, graphene oxide-iron tetroxide, and nylon 66, and stabilizing the far-infrared heat-generating performance, magnetic therapy performance, antibacterial performance, and antistatic performance. BRIEF DESCRIPTION OF THE DRAWINGS

[0030] Figure 1 It is a process flow chart of the preparation of the additives in the present invention;

[0031] Figure 2 It is a bar chart of the heat-generating performance measurement results of the polyamide fabrics prepared in Examples 1-4 and Comparative Examples 1-2 of the present invention;

[0032] Figure 3 It is a bar chart of the magnetic property measurement results of the polyamide fabrics prepared in Examples 1-4 and Comparative Examples 1-2 of the present invention;

[0033] Figure 4 It is a bar chart of the antibacterial property measurement results of the polyamide fabrics prepared in Examples 1-4 and Comparative Examples 1-2 of the present invention;

[0034] Figure 5 Bar chart of the antistatic performance measurement results of the nylon fabrics prepared in Examples 1-4 and Comparative Examples 1-2 of the present invention. Detailed implementation manners

[0035] Next, in combination with the embodiments of the present invention, the technical solutions in the embodiments of the present invention will be clearly and completely described. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without making creative efforts belong to the protection scope of the present invention.

[0036] Example 1

[0037] This example discloses a preparation method of a magnetic therapy fabric containing heat-generating nylon fibers, including the following steps:

[0038] Step 1: Under nitrogen protection, N,N-dimethyl-1,3-propanediamine is added dropwise to oleic acid. The molar ratio of oleic acid to N,N-dimethyl-1,3-propanediamine is 1:1.5, and the dropping rate of N,N-dimethyl-1,3-propanediamine is 1 mL / min. After the dropping is completed, the reaction is carried out in a closed state at a temperature of 130 °C for 10 h under nitrogen protection. After the reaction is completed, under a temperature of 80 °C and a pressure of 0.1 MPa, vacuum distillation is carried out to remove unreacted N,N-dimethyl-1,3-propanediamine and the generated water. N-hexane with a mass 3 times that of oleic acid is added for crystallization, and filtration is carried out. The filtration residue is washed 3 times with n-hexane and then vacuum dried to constant weight at a temperature of 60 °C and a pressure of 0.1 MPa to obtain oleic acid amide propyl-N,N-dimethyl tertiary amine;

[0039] Step 2: Oleic acid amide propyl-N,N-dimethyl tertiary amine is dissolved in isopropanol-deionized water, and bromobutane is added. The molar ratio of oleic acid amide propyl-N,N-dimethyl tertiary amine to bromobutane is 1:1.1, and the amount of isopropanol-deionized water used is 3 times the mass of oleic acid amide propyl-N,N-dimethyl tertiary amine. The reaction is carried out at a temperature of 80 °C for 6 h. After the reaction is completed, under a temperature of 70 °C and a pressure of 0.1 MPa, vacuum distillation is carried out to remove isopropanol and deionized water. A mixed solvent of n-hexane-ethyl acetate with a mass 3 times that of oleic acid amide propyl-N,N-dimethyl tertiary amine is added for crystallization, and filtration is carried out. The filtration residue is washed 3 times with the mixed solvent of n-hexane-ethyl acetate and then vacuum dried to constant weight at a temperature of 60 °C and a pressure of 0.1 MPa to obtain oleic acid amide propyl-N,N-dimethyl quaternary ammonium salt; wherein, the isopropanol-deionized water is a mixture of isopropanol and deionized water in a mass ratio of 1:2;

[0040] Step 3: Dissolve γ-methacryloxypropyltrimethoxysilane in a 75 wt% ethanol aqueous solution, adjust the pH value to 4.5 with acetic acid, add the graphene oxide-ferroferric oxide composite material. The mass ratio of the graphene oxide-ferroferric oxide composite material, γ-methacryloxypropyltrimethoxysilane, and the 75 wt% ethanol aqueous solution is 0.2:1:80. After ultrasonic dispersion at a frequency of 50 kHz for 30 min, react at a temperature of 60 °C for 7 h. After the reaction is completed, filter, wash with ethanol 3 times, and place in a vacuum drying oven at 50 °C for drying for 24 h to obtain an alkenyl-modified graphene oxide-ferroferric oxide composite material; among them, the graphene oxide-ferroferric oxide composite material is prepared by the following steps: Add amino-modified nano-ferroferric oxide and nano-graphene oxide to deionized water. After ultrasonic dispersion at a frequency of 50 kHz for 30 min, add 1-ethyl-(3-dimethylaminopropyl)carbodiimide. The mass ratio of amino-modified nano-ferroferric oxide, nano-graphene oxide, deionized water, and 1-ethyl-(3-dimethylaminopropyl)carbodiimide is 20:80:1000:20. Stir and react at a temperature of 80 °C and a stirring speed of 300 r / min for 24 h. After the reaction is completed, filter, wash with deionized water 3 times, and place in a vacuum drying oven at 50 °C for drying for 24 h to obtain the graphene oxide-ferroferric oxide composite material; among them, the amino-modified nano-ferroferric oxide is prepared by the following steps: Add nano-ferroferric oxide to a 75 wt% ethanol aqueous solution. After ultrasonic dispersion at a frequency of 50 kHz for 30 min, add 3-aminopropyltrimethoxysilane. The mass ratio of nano-ferroferric oxide, 3-aminopropyltrimethoxysilane, and the 75 wt% ethanol aqueous solution is 0.1:1:60. React at a temperature of 45 °C for 8 h. After the reaction is completed, filter, wash with ethanol 3 times, and place in a vacuum drying oven at 50 °C for drying for 24 h to obtain amino-modified nano-ferroferric oxide; Immerse nylon 66 powder in a 0.2 wt% potassium persulfate aqueous solution. The nylon 66 powder and 0.The mass ratio of the 2 wt% potassium persulfate aqueous solution is 1:20, and a pre-initiation reaction is carried out under microwave radiation conditions. After the reaction is completed, filtration is carried out to obtain pre-initiated nylon 66 powder; among them, the microwave power is 350 W, the temperature of the pre-initiation reaction is 60 °C, and the time of the pre-initiation reaction is 40 min; oleic acid amide propyl-N,N-dimethyl quaternary ammonium salt, vinyl-modified graphene oxide-ferroferric oxide composite material, and span 20 are added to deionized water, and ultrasonic dispersion is carried out for 30 min at a frequency of 50 kHz, and then the pre-initiated nylon 66 powder is added. The mass ratio of oleic acid amide propyl-N,N-dimethyl quaternary ammonium salt, vinyl-modified graphene oxide-ferroferric oxide composite material, span 20, deionized water, and pre-initiated nylon 66 powder is 2:4:3:600:100, and a grafting reaction is carried out under microwave radiation conditions. After the reaction is completed, filtration is carried out, and it is washed 3 times with deionized water and placed in a vacuum drying oven at 50 °C for drying for 24 h to obtain an additive; among them, the microwave power is 350 W, the temperature of the grafting reaction is 60 °C, and the time of the grafting reaction is 75 min;.

[0041] Step 4: Blend and melt the additive with nylon 66 resin. The mass ratio of the additive to nylon 66 resin is 18:100, the melting temperature is 285 °C, the melt is ejected through a spinneret to form fiber filaments, the pressure of the spinneret is 18 MPa, side blowing cooling is carried out, the temperature of the side blowing is 18 °C, drawing is carried out, the draw ratio is 1.4 times, and short cutting is carried out to obtain heat-generating polyamide fibers. The length of the heat-generating polyamide fibers is 38 mm; the heat-generating polyamide fibers are spun into yarns to obtain heat-generating polyamide yarns. The yarn count of the heat-generating polyamide yarns is 25S. The heat-generating polyamide yarns are spun into fabrics through a knitting process to obtain polyamide fabrics. The gram weight of the polyamide fabrics is 210 g / m 2 ; The polyamide fabric is placed in a finishing solution for impregnation treatment. The mass ratio of the polyamide fabric to the finishing solution is 1:15. The impregnation treatment is carried out at room temperature, double dipping and double rolling are carried out, and the liquor pickup rate is 90%. After the impregnation is completed, both sides of the impregnated polyamide fabric are irradiated with blue light with a wavelength of 405 nm for 30 min for a curing reaction, washed 3 times with deionized water, and dried at a temperature of 50 °C to obtain a modified polyamide fabric; among them, the finishing solution is prepared by the following steps: Dimethyldiallylammonium chloride, acrylamide, 2-hydroxyethyl methacrylate, and phenyl(2,4,6-trimethylbenzoyl)phosphate lithium salt are added to deionized water, and ultrasonic dispersion is carried out for 30 min at a frequency of 50 kHz to obtain a finishing solution; among them, the mass ratio of dimethyldiallylammonium chloride, acrylamide, 2-hydroxyethyl methacrylate, phenyl(2,4,6-trimethylbenzoyl)phosphate lithium salt, and deionized water is 18:8:15:5:400; Using the modified polyamide fabric as the outer fabric and the inner fabric respectively, the outer fabric and the inner fabric are sewn with equal area using polyester sewing thread, and the gap between the outer fabric and the inner fabric forms an air layer to obtain a magnetic therapy fabric containing heat-generating polyamide fibers.

[0042] Example 2

[0043] This example discloses a preparation method of a magnetic therapy fabric containing heat-generating polyamide fiber, which includes the following steps:

[0044] Step 1: Under nitrogen protection, drop N,N-dimethyl-1,3-propanediamine into oleic acid. The molar ratio of oleic acid to N,N-dimethyl-1,3-propanediamine is 1:2.5, and the dropping rate of N,N-dimethyl-1,3-propanediamine is 2 mL / min. After the dropping is completed, carry out a closed reaction at 150 °C for 8 h under nitrogen protection. After the reaction ends, carry out vacuum distillation at 80 °C and 0.1 MPa to remove unreacted N,N-dimethyl-1,3-propanediamine and the generated water. Add n-hexane for crystallization with a mass 3 times that of oleic acid, filter, wash the filter residue with n-hexane 3 times, and then carry out vacuum drying at 60 °C and 0.1 MPa until constant weight to obtain oleic acid amide propyl-N,N-dimethyl tertiary amine;

[0045] Step 2: Dissolve oleic acid amide propyl-N,N-dimethyl tertiary amine in isopropanol-deionized water, add n-butyl bromide. The molar ratio of oleic acid amide propyl-N,N-dimethyl tertiary amine to n-butyl bromide is 1:1.3, and the dosage of isopropanol-deionized water is 5 times the mass of oleic acid amide propyl-N,N-dimethyl tertiary amine. React at 90 °C for 4 h. After the reaction ends, carry out vacuum distillation at 70 °C and 0.1 MPa to remove isopropanol and deionized water. Add a mixed solvent of n-hexane-ethyl acetate for crystallization with a mass 3 times that of oleic acid amide propyl-N,N-dimethyl tertiary amine, filter, wash the filter residue with the mixed solvent of n-hexane-ethyl acetate 3 times, and then carry out vacuum drying at 60 °C and 0.1 MPa until constant weight to obtain oleic acid amide propyl-N,N-dimethyl quaternary ammonium salt; wherein, isopropanol-deionized water is a mixture of isopropanol and deionized water in a mass ratio of 1:2;

[0046] Step 3: Prepare the alkenyl-modified graphene oxide-ferroferric oxide composite material; the preparation method of the alkenyl-modified graphene oxide-ferroferric oxide composite material is the same as that in Example 1; immerse nylon 66 powder in an aqueous solution of potassium persulfate at 0.4 wt%, and the mass ratio of nylon 66 powder to the aqueous solution of potassium persulfate at 0.4 wt% is 1:30. Carry out a pre-initiation reaction under microwave radiation conditions. After the reaction is completed, filter to obtain the pre-initiated nylon 66 powder; among them, the microwave power is 450 W, the temperature of the pre-initiation reaction is 80 °C, and the time of the pre-initiation reaction is 20 min; add oleic acid amide propyl-N,N-dimethyl quaternary ammonium salt, alkenyl-modified graphene oxide-ferroferric oxide composite material, and Span 20 to deionized water. After ultrasonic dispersion at a frequency of 50 kHz for 30 min, add the pre-initiated nylon 66 powder. The mass ratio of oleic acid amide propyl-N,N-dimethyl quaternary ammonium salt, alkenyl-modified graphene oxide-ferroferric oxide composite material, Span 20, deionized water, and pre-initiated nylon 66 powder is 4:8:5:800:100. Carry out a grafting reaction under microwave radiation conditions. After the reaction is completed, filter and wash 3 times with deionized water, and place it in a vacuum drying oven at 50 °C for drying for 24 h to obtain the additive; among them, the microwave power is 450 W, the temperature of the grafting reaction is 80 °C, and the time of the grafting reaction is 45 min;

[0047] Step 4: Blend and melt the additive with nylon 66 resin. The mass ratio of the additive to nylon 66 resin is 24:100. The melting temperature is 295 °C. The melt is ejected through a spinneret to form fiber filaments. The pressure of the spinneret is 18 MPa. Side blow cooling is carried out, and the temperature of the side blow is 18 °C. Draw, the draw ratio is 1.4 times, and cut short to obtain heat-generating polyamide fibers. The length of the heat-generating polyamide fibers is 38 mm; spin the heat-generating polyamide fibers into yarns to obtain heat-generating polyamide yarns. The yarn count of the heat-generating polyamide yarns is 25S. Spin the heat-generating polyamide yarns into fabrics through a knitting process to obtain polyamide fabrics. The gram weight of the polyamide fabrics is 210 g / m 2 ; Immerse the polyamide fabric in the finishing solution for impregnation treatment. The mass ratio of the polyamide fabric to the finishing solution is 1:25. The impregnation treatment is carried out at room temperature. Dip two times and roll two times, and the liquor pickup rate is 90%. After the impregnation is completed, irradiate both sides of the impregnated polyamide fabric with blue light with a wavelength of 405 nm for 30 min for a curing reaction, wash 3 times with deionized water, and dry at a temperature of 50 °C to obtain the modified polyamide fabric; among them, the preparation method of the finishing solution is the same as that in Example 1; use the modified polyamide fabric as the outer fabric and the inner fabric respectively, and sew the outer fabric and the inner fabric with equal area using polyester sewing thread. The gap between the outer fabric and the inner fabric forms an air layer to obtain a magnetic therapy fabric containing heat-generating polyamide fibers.

[0048] Example 3

[0049] This embodiment discloses a preparation method of a magnetic therapy fabric containing heat-generating polyamide fiber, comprising the following steps:

[0050] Step 1: Under nitrogen protection, drop N,N-dimethyl-1,3-propanediamine into oleic acid. The molar ratio of oleic acid to N,N-dimethyl-1,3-propanediamine is 1:1.8, and the dropping rate of N,N-dimethyl-1,3-propanediamine is 1.5 mL / min. After the dropping is completed, carry out a closed reaction at 140 °C for 9 h under nitrogen protection. After the reaction ends, carry out vacuum distillation at 80 °C and 0.1 MPa to remove unreacted N,N-dimethyl-1,3-propanediamine and the generated water. Add n-hexane for crystallization with a mass 3 times that of oleic acid, filter, wash the filter residue with n-hexane 3 times, and then carry out vacuum drying at 60 °C and 0.1 MPa until constant weight to obtain oleic acid amide propyl-N,N-dimethyl tertiary amine;

[0051] Step 2: Dissolve oleic acid amide propyl-N,N-dimethyl tertiary amine in isopropanol-deionized water, add n-butyl bromide. The molar ratio of oleic acid amide propyl-N,N-dimethyl tertiary amine to n-butyl bromide is 1:1.15, and the dosage of isopropanol-deionized water is 4 times the mass of oleic acid amide propyl-N,N-dimethyl tertiary amine. React at 85 °C for 5 h. After the reaction ends, carry out vacuum distillation at 70 °C and 0.1 MPa to remove isopropanol and deionized water. Add a mixed solvent of n-hexane-ethyl acetate for crystallization with a mass 3 times that of oleic acid amide propyl-N,N-dimethyl tertiary amine, filter, wash the filter residue with the mixed solvent of n-hexane-ethyl acetate 3 times, and then carry out vacuum drying at 60 °C and 0.1 MPa until constant weight to obtain oleic acid amide propyl-N,N-dimethyl quaternary ammonium salt; wherein, the isopropanol-deionized water is a mixture of isopropanol and deionized water in a mass ratio of 1:2.

[0052] Step 3: Prepare vinyl-modified graphene oxide-ferroferric oxide composite; the preparation method of the vinyl-modified graphene oxide-ferroferric oxide composite is the same as that in Example 1; Immerse nylon 66 powder in an aqueous solution of 0.3 wt% potassium persulfate, and the mass ratio of nylon 66 powder to the aqueous solution of 0.3 wt% potassium persulfate is 1:25. Carry out a pre-initiation reaction under microwave radiation conditions. After the reaction is completed, filter to obtain pre-initiated nylon 66 powder; among them, the microwave power is 400 W, the temperature of the pre-initiation reaction is 70 °C, and the time of the pre-initiation reaction is 30 min; Add oleic acid amide propyl-N,N-dimethyl quaternary ammonium salt, vinyl-modified graphene oxide-ferroferric oxide composite, and Span 20 into deionized water, ultrasonically disperse for 30 min at a frequency of 50 kHz, then add the pre-initiated nylon 66 powder. The mass ratio of oleic acid amide propyl-N,N-dimethyl quaternary ammonium salt, vinyl-modified graphene oxide-ferroferric oxide composite, Span 20, deionized water, and pre-initiated nylon 66 powder is 2.5:5:3.5:650:100. Carry out a grafting reaction under microwave radiation conditions. After the reaction is completed, filter, wash 3 times with deionized water, and place in a vacuum drying oven at 50 °C for drying for 24 h to obtain an additive; among them, the microwave power is 400 W, the temperature of the grafting reaction is 70 °C, and the time of the grafting reaction is 60 min;

[0053] Step 4: Blend and melt the additive with nylon 66 resin. The mass ratio of the additive to nylon 66 resin is 20:100. The melting temperature is 290 °C. The melt is ejected through a spinneret to form fiber filaments. The pressure of the spinneret is 18 MPa. Cool with side blowing air, and the temperature of the side blowing air is 18 °C. Draw, and the draw ratio is 1.4 times. Cut short to obtain heat-generating polyamide fiber, and the length of the heat-generating polyamide fiber is 38 mm; Spin the heat-generating polyamide fiber into yarn to obtain heat-generating polyamide yarn, and the yarn count of the heat-generating polyamide yarn is 25S. Spin the heat-generating polyamide yarn into a fabric through a knitting process to obtain a polyamide fabric, and the gram weight of the polyamide fabric is 210 g / m 2 ; Immerse the polyamide fabric in a finishing solution for impregnation treatment. The mass ratio of the polyamide fabric to the finishing solution is 1:25. The impregnation treatment is carried out at room temperature. Dip two times and roll two times, and the liquor pickup rate is 90%. After the impregnation is completed, irradiate both sides of the impregnated polyamide fabric with blue light with a wavelength of 405 nm for 30 min for a curing reaction, wash 3 times with deionized water, and dry at a temperature of 50 °C to obtain a modified polyamide fabric; among them, the preparation method of the finishing solution is the same as that in Example 1; Use the modified polyamide fabric as the outer fabric and the inner fabric respectively, and sew the outer fabric and the inner fabric with equal area using polyester sewing thread. The gap between the outer fabric and the inner fabric forms an air layer to obtain a magnetic therapy fabric containing heat-generating polyamide fiber.

[0054] Example 4

[0055] This embodiment discloses a preparation method of a magnetic therapy fabric containing heat-generating polyamide fiber, which comprises the following steps:

[0056] Step 1: Under nitrogen protection, N,N-dimethyl-1,3-propanediamine is added dropwise to oleic acid. The molar ratio of oleic acid to N,N-dimethyl-1,3-propanediamine is 1:2.2, and the dropping rate of N,N-dimethyl-1,3-propanediamine is 1.5 mL / min. After the dropping is completed, the reaction is carried out in a sealed manner at a temperature of 140 °C for 9 h under nitrogen protection. After the reaction is completed, vacuum distillation is carried out at a temperature of 80 °C and a pressure of 0.1 MPa to remove unreacted N,N-dimethyl-1,3-propanediamine and the generated water. n-Hexane with a mass 3 times that of oleic acid is added for crystallization, and filtration is carried out. The filtration residue is washed 3 times with n-hexane and then vacuum dried to constant weight at a temperature of 60 °C and a pressure of 0.1 MPa to obtain oleic acid amide propyl-N,N-dimethyl tertiary amine;

[0057] Step 2: Oleic acid amide propyl-N,N-dimethyl tertiary amine is dissolved in isopropanol-deionized water, and bromobutane is added. The molar ratio of oleic acid amide propyl-N,N-dimethyl tertiary amine to bromobutane is 1:1.25, and the amount of isopropanol-deionized water used is 4 times the mass of oleic acid amide propyl-N,N-dimethyl tertiary amine. The reaction is carried out at a temperature of 85 °C for 5 h. After the reaction is completed, vacuum distillation is carried out at a temperature of 70 °C and a pressure of 0.1 MPa to remove isopropanol and deionized water. A mixed solvent of n-hexane-ethyl acetate with a mass 3 times that of oleic acid amide propyl-N,N-dimethyl tertiary amine is added for crystallization, and filtration is carried out. The filtration residue is washed 3 times with the mixed solvent of n-hexane-ethyl acetate and then vacuum dried to constant weight at a temperature of 60 °C and a pressure of 0.1 MPa to obtain oleic acid amide propyl-N,N-dimethyl quaternary ammonium salt; wherein, isopropanol-deionized water is a mixture of isopropanol and deionized water in a mass ratio of 1:2;

[0058] Step 3. Prepare alkenyl-modified graphene oxide-ferroferric oxide composite; the preparation method of the alkenyl-modified graphene oxide-ferroferric oxide composite is the same as that in Example 1; immerse nylon 66 powder in an aqueous solution of potassium persulfate at 0.3 wt%, and the mass ratio of nylon 66 powder to the aqueous solution of potassium persulfate at 0.3 wt% is 1:25, and perform a pre-initiation reaction under microwave radiation conditions. After the reaction is completed, filter to obtain pre-initiated nylon 66 powder; wherein, the microwave power is 400 W, the temperature of the pre-initiation reaction is 70 °C, and the time of the pre-initiation reaction is 30 min; add oleic acid amide propyl-N,N-dimethyl quaternary ammonium salt, alkenyl-modified graphene oxide-ferroferric oxide composite, and Span 20 into deionized water, ultrasonically disperse for 30 min at a frequency of 50 kHz, then add the pre-initiated nylon 66 powder. The mass ratio of oleic acid amide propyl-N,N-dimethyl quaternary ammonium salt, alkenyl-modified graphene oxide-ferroferric oxide composite, Span 20, deionized water, and pre-initiated nylon 66 powder is 3.5:7:4.5:750:100, and perform a grafting reaction under microwave radiation conditions. After the reaction is completed, filter, wash 3 times with deionized water, and place in a vacuum drying oven at 50 °C for drying for 24 h to obtain an auxiliary agent; wherein, the microwave power is 400 W, the temperature of the grafting reaction is 70 °C, and the time of the grafting reaction is 60 min;

[0059] Step 4. Blend and melt the auxiliary agent with nylon 66 resin. The mass ratio of the auxiliary agent to nylon 66 resin is 22:100, the melting temperature is 290 °C, the melt is ejected through a spinneret to form fiber filaments, the pressure of the spinneret is 18 MPa, and it is cooled by side blowing air. The temperature of the side blowing air is 18 °C, and it is drawn, and the draw ratio is 1.4 times. Then it is cut short to obtain heat-generating polyamide fiber, and the length of the heat-generating polyamide fiber is 38 mm; spin the heat-generating polyamide fiber into yarn to obtain heat-generating polyamide yarn, and the yarn count of the heat-generating polyamide yarn is 25 S. Weave the heat-generating polyamide yarn into a fabric through a knitting process to obtain a polyamide fabric, and the gram weight of the polyamide fabric is 210 g / m 2 ; Immerse the polyamide fabric in a finishing solution for impregnation treatment. The mass ratio of the polyamide fabric to the finishing solution is 1:25, and the impregnation treatment is carried out at room temperature, dip-dyeing and padding twice, and the liquor ratio is 90%. After the impregnation is completed, irradiate both sides of the impregnated polyamide fabric with blue light with a wavelength of 405 nm for 30 min for a curing reaction, wash 3 times with deionized water, and dry at a temperature of 50 °C to obtain a modified polyamide fabric; wherein, the preparation method of the finishing solution is the same as that in Example 1; use the modified polyamide fabric as the outer fabric and the inner fabric respectively, and sew the outer fabric and the inner fabric with equal area using polyester sewing thread. The gap between the outer fabric and the inner fabric forms an air layer to obtain a magnetic therapy fabric containing heat-generating polyamide fiber.

[0060] Comparative Example 1

[0061] This comparative example discloses a preparation method of a magnetic therapy fabric containing heat-generating polyamide fiber, which includes the following steps:

[0062] Step 1: Prepare an alkenyl-modified graphene oxide-ferroferric oxide composite material; the preparation method of the alkenyl-modified graphene oxide-ferroferric oxide composite material is the same as that in Example 1; Immerse nylon 66 powder in an aqueous solution of 0.2 wt% potassium persulfate, and the mass ratio of nylon 66 powder to the aqueous solution of 0.2 wt% potassium persulfate is 1:20. Carry out a pre-initiation reaction under microwave radiation conditions. After the reaction ends, filter to obtain pre-initiated nylon 66 powder; among them, the microwave power is 350 W, the temperature of the pre-initiation reaction is 60 °C, and the time of the pre-initiation reaction is 40 min; Add the alkenyl-modified graphene oxide-ferroferric oxide composite material and Span 20 to deionized water, ultrasonically disperse for 30 min at a frequency of 50 kHz, and then add the pre-initiated nylon 66 powder. The mass ratio of the alkenyl-modified graphene oxide-ferroferric oxide composite material, Span 20, deionized water, and pre-initiated nylon 66 powder is 4:3:600:102. Carry out a grafting reaction under microwave radiation conditions. After the reaction ends, filter and wash 3 times with deionized water, and place in a vacuum drying oven at 50 °C for drying for 24 h to obtain an auxiliary agent; among them, the microwave power is 350 W, the temperature of the grafting reaction is 60 °C, and the time of the grafting reaction is 75 min;

[0063] Step 2: Blend and melt the auxiliary agent with nylon 66 resin. The mass ratio of the auxiliary agent to nylon 66 resin is 18:100, the melting temperature is 285 °C, the melt is ejected through a spinneret to form fiber filaments, the pressure of the spinneret is 18 MPa, and it is cooled by side blowing. The temperature of the side blowing is 18 °C, and it is drawn, and the draw ratio is 1.4 times. Short cut to obtain heat-generating polyamide fiber, and the length of the heat-generating polyamide fiber is 38 mm; Spin the heat-generating polyamide fiber into yarn to obtain heat-generating polyamide yarn, and the yarn count of the heat-generating polyamide yarn is 25S. Spin the heat-generating polyamide yarn into a fabric through a knitting process to obtain a polyamide fabric, and the gram weight of the polyamide fabric is 210 g / m 2 ; Immerse the polyamide fabric in a finishing solution for impregnation treatment. The mass ratio of the polyamide fabric to the finishing solution is 1:15. The impregnation treatment is carried out at room temperature, dip-dyeing and padding twice, and the liquor pickup rate is 90%. After the impregnation is completed, irradiate both sides of the impregnated polyamide fabric with blue light with a wavelength of 405 nm for 30 min for a curing reaction, wash 3 times with deionized water, and dry at a temperature of 50 °C to obtain a modified polyamide fabric; among them, the preparation method of the finishing solution is the same as that in Example 1; Use the modified polyamide fabric as the outer fabric and the inner fabric respectively, and sew the outer fabric and the inner fabric with equal area using polyester sewing thread. The gap between the outer fabric and the inner fabric forms an air layer to obtain a magnetic therapy fabric containing heat-generating polyamide fiber.

[0064] Comparative Example 2

[0065] This comparative example discloses a preparation method of a magnetic therapy fabric containing heat-generating polyamide fiber, which includes the following steps:

[0066] Step 1: Under nitrogen protection, drop N,N-dimethyl-1,3-propanediamine into oleic acid. The molar ratio of oleic acid to N,N-dimethyl-1,3-propanediamine is 1:1.5, and the dropping rate of N,N-dimethyl-1,3-propanediamine is 1 mL / min. After the dropping is completed, carry out a closed reaction at 130 °C for 10 h under nitrogen protection. After the reaction ends, carry out vacuum distillation at 80 °C and 0.1 MPa to remove unreacted N,N-dimethyl-1,3-propanediamine and the generated water. Add n-hexane for crystallization with a mass 3 times that of oleic acid, filter, wash the filter residue with n-hexane 3 times, and then carry out vacuum drying at 60 °C and 0.1 MPa until constant weight to obtain oleic acid amide propyl-N,N-dimethyl tertiary amine;

[0067] Step 2: Dissolve oleic acid amide propyl-N,N-dimethyl tertiary amine in isopropanol-deionized water, add n-butyl bromide. The molar ratio of oleic acid amide propyl-N,N-dimethyl tertiary amine to n-butyl bromide is 1:1.1, and the dosage of isopropanol-deionized water is 3 times the mass of oleic acid amide propyl-N,N-dimethyl tertiary amine. React at 80 °C for 6 h. After the reaction ends, carry out vacuum distillation at 70 °C and 0.1 MPa to remove isopropanol and deionized water. Add a mixed solvent of n-hexane-ethyl acetate for crystallization with a mass 3 times that of oleic acid amide propyl-N,N-dimethyl tertiary amine, filter, wash the filter residue with the mixed solvent of n-hexane-ethyl acetate 3 times, and then carry out vacuum drying at 60 °C and 0.1 MPa until constant weight to obtain oleic acid amide propyl-N,N-dimethyl quaternary ammonium salt; wherein, isopropanol-deionized water is a mixture of isopropanol and deionized water in a mass ratio of 1:2;

[0068] Step 3: Immerse nylon 66 powder in 0.2 wt% potassium persulfate aqueous solution. The mass ratio of nylon 66 powder to 0.2 wt% potassium persulfate aqueous solution is 1:20. Carry out pre-initiation reaction under microwave radiation. After the reaction ends, filter to obtain pre-initiated nylon 66 powder. Among them, the microwave power is 350 W, the temperature of the pre-initiation reaction is 60 °C, and the time of the pre-initiation reaction is 40 min. Add oleic acid amide propyl-N,N-dimethyl quaternary ammonium salt and Span 20 into deionized water, ultrasonically disperse for 30 min at a frequency of 50 kHz, then add the pre-initiated nylon 66 powder. The mass ratio of oleic acid amide propyl-N,N-dimethyl quaternary ammonium salt, Span 20, deionized water, and pre-initiated nylon 66 powder is 2:3:600:100. Carry out grafting reaction under microwave radiation. After the reaction ends, filter, wash 3 times with deionized water, and place in a vacuum drying oven at 50 °C for drying for 24 h to obtain the additive. Among them, the microwave power is 350 W, the temperature of the grafting reaction is 60 °C, and the time of the grafting reaction is 75 min;

[0069] Step 4: Blend and melt the additive, graphene oxide-magnetite composite material and nylon 66 resin. The mass ratio of the additive, graphene oxide-magnetite composite material and nylon 66 resin is 17.2:0.8:100. The melting temperature is 285 °C. The melt is ejected through a spinneret to form fiber filaments. The pressure of the spinneret is 18 MPa. Cool with side blowing air, and the temperature of the side blowing air is 18 °C. Carry out drawing, and the drawing ratio is 1.4 times. Cut into short lengths to obtain heat-generating polyamide fiber, and the length of the heat-generating polyamide fiber is 38 mm. Spin the heat-generating polyamide fiber into yarn to obtain heat-generating polyamide yarn. The yarn count of the heat-generating polyamide yarn is 25S. Spin the heat-generating polyamide yarn into fabric through knitting process to obtain polyamide fabric, and the gram weight of the polyamide fabric is 210 g / m 2 ; Immerse the polyamide fabric in the finishing solution for impregnation treatment. The mass ratio of the polyamide fabric to the finishing solution is 1:15. The impregnation treatment is carried out at room temperature, dip two times and roll two times, and the liquor pickup rate is 90%. After the impregnation is completed, irradiate both sides of the impregnated polyamide fabric under blue light with a wavelength of 405 nm for 30 min for curing reaction, wash 3 times with deionized water, and dry at 50 °C to obtain the modified polyamide fabric. Among them, the preparation method of the finishing solution is the same as that in Example 1; Use the modified polyamide fabric as the outer fabric and the inner fabric respectively, and sew the outer fabric and the inner fabric with equal area using polyester sewing thread. The gap between the outer fabric and the inner fabric forms an air layer to obtain the magnetic therapy fabric containing heat-generating polyamide fiber.

[0070] In the above examples and comparative examples, oleic acid (cis-9-octadecenoic acid) was purchased from Guangzhou Xiangmei Chemical Technology Co., Ltd., CAS No.: 112-80-1, content: 99%; nano-graphene oxide was graphene oxide nanosheets, purchased from Shanghai Naiou Nano Technology Co., Ltd., product number: NO-C-068-1, thickness: <2 nm, diameter: <20 μm; nano-ferroferric oxide was purchased from Wenzhou Jingcheng Chemical Co., Ltd., model: SS-F908M, average particle size: 30-50 nm; nylon 66 powder was purchased from Dongguan Chengjie Plastic Raw Materials Co., Ltd., brand: DuPont, grade: 101L, particle size: 150 mesh; nylon 66 resin was purchased from Dongguan Heyue Plastic Co., Ltd., product name: polyamide 66, specification model: 101L, product state: granular; acrylic fiber was cut from acrylic filaments, the length of the acrylic fiber was 38 mm, the acrylic filaments were purchased from Shaoxing Xinen Textile Technology Co., Ltd., product number: JL-1, fineness: 150D; polyester sewing thread was purchased from Guangzhou Hongqiao Industrial Co., Ltd., specification: 120D / 3-80#.

[0071] Test Example

[0072] (1) Heat generation performance: Referring to the "Far-infrared irradiation temperature rise test" in the standard GB / T30127-2013 "Textiles - Detection and evaluation of far-infrared performance", the temperature rise value (°C) of the polyamide fabric (outer fabric) specimens prepared in Examples 1-4 and Comparative Examples 1-2 after 30 s of far-infrared irradiation was measured. Each specimen was tested three times, and the average value of the three temperature rises of each specimen was used as the measurement result. The measurement results are shown in Table 1:

[0073]

[0074] As can be seen from Table 1, the polyamide fabric prepared by the present invention has good far-infrared heat generation performance due to the addition of the far-infrared heat generation material graphene oxide. Compared with Example 1, in Comparative Example 2, the graphene oxide-ferroferric oxide composite material was not connected to the nylon 66 molecule through a stable chemical bond to prepare the additive, resulting in a decrease in its dispersion uniformity in the nylon 66 resin and a decrease in the far-infrared heat generation performance.

[0075] (2) Magnetic properties: Referring to the standard FZ / T01116-2012 "Textiles - Detection and evaluation of magnetic properties determination", the magnetic induction intensity of the polyamide fabric (outer fabric) specimens prepared in Examples 1-4 and Comparative Examples 1-2 was measured. The measurement results are shown in Table 2:

[0076]

[0077] As can be seen from Table 2, the polyamide fabric prepared by the present invention has good magnetic properties due to the addition of the magnetic material magnetite. Compared with Example 1, in Comparative Example 2, the graphene oxide-magnetite composite material was not connected to the nylon 66 molecule through stable chemical bonds to prepare the additive, resulting in a decrease in its dispersion uniformity in the nylon 66 resin and a decrease in magnetic properties.

[0078] Antibacterial property: The antibacterial rates of the polyamide fabric (outer fabric) samples prepared in Examples 1-4 and Comparative Examples 1-2 after 50 washes were measured with reference to the standard FZ / T 73023-2006 "Antibacterial Knitted Fabrics". The measurement results are shown in Table 3:

[0079]

[0080] As can be seen from Table 3, the polyamide fabric prepared by the present invention has good antibacterial properties due to the introduction of graphene oxide and quaternary ammonium salt. Compared with Example 1, in Comparative Example 1, the antibacterial property decreased due to the absence of quaternary ammonium salt; in Comparative Example 2, the graphene oxide-magnetite composite material was not connected to the nylon 66 molecule through stable chemical bonds to prepare the additive, resulting in a decrease in its dispersion uniformity in the nylon 66 resin and a decrease in antibacterial property.

[0081] (4) Antistatic property: The antistatic properties of the polyamide fabric (outer fabric) samples prepared in Examples 1-4 and Comparative Examples 1-2 were measured with reference to the standard GB / T 12703.2-2009 "Textiles - Evaluation of electrostatic properties - Part 2: Surface charge density". The measurement results of the surface charge density are shown in Table 4:

[0082]

[0083] As can be seen from Table 4, the polyamide fabric prepared by the present invention has good antistatic properties due to the introduction of graphene oxide and quaternary ammonium salt. Compared with Example 1, in Comparative Example 1, the antistatic property decreased due to the absence of quaternary ammonium salt; in Comparative Example 2, the graphene oxide-magnetite composite material was not connected to the nylon 66 molecule through stable chemical bonds to prepare the additive, resulting in a decrease in its dispersion uniformity in the nylon 66 resin and a decrease in antistatic property.

[0084] Although the embodiments of the present invention have been shown and described, it will be understood by those of ordinary skill in the art that various changes, modifications, substitutions and variations can be made therein without departing from the principles and spirit of the present invention. The scope of the present invention is defined by the appended claims and their equivalents.

Claims

1. A preparation method of a magnetic therapy fabric containing heat-generating polyamide fiber, characterized in that, It includes the following steps: Step 1: Drop N,N-dimethyl-1,3-propanediamine into oleic acid. After the dropping is completed, conduct a reaction. After the reaction ends, conduct purification to obtain oleic acid amide propyl-N,N-dimethyl tertiary amine; Step 2: Dissolve oleic acid amide propyl-N,N-dimethyl tertiary amine in isopropanol-deionized water, add a quaternization reagent, conduct a reaction. After the reaction ends, conduct purification to obtain oleic acid amide propyl-N,N-dimethyl quaternary ammonium salt; Step 3: Dissolve γ-methacryloyloxypropyltrimethoxysilane in an ethanol aqueous solution, adjust the pH value to 4-5, add a graphene oxide-ferroferric oxide composite material, conduct ultrasonic dispersion, then conduct a reaction. After the reaction ends, conduct filtration, washing, and drying to obtain an alkenyl-modified graphene oxide-ferroferric oxide composite material; Immerse nylon 66 powder in an initiator solution, conduct a pre-initiation reaction under microwave radiation conditions. After the reaction ends, conduct filtration to obtain pre-initiated nylon 66 powder; Add oleic acid amide propyl-N,N-dimethyl quaternary ammonium salt, alkenyl-modified graphene oxide-ferroferric oxide composite material, and an emulsifier into deionized water, conduct ultrasonic dispersion, then add the pre-initiated nylon 66 powder, and conduct a grafting reaction under microwave radiation conditions. After the reaction ends, conduct filtration, washing, and drying to obtain an auxiliary agent; Step 4: Blend and melt the auxiliary agent with nylon 66 resin. The melt is extruded through a spinneret to form fiber filaments, which are cooled by side blowing, drawn, and cut short to obtain heat-generating polyamide fibers; Spin the heat-generating polyamide fibers into yarns to obtain heat-generating polyamide yarns, spin the heat-generating polyamide yarns into fabrics to obtain polyamide fabrics; Immerse the polyamide fabrics in a finishing solution for impregnation treatment. After the impregnation is completed, conduct photocuring treatment, washing, and drying to obtain modified polyamide fabrics; The mass ratio of the polyamide fabric to the finishing solution is 1:(15-25). The impregnation treatment is carried out at room temperature, with two dips and two rolls, and the liquor pickup rate is 90%; The finishing solution is prepared through the following steps: Add dimethyldiallylammonium chloride, acrylamide, 2-hydroxyethyl methacrylate, and a photoinitiator into deionized water, and conduct ultrasonic dispersion to obtain the finishing solution; Among them, the mass ratio of dimethyldiallylammonium chloride, acrylamide, 2-hydroxyethyl methacrylate, the photoinitiator, and deionized water is (16-20):(7-10):(13-18):(3.5-6):(300-500); The photoinitiator includes lithium phenyl(2,4,6-trimethylbenzoyl)phosphate; Use the modified polyamide fabrics as the outer fabric and the inner fabric respectively, sew the outer fabric and the inner fabric with equal areas, and the gap between the outer fabric and the inner fabric forms an air layer to obtain a magnetic therapy fabric containing heat-generating polyamide fibers.

2. The preparation method of a magnetic therapy fabric containing heat-generating polyamide fiber according to claim 1, characterized in that, In the said Step 1, the molar ratio of oleic acid to N,N-dimethyl-1,3-propanediamine is 1:(1.5-2.5), the dropping rate of N,N-dimethyl-1,3-propanediamine is 1-2 mL / min, and the reaction conditions are to conduct a closed reaction at 130-150 °C for 8-10 h under nitrogen protection.

3. The preparation method of a magnetic therapy fabric containing heat-generating polyamide fiber according to claim 1, characterized in that, In the second step, the molar ratio of oleamide propyl-N,N-dimethyl tertiary amine to the quaternization reagent is 1:(1.1 - 1.3), the amount of isopropanol-deionized water is 3 - 5 times the mass of oleamide propyl-N,N-dimethyl tertiary amine, and the reaction conditions are to react at a temperature of 80 - 90 °C for 4 - 6 h; the quaternization reagent includes n-butyl bromide; the isopropanol-deionized water is a mixture of isopropanol and deionized water in a mass ratio of 1:

2.

4. The preparation method of a magnetic therapy fabric containing heat-generating polyamide fiber according to claim 1, characterized in that, In the third step, when preparing the alkenyl-modified graphene oxide-ferroferric oxide composite material, the mass ratio of the graphene oxide-ferroferric oxide composite material, γ-methacryloxypropyltrimethoxysilane, and ethanol aqueous solution is 0.2:(0.8 - 1.2):(60 - 100), and the reaction conditions are to react at a temperature of 50 - 70 °C for 6 - 8 h; among them, the graphene oxide-ferroferric oxide composite material is prepared by the following steps: adding amino-modified nano-ferroferric oxide and nano-graphene oxide into deionized water, ultrasonically dispersing, adding 1-ethyl-(3-dimethylaminopropyl)carbodiimide, reacting, filtering, washing, and drying after the reaction to obtain the graphene oxide-ferroferric oxide composite material; the mass ratio of the amino-modified nano-ferroferric oxide, nano-graphene oxide, deionized water, and 1-ethyl-(3-dimethylaminopropyl)carbodiimide is (15 - 25):(75 - 85):(800 - 1200):(15 - 25), and the reaction conditions are to stir and react at a temperature of 75 - 85 °C for 20 - 30 h; among them, the amino-modified nano-ferroferric oxide is prepared by the following steps: adding nano-ferroferric oxide into ethanol aqueous solution, ultrasonically dispersing, adding 3-aminopropyltrimethoxysilane, reacting, filtering, washing, and drying after the reaction to obtain the amino-modified nano-ferroferric oxide; the mass ratio of nano-ferroferric oxide, 3-aminopropyltrimethoxysilane, and ethanol aqueous solution is 0.1:(0.5 - 1.5):(50 - 70), and the reaction conditions are to react at a temperature of 40 - 50 °C for 6 - 10 h.

5. The preparation method of a magnetic therapy fabric containing heat-generating polyamide fiber according to claim 1, characterized in that, In the third step, when preparing the pre-initiated nylon 66 powder, the mass ratio of nylon 66 powder to the initiator solution is 1:(20 - 30), the microwave power is 350 - 450 W, the temperature of the pre-initiation reaction is 60 - 80 °C, and the time of the pre-initiation reaction is 20 - 40 min; the initiator solution includes an aqueous solution of potassium persulfate; the mass percentage content of potassium persulfate in the aqueous solution of potassium persulfate is 0.2 wt% - 0.4 wt%.

6. The preparation method of a magnetic therapy fabric containing heat-generating polyamide fiber according to claim 1, characterized in that, In the third step, when preparing the additive, the mass ratio of oleamide propyl-N,N-dimethyl quaternary ammonium salt, alkenyl-modified graphene oxide-ferroferric oxide composite material, emulsifier, deionized water, and pre-initiated nylon 66 powder is (2 - 4):(4 - 8):(3 - 5):(600 - 800):100, the microwave power is 350 - 450 W, the temperature of the grafting reaction is 60 - 80 °C, and the time of the grafting reaction is 45 - 75 min.

7. The preparation method of a magnetic therapy fabric containing heat-generating polyamide fiber according to claim 1, characterized in that, In the fourth step, the mass ratio of the auxiliary agent to the nylon 66 resin is (18 - 24):100, the melting temperature is 285 - 295 °C, the pressure of the spinneret is 16 - 20 MPa, the temperature of the side blowing air is 15 - 20 °C, and the draft ratio is 1.3 - 1.5 times; the yarn count of the heat-generating polyamide yarn is 20 - 30 S, and the gram weight of the polyamide fabric is 200 - 220 g / m 2 .

8. A magnetic therapy fabric containing heat-generating polyamide fiber prepared by the preparation method of the magnetic therapy fabric containing heat-generating polyamide fiber as described in any one of claims 1-7.

9. An application of the magnetic therapy fabric containing heat-generating polyamide fiber as described in claim 8 in textiles.

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