Graphene heating garment fabric and preparation method thereof

Abstract

The invention relates to the technical field of textile materials, in particular to a graphene heating garment fabric and a preparation method thereof, and is used for solving the problems that the heating performance of an existing graphene heating garment fabric is difficult to give full play and the antibacterial effect is limited. According to the preparation method, by adding the modified graphene and various metal elements, the garment material is endowed with heating and heat storage performance, extra heat is actively provided for a human body, the warm keeping effect is remarkably improved, meanwhile, by adding the modified graphene, the garment material is endowed with excellent antibacterial performance, and the prepared garment material has the warm keeping, health care and antibacterial functions and is worthy of popularization. According to the present invention, the fabric has characteristics of softness, moisture absorption and comfort, such that the fabric has good wearing experience, and the preparation method is simple, is easy to operate, is suitable for large-scale industrial production, and has wide market application prospects.

Description

Technical Field

[0001] The invention relates to the technical field of textile materials, and in particular to a graphene heating clothing fabric and a preparation method thereof. Background Art

[0002] With the improvement of living standards, people's demand for textiles and clothing is no longer limited to the traditional body covering, warmth keeping and beautiful decoration. Clothing fabrics with heating function are receiving more and more attention.

[0003] Graphene is a two-dimensional material with excellent thermal and electrical conductivity. It is widely considered to be an ideal material for preparing new heat-generating clothing fabrics because of its thinness, lightness, flexibility, and medical antibacterial properties. However, due to its own chemical structure and properties, graphene has problems such as poor dispersibility and weak interface bonding when compounded with fiber materials, which makes it difficult to fully exert its heat-generating performance and stability, and its antibacterial effect is limited, limiting the wide application of graphene in the field of heat-generating clothing fabrics.

[0004] Therefore, developing a graphene heating clothing fabric and a preparation method thereof is of great significance for improving the heating performance and antibacterial properties of clothing fabrics.

[0005] In view of the above technical defects, a solution is now proposed. Summary of the invention

[0006] In order to overcome the above-mentioned technical problems, the purpose of the present invention is to provide a graphene heating clothing fabric and a preparation method thereof, which solves the problem that the heating performance of existing graphene heating clothing fabrics is difficult to fully exert and the antibacterial effect is limited.

[0007] The purpose of the present invention can be achieved through the following technical solutions:

[0008] A method for preparing a graphene heating clothing fabric comprises the following steps:

[0009] Step 1: Weigh 100 parts of PET slices, 0.5-2.5 parts of modified graphene, 0.05-0.15 parts of iron oxide, 0.05-0.15 parts of aluminum oxide, 0.05-0.15 parts of zinc oxide, 0.05-0.15 parts of titanium dioxide, 1-5 parts of calcium stearate and 1-5 parts of magnesium stearate according to weight parts, and set aside;

[0010] Step 2: adding PET slices, modified graphene, iron oxide, aluminum oxide, zinc oxide, titanium dioxide, calcium stearate and magnesium stearate into a mixer, mixing them evenly, and then melting and extruding them through an extruder, and then conveying them to a spinning assembly, and then extruding them through a spinneret to obtain modified graphene fibers;

[0011] Step 3: uniformly mixing the modified graphene fiber and the cotton fiber in a mass ratio of 2:8 to obtain mixed fiber;

[0012] Step 4: Weaving the mixed fiber into a shape to obtain a weight of 250±10g / m 2 , graphene heating clothing fabric with a thickness of 0.65±0.05mm.

[0013] As a further solution of the present invention: the PET chips are Yizheng chemical fiber polyester chips PET with a melting point of 260° C. and a viscosity of 0.68 dl / g.

[0014] As a further solution of the present invention: the linear density of the modified graphene fiber is 1.66 dtex.

[0015] As a further solution of the present invention: the linear density of the cotton fiber is 1.47 dtex.

[0016] As a further solution of the present invention: the modified graphene is prepared by the following steps:

[0017] Step s1: adding graphite powder, concentrated sulfuric acid and sodium nitrate to a three-necked flask equipped with a stirrer and a thermometer, stirring and reacting for 30-40 minutes at a temperature of -5-0°C and a stirring rate of 300-400r / min, then adding potassium permanganate and continuing to stir and react for 20-30 minutes, then heating to 15-20°C and continuing to stir and react for 1-2 hours, then heating to 35-40°C and continuing to stir and react for 30-40 minutes, then adding deionized water and heating to 95-100°C and continuing to stir and react for 20-30 minutes, then adding hydrogen peroxide solution and continuing to stir and react for 20-30 minutes, after the reaction is completed, the reaction product is cooled to room temperature, then centrifuged, the precipitate is washed with hydrochloric acid solution and distilled water for 3-5 times in sequence, then placed in a vacuum drying oven, and dried at a temperature of 50-55°C for 3-5 hours to obtain graphene oxide;

[0018] Step s2: adding imidazole, sodium hydroxide and dimethyl sulfoxide to a three-necked flask equipped with a stirrer, a thermometer, an air guide tube and a constant pressure dropping funnel, introducing nitrogen protection, stirring the reaction for 20-30 minutes at a temperature of 25-30°C and a stirring rate of 300-400r / min, then heating to 60-65°C and continuing to stir the reaction for 1-2 hours, then adding 1,4-dibromobutane dropwise while stirring, controlling the dropping rate to 1-2 drops / s, and continuing to stir the reaction for 3-4 hours after the dropwise addition is completed. After the reaction is completed, the reaction product is cooled to room temperature, then added to ice water, and then vacuum filtered, and the filter cake is placed in a vacuum drying oven, and dried at a temperature of 60-65°C for 2-3 hours to obtain a bisimidazole intermediate;

[0019] Step s3: Add the bisimidazole intermediate, 3-chloropropyltrimethoxysilane, potassium iodide and N,N-dimethylformamide into a three-necked flask equipped with a stirrer, a thermometer and an air duct, introduce nitrogen protection, stir the reaction at a temperature of 25-30°C and a stirring rate of 300-400r / min for 30-40min, then heat the temperature to 125-130°C and continue stirring the reaction for 10-15h. After the reaction is completed, cool the reaction product to room temperature, then rotary evaporate to remove the solvent, then wash with anhydrous ether 3-5 times, then place in a vacuum drying oven, and dry at a temperature of 50-55°C for 3-5h to obtain a quaternary ammonium siloxane modifier;

[0020] Step s4: Add graphene oxide, anhydrous ethanol and deionized water to a three-necked flask equipped with a stirrer and a thermometer, perform ultrasonic treatment for 20-30 minutes at an ultrasonic frequency of 45-55kHz, then add a quaternary ammonium siloxane modifier and stir the reaction for 10-15 minutes at a temperature of 25-30°C and a stirring rate of 300-400r / min, then raise the temperature to 80-85°C and continue stirring the reaction for 4-5 hours. After the reaction is completed, cool the reaction product to room temperature, then vacuum filter, wash the filter cake with anhydrous methanol and distilled water for 3-5 times in turn, then place it in a vacuum drying oven, and dry it at a temperature of 50-55°C for 5-6 hours to obtain modified graphene.

[0021] As a further solution of the present invention: the usage ratio of the graphite powder, concentrated sulfuric acid, sodium nitrate, potassium permanganate, deionized water and hydrogen peroxide solution in step s1 is 2g:45-55mL:1-1.5g:6-8g:50-60mL:40-45mL.

[0022] As a further solution of the present invention: the mass fraction of the concentrated sulfuric acid in step s1 is 98%; the mass fraction of the hydrogen peroxide solution is 40%; and the mass fraction of the hydrochloric acid solution is 5%.

[0023] As a further solution of the present invention: the usage ratio of the imidazole, sodium hydroxide, dimethyl sulfoxide and 1,4-dibromobutane in step s2 is 22-25 mmol: 8-10 g: 40-50 mL: 10 mmol.

[0024] As a further solution of the present invention: the usage ratio of the bisimidazole intermediate, 3-chloropropyltrimethoxysilane, potassium iodide and N,N-dimethylformamide in step s3 is 10 mmol: 20 mmol: 0.05-0.07 g: 40-50 mL.

[0025] As a further solution of the present invention: the usage ratio of the graphene oxide, anhydrous ethanol, deionized water and quaternary ammonium siloxane modifier in step s4 is 2g:20-25mL:20-25mL:0.3-1.5g.

[0026] As a further solution of the present invention: the graphene heating clothing fabric is prepared according to the preparation method of the graphene heating clothing fabric.

[0027] Beneficial effects of the present invention:

[0028] The invention discloses a graphene heating clothing fabric and a preparation method thereof. The method comprises the following steps: adding PET slices, modified graphene, iron oxide, aluminum oxide, zinc oxide, titanium dioxide, calcium stearate and magnesium stearate into a mixer, melting and extruding the mixture through an extruder after uniform mixing, and then conveying the mixture into a spinning assembly, and then extruding the mixture through a spinneret to obtain modified graphene fibers; uniformly mixing the modified graphene fibers and cotton fibers to obtain mixed fibers; and weaving the mixed fibers into a shape to obtain the graphene heating clothing fabric. The preparation method adds modified graphene and a plurality of metal elements to give the clothing fabric heating and heat storage properties, actively provides additional heat to the human body, and significantly improves the warming effect. Meanwhile, the addition of modified graphene also gives the clothing fabric excellent antibacterial properties, so that the prepared clothing fabric has both warming, health care and antibacterial functions, and also takes into account softness, hygroscopicity and comfort, so that the fabric has a good wearing experience. The preparation method is simple and easy to operate, suitable for large-scale industrial production, and has broad market application prospects.

[0029] In the process of preparing graphene heating clothing fabric, a modified graphene is first prepared. First, graphite powder is used as a raw material to prepare graphene oxide, and then imidazole and 1,4-dibromobutane are reacted, and the NH on the imidazole reacts with the bromine atom on the 1,4-dibromobutane to obtain a biimidazole intermediate. Then, the biimidazole intermediate and 3-chloropropyltrimethoxysilane are reacted, and the imidazole ring on the biimidazole intermediate reacts with the chlorine atom on the 3-chloropropyltrimethoxysilane to form an imidazole cation, and a large amount of siloxane is introduced to obtain a quaternary ammonium siloxane modifier. Finally, the quaternary ammonium siloxane modifier is used to modify the graphene oxide, and the siloxane on the quaternary ammonium siloxane modifier is hydrolyzed to form silanol, which is dehydrated and condensed and grafted to the surface of the graphene oxide to obtain the modified graphene. Graphene can absorb external energy (such as solar After absorbing the energy of infrared radiation, the energy emitted by the human body, and the far-infrared energy emitted by various metal elements, the electrons inside it jump to a high energy level. When these electrons return to a low energy level, they release energy in the form of infrared radiation. This infrared radiation can be absorbed by the human body, making people feel warm. Infrared radiation has a certain penetrability and can penetrate deep into the human skin and subcutaneous tissue, resonate with human cells, promote blood circulation, accelerate the metabolism in the body, and enhance the body's sense of warmth. Graphene itself has excellent antibacterial properties. After modification with a quaternary ammonium siloxane modifier, its dispersibility is greatly improved, so that it can be evenly and stably distributed in the modified graphene fiber. The large amount of imidazole cations introduced play the role of a quaternary ammonium salt antibacterial agent, thereby significantly improving the heating and antibacterial properties of the fabric. DETAILED DESCRIPTION

[0030] In order to enable those skilled in the art to better understand the solutions of the present invention, the technical solutions in the embodiments of the present invention are described clearly and completely below. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0031] Embodiment 1:

[0032] This embodiment is a method for preparing a graphene heating clothing fabric, comprising the following steps:

[0033] Step S1: 2g of graphite powder, 45mL of concentrated sulfuric acid with a mass fraction of 98% and 1g of sodium nitrate are added to a three-necked flask equipped with a stirrer and a thermometer, and stirred for 30min at a temperature of -5°C and a stirring rate of 300r / min, then 6g of potassium permanganate is added and stirred for 20min, then the temperature is raised to 15°C and the stirring reaction is continued for 1h, then the temperature is raised to 35°C and the stirring reaction is continued for 30min, then 50mL of deionized water is added and the temperature is raised to 95°C and the stirring reaction is continued for 20min, then 40mL of a 40% hydrogen peroxide solution is added and the stirring reaction is continued for 20min, after the reaction is completed, the reaction product is cooled to room temperature, and then centrifuged, the precipitate is washed 3 times with a 5% hydrochloric acid solution and distilled water in sequence, and then placed in a vacuum drying oven and dried at a temperature of 50°C for 3h to obtain graphene oxide;

[0034] Step S2: 22mmol imidazole, 8g sodium hydroxide and 40mL dimethyl sulfoxide are added to a three-necked flask equipped with a stirrer, a thermometer, an air guide tube and a constant pressure dropping funnel, and nitrogen is introduced for protection. The mixture is stirred for reaction at a temperature of 25°C and a stirring rate of 300r / min for 20min, and then the temperature is raised to 60°C and the stirring reaction is continued for 1h. Then, 10mmol 1,4-dibromobutane is added dropwise while stirring, and the dropping rate is controlled to be 1 drop / s. After the dropwise addition is completed, the stirring reaction is continued for 3h. After the reaction is completed, the reaction product is cooled to room temperature, and then added to ice water, and then vacuum filtered. The filter cake is placed in a vacuum drying oven and dried at a temperature of 60°C for 2h to obtain a bisimidazole intermediate;

[0035] Step S3: 10 mmol of a bisimidazole intermediate, 20 mmol of 3-chloropropyltrimethoxysilane, 0.05 g of potassium iodide and 40 mL of N,N-dimethylformamide were added to a three-necked flask equipped with a stirrer, a thermometer and an air duct, and nitrogen was introduced for protection. The mixture was stirred at 25° C. and a stirring rate of 300 r / min for 30 min, and then the mixture was heated to 125° C. and the stirring reaction was continued for 10 h. After the reaction was completed, the reaction product was cooled to room temperature, and then the solvent was removed by rotary evaporation. The mixture was then washed with anhydrous ether 3 times, and then placed in a vacuum drying oven and dried at 50° C. for 3 h to obtain a quaternary ammonium siloxane modifier.

[0036] Step S4: 2 g of graphene oxide, 20 mL of anhydrous ethanol and 20 mL of deionized water are added to a three-necked flask equipped with a stirrer and a thermometer, and ultrasonically treated for 20 min at an ultrasonic frequency of 45 kHz, then 0.3 g of a quaternary ammonium siloxane modifier is added and stirred for 10 min at a temperature of 25° C. and a stirring rate of 300 r / min, then the temperature is raised to 80° C. and the stirring reaction is continued for 4 h. After the reaction is completed, the reaction product is cooled to room temperature, and then vacuum filtered. The filter cake is washed three times with anhydrous methanol and distilled water in sequence, and then placed in a vacuum drying oven and dried at a temperature of 50° C. for 5 h to obtain modified graphene;

[0037] Step S5: weigh 100 parts of PET slices, 0.5 parts of modified graphene, 0.05 parts of iron oxide, 0.05 parts of aluminum oxide, 0.05 parts of zinc oxide, 0.05 parts of titanium dioxide, 1 part of calcium stearate and 1 part of magnesium stearate according to weight parts for later use; the PET slices are Yizheng chemical fiber polyester slices PET with a melting point of 260° C. and a viscosity of 0.68 dl / g;

[0038] Step S6: adding PET slices, modified graphene, iron oxide, aluminum oxide, zinc oxide, titanium dioxide, calcium stearate and magnesium stearate into a mixer, mixing them evenly, and then melting and extruding them through an extruder, and then conveying them to a spinning assembly, and then extruding them through a spinneret to obtain modified graphene fibers;

[0039] Step S7: uniformly mixing the modified graphene fiber and the cotton fiber in a mass ratio of 2:8 to obtain mixed fiber; the linear density of the modified graphene fiber is 1.66 dtex; the linear density of the cotton fiber is 1.47 dtex;

[0040] Step S8: Weaving the mixed fiber into a shape to obtain a weight of 252 g / m 2 , graphene heating clothing fabric with a thickness of 0.61mm.

[0041] Embodiment 2:

[0042] This embodiment is a method for preparing a graphene heating clothing fabric, comprising the following steps:

[0043] Step S1: 2g of graphite powder, 50mL of concentrated sulfuric acid with a mass fraction of 98% and 1.2g of sodium nitrate are added to a three-necked flask equipped with a stirrer and a thermometer, and stirred for 35min at a temperature of -3°C and a stirring rate of 350r / min, then 7g of potassium permanganate is added and the stirring reaction is continued for 25min, then the temperature is raised to 18°C ​​and the stirring reaction is continued for 1.5h, then the temperature is raised to 38°C and the stirring reaction is continued for 35min, then 55mL of deionized water is added and the temperature is raised to 98°C and the stirring reaction is continued for 25min, then 42mL of a 40% hydrogen peroxide solution is added and the stirring reaction is continued for 25min, the reaction is completed and the reaction product is cooled to room temperature, then centrifuged, and the precipitate is washed 4 times with a mass fraction of 5% hydrochloric acid solution and distilled water in turn, then placed in a vacuum drying oven, and dried at a temperature of 52°C for 4h to obtain graphene oxide;

[0044] Step S2: 24mmol imidazole, 9g sodium hydroxide and 45mL dimethyl sulfoxide are added to a three-necked flask equipped with a stirrer, a thermometer, an air guide tube and a constant pressure dropping funnel, and nitrogen is introduced for protection. The reaction is stirred for 25min at a temperature of 28°C and a stirring rate of 350r / min, and then the temperature is raised to 62°C and the stirring reaction is continued for 1.5h. Then, 10mmol 1,4-dibromobutane is added dropwise while stirring, and the dropping rate is controlled to be 1 drop / s. After the dropwise addition is completed, the stirring reaction is continued for 3.5h. After the reaction is completed, the reaction product is cooled to room temperature, and then added to ice water, and then vacuum filtered. The filter cake is placed in a vacuum drying oven and dried at a temperature of 62°C for 2.5h to obtain a bisimidazole intermediate;

[0045] Step S3: 10 mmol of a bisimidazole intermediate, 20 mmol of 3-chloropropyltrimethoxysilane, 0.06 g of potassium iodide and 45 mL of N,N-dimethylformamide were added to a three-necked flask equipped with a stirrer, a thermometer and an air duct, and nitrogen was introduced for protection. The mixture was stirred at 28° C. and a stirring rate of 350 r / min for 35 min, and then the mixture was heated to 128° C. and the stirring reaction was continued for 12 h. After the reaction was completed, the reaction product was cooled to room temperature, and then the solvent was removed by rotary evaporation. The mixture was then washed with anhydrous ether 4 times, and then placed in a vacuum drying oven and dried at 52° C. for 4 h to obtain a quaternary ammonium siloxane modifier.

[0046] Step S4: 2 g of graphene oxide, 22 mL of anhydrous ethanol and 22 mL of deionized water were added to a three-necked flask equipped with a stirrer and a thermometer, and ultrasonically treated for 25 min at an ultrasonic frequency of 50 kHz, then 0.9 g of a quaternary ammonium siloxane modifier was added and stirred for 12 min at a temperature of 28 ° C and a stirring rate of 350 r / min, then the temperature was raised to 82 ° C and the stirring reaction was continued for 4.5 h. After the reaction was completed, the reaction product was cooled to room temperature, and then vacuum filtered, and the filter cake was washed with anhydrous methanol and distilled water for 4 times in sequence, and then placed in a vacuum drying oven and dried at a temperature of 52 ° C for 5.5 h to obtain modified graphene;

[0047] Step S5: weigh 100 parts of PET slices, 1.5 parts of modified graphene, 0.1 parts of iron oxide, 0.1 parts of aluminum oxide, 0.1 parts of zinc oxide, 0.1 parts of titanium dioxide, 3 parts of calcium stearate and 3 parts of magnesium stearate according to weight parts for later use; the PET slices are Yizheng chemical fiber polyester slices PET with a melting point of 260° C. and a viscosity of 0.68 dl / g;

[0048] Step S6: adding PET slices, modified graphene, iron oxide, aluminum oxide, zinc oxide, titanium dioxide, calcium stearate and magnesium stearate into a mixer, mixing them evenly, and then melting and extruding them through an extruder, and then conveying them to a spinning assembly, and then extruding them through a spinneret to obtain modified graphene fibers;

[0049] Step S7: uniformly mixing the modified graphene fiber and the cotton fiber in a mass ratio of 2:8 to obtain mixed fiber; the linear density of the modified graphene fiber is 1.66 dtex; the linear density of the cotton fiber is 1.47 dtex;

[0050] Step S8: spinning the mixed fiber into a shape to obtain a weight of 257 g / m 2 , graphene heating clothing fabric with a thickness of 0.65mm.

[0051] Embodiment 3:

[0052] This embodiment is a method for preparing a graphene heating clothing fabric, comprising the following steps:

[0053] Step S1: 2g of graphite powder, 55mL of concentrated sulfuric acid with a mass fraction of 98% and 1.5g of sodium nitrate are added to a three-necked flask equipped with a stirrer and a thermometer, and stirred for 40min at a temperature of 0°C and a stirring rate of 400r / min, then 8g of potassium permanganate is added and stirred for 30min, then the mixture is heated to 20°C and stirred for 2h, then the mixture is heated to 40°C and stirred for 40min, then 60mL of deionized water is added and the mixture is heated to 100°C and stirred for 30min, then 45mL of a 40% hydrogen peroxide solution is added and stirred for 30min, after the reaction is completed, the reaction product is cooled to room temperature, then centrifuged, and the precipitate is washed 5 times with a 5% hydrochloric acid solution and distilled water in sequence, then placed in a vacuum drying oven, and dried at a temperature of 55°C for 5h to obtain graphene oxide;

[0054] Step S2: 25mmol imidazole, 10g sodium hydroxide and 50mL dimethyl sulfoxide are added to a three-necked flask equipped with a stirrer, a thermometer, an air guide tube and a constant pressure dropping funnel, and nitrogen is introduced for protection. The mixture is stirred for reaction at a temperature of 30°C and a stirring rate of 400r / min for 30min, and then the temperature is raised to 65°C and the stirring reaction is continued for 2h. Then, 10mmol 1,4-dibromobutane is added dropwise while stirring, and the dropping rate is controlled to 2 drops / s. After the dropwise addition is completed, the stirring reaction is continued for 4h. After the reaction is completed, the reaction product is cooled to room temperature, and then added to ice water, and then vacuum filtered. The filter cake is placed in a vacuum drying oven and dried at a temperature of 65°C for 3h to obtain a bisimidazole intermediate;

[0055] Step S3: 10 mmol of a bisimidazole intermediate, 20 mmol of 3-chloropropyltrimethoxysilane, 0.07 g of potassium iodide and 50 mL of N,N-dimethylformamide were added to a three-necked flask equipped with a stirrer, a thermometer and an air duct, and nitrogen was introduced for protection. The mixture was stirred at 30° C. and a stirring rate of 400 r / min for 40 min, and then the mixture was heated to 130° C. and the stirring reaction was continued for 15 h. After the reaction was completed, the reaction product was cooled to room temperature, and then the solvent was removed by rotary evaporation. The mixture was then washed with anhydrous ether 5 times, and then placed in a vacuum drying oven and dried at 55° C. for 5 h to obtain a quaternary ammonium siloxane modifier.

[0056] Step S4: 2 g of graphene oxide, 25 mL of anhydrous ethanol and 25 mL of deionized water were added to a three-necked flask equipped with a stirrer and a thermometer, and ultrasonically treated for 30 min at an ultrasonic frequency of 55 kHz, then 1.5 g of a quaternary ammonium siloxane modifier was added and stirred for 15 min at a temperature of 30° C. and a stirring rate of 400 r / min, then the temperature was raised to 85° C. and the stirring reaction was continued for 5 h. After the reaction was completed, the reaction product was cooled to room temperature, and then vacuum filtered. The filter cake was washed 5 times with anhydrous methanol and distilled water in sequence, and then placed in a vacuum drying oven and dried at a temperature of 55° C. for 6 h to obtain modified graphene;

[0057] Step S5: weigh 100 parts of PET slices, 2.5 parts of modified graphene, 0.15 parts of iron oxide, 0.15 parts of aluminum oxide, 0.15 parts of zinc oxide, 0.15 parts of titanium dioxide, 5 parts of calcium stearate and 5 parts of magnesium stearate according to weight parts for later use; the PET slices are Yizheng chemical fiber polyester slices PET with a melting point of 260° C. and a viscosity of 0.68 dl / g;

[0058] Step S6: adding PET slices, modified graphene, iron oxide, aluminum oxide, zinc oxide, titanium dioxide, calcium stearate and magnesium stearate into a mixer, mixing them evenly, and then melting and extruding them through an extruder, and then conveying them to a spinning assembly, and then extruding them through a spinneret to obtain modified graphene fibers;

[0059] Step S7: uniformly mixing the modified graphene fiber and the cotton fiber in a mass ratio of 2:8 to obtain mixed fiber; the linear density of the modified graphene fiber is 1.66 dtex; the linear density of the cotton fiber is 1.47 dtex;

[0060] Step S8: Weaving the mixed fiber into a shape to obtain a weight of 245 g / m 2 , graphene heating clothing fabric with a thickness of 0.63mm.

[0061] Comparative Example 1:

[0062] This comparative example is a method for preparing a graphene heating clothing fabric, comprising the following steps:

[0063] Step S1: weigh 100 parts of PET slices, 0.15 parts of iron oxide, 0.15 parts of aluminum oxide, 0.15 parts of zinc oxide, 0.15 parts of titanium dioxide, 5 parts of calcium stearate and 5 parts of magnesium stearate according to weight parts, and set aside; the PET slices are Yizheng chemical fiber polyester slices PET with a melting point of 260° C. and a viscosity of 0.68 dl / g;

[0064] Step S2: adding PET chips, iron oxide, aluminum oxide, zinc oxide, titanium dioxide, calcium stearate and magnesium stearate into a mixer, mixing them evenly, and then melting and extruding them through an extruder, and then conveying them to a spinning assembly, and then extruding them through a spinneret to obtain modified fibers;

[0065] Step S3: uniformly mixing the modified fiber and the cotton fiber in a mass ratio of 2:8 to obtain mixed fiber; the linear density of the modified fiber is 1.66 dtex; the linear density of the cotton fiber is 1.47 dtex;

[0066] Step S4: spinning the mixed fiber into a shape to obtain a fiber having a gram weight of 253 g / m 2 , graphene heating clothing fabric with a thickness of 0.68mm.

[0067] Comparative Example 2:

[0068] This comparative example is a method for preparing a graphene heating clothing fabric, comprising the following steps:

[0069] Step S1: 2g of graphite powder, 55mL of concentrated sulfuric acid with a mass fraction of 98% and 1.5g of sodium nitrate are added to a three-necked flask equipped with a stirrer and a thermometer, and stirred for 40min at a temperature of 0°C and a stirring rate of 400r / min, then 8g of potassium permanganate is added and stirred for 30min, then the mixture is heated to 20°C and stirred for 2h, then the mixture is heated to 40°C and stirred for 40min, then 60mL of deionized water is added and the mixture is heated to 100°C and stirred for 30min, then 45mL of a 40% hydrogen peroxide solution is added and stirred for 30min, after the reaction is completed, the reaction product is cooled to room temperature, then centrifuged, and the precipitate is washed 5 times with a 5% hydrochloric acid solution and distilled water in sequence, then placed in a vacuum drying oven, and dried at a temperature of 55°C for 5h to obtain graphene oxide;

[0070] Step S2: weigh 100 parts of PET slices, 2.5 parts of graphene oxide, 0.15 parts of iron oxide, 0.15 parts of aluminum oxide, 0.15 parts of zinc oxide, 0.15 parts of titanium dioxide, 5 parts of calcium stearate and 5 parts of magnesium stearate according to weight parts for later use; the PET slices are Yizheng chemical fiber polyester slices PET with a melting point of 260° C. and a viscosity of 0.68 dl / g;

[0071] Step S3: adding PET chips, graphene oxide, iron oxide, aluminum oxide, zinc oxide, titanium dioxide, calcium stearate and magnesium stearate into a mixer, mixing them evenly, and then melting and extruding them through an extruder, and then conveying them to a spinning assembly, and then extruding them through a spinneret to obtain modified graphene fibers;

[0072] Step S4: uniformly mixing the modified graphene fiber and the cotton fiber in a mass ratio of 2:8 to obtain mixed fiber; the linear density of the modified graphene fiber is 1.66 dtex; the linear density of the cotton fiber is 1.47 dtex;

[0073] Step S5: spinning the mixed fiber into a shape to obtain a fiber having a gram weight of 255 g / m 2 , graphene heating clothing fabric with a thickness of 0.66mm.

[0074] Comparative Example 3:

[0075] This comparative example is a method for preparing a graphene heating clothing fabric, comprising the following steps:

[0076] Step S1: 2g of graphite powder, 55mL of concentrated sulfuric acid with a mass fraction of 98% and 1.5g of sodium nitrate are added to a three-necked flask equipped with a stirrer and a thermometer, and stirred for 40min at a temperature of 0°C and a stirring rate of 400r / min, then 8g of potassium permanganate is added and stirred for 30min, then the mixture is heated to 20°C and stirred for 2h, then the mixture is heated to 40°C and stirred for 40min, then 60mL of deionized water is added and the mixture is heated to 100°C and stirred for 30min, then 45mL of a 40% hydrogen peroxide solution is added and stirred for 30min, after the reaction is completed, the reaction product is cooled to room temperature, then centrifuged, and the precipitate is washed 5 times with a 5% hydrochloric acid solution and distilled water in sequence, then placed in a vacuum drying oven, and dried at a temperature of 55°C for 5h to obtain graphene oxide;

[0077] Step S2: 2 g of graphene oxide, 25 mL of anhydrous ethanol and 25 mL of deionized water were added to a three-necked flask equipped with a stirrer and a thermometer, and ultrasonically treated for 30 min at an ultrasonic frequency of 55 kHz, then 1.5 g of 3-chloropropyltrimethoxysilane was added and stirred for 15 min at a temperature of 30° C. and a stirring rate of 400 r / min, then the temperature was raised to 85° C. and the stirring reaction was continued for 5 h. After the reaction was completed, the reaction product was cooled to room temperature, and then vacuum filtered. The filter cake was washed 5 times with anhydrous methanol and distilled water in sequence, and then placed in a vacuum drying oven and dried at a temperature of 55° C. for 6 h to obtain modified graphene;

[0078] Step S3: weigh 100 parts of PET slices, 2.5 parts of modified graphene, 0.15 parts of iron oxide, 0.15 parts of aluminum oxide, 0.15 parts of zinc oxide, 0.15 parts of titanium dioxide, 5 parts of calcium stearate and 5 parts of magnesium stearate according to weight parts, and set aside; the PET slices are Yizheng chemical fiber polyester slices PET with a melting point of 260° C. and a viscosity of 0.68 dl / g;

[0079] Step S4: adding PET slices, modified graphene, iron oxide, aluminum oxide, zinc oxide, titanium dioxide, calcium stearate and magnesium stearate into a mixer, mixing them evenly, and then melting and extruding them through an extruder, and then conveying them to a spinning assembly, and then extruding them through a spinneret to obtain modified graphene fibers;

[0080] Step S5: uniformly mixing the modified graphene fiber and the cotton fiber in a mass ratio of 2:8 to obtain mixed fiber; the linear density of the modified graphene fiber is 1.66 dtex; the linear density of the cotton fiber is 1.47 dtex;

[0081] Step S6: Weaving the mixed fiber into a shape to obtain a fiber having a gram weight of 251 g / m 2 , graphene heating clothing fabric with a thickness of 0.62mm.

[0082] Comparative Example 4:

[0083] This comparative example is a method for preparing a graphene heating clothing fabric, comprising the following steps:

[0084] Step S1: 25mmol imidazole, 10g sodium hydroxide and 50mL dimethyl sulfoxide are added to a three-necked flask equipped with a stirrer, a thermometer, an air guide tube and a constant pressure dropping funnel, and nitrogen is introduced for protection. The mixture is stirred for reaction at a temperature of 30°C and a stirring rate of 400r / min for 30min, and then the temperature is raised to 65°C and the stirring reaction is continued for 2h. Then, 10mmol 1,4-dibromobutane is added dropwise while stirring, and the dropping rate is controlled to 2 drops / s. After the dropwise addition is completed, the stirring reaction is continued for 4h. After the reaction is completed, the reaction product is cooled to room temperature, and then added to ice water, and then vacuum filtered. The filter cake is placed in a vacuum drying oven and dried at a temperature of 65°C for 3h to obtain a bisimidazole intermediate;

[0085] Step S2: 10 mmol of a bisimidazole intermediate, 20 mmol of 3-chloropropyltrimethoxysilane, 0.07 g of potassium iodide and 50 mL of N,N-dimethylformamide were added to a three-necked flask equipped with a stirrer, a thermometer and an air duct, and nitrogen was introduced for protection. The mixture was stirred at 30° C. and a stirring rate of 400 r / min for 40 min, and then the mixture was heated to 130° C. and the stirring reaction was continued for 15 h. After the reaction was completed, the reaction product was cooled to room temperature, and then the solvent was removed by rotary evaporation. The mixture was then washed with anhydrous ether 5 times, and then placed in a vacuum drying oven and dried at 55° C. for 5 h to obtain a quaternary ammonium siloxane modifier.

[0086] Step S3: weigh 100 parts of PET slices, 2.5 parts of quaternary ammonium siloxane modifier, 0.15 parts of iron oxide, 0.15 parts of aluminum oxide, 0.15 parts of zinc oxide, 0.15 parts of titanium dioxide, 5 parts of calcium stearate and 5 parts of magnesium stearate according to weight parts, and set aside; the PET slices are Yizheng chemical fiber polyester slices PET with a melting point of 260° C. and a viscosity of 0.68 dl / g;

[0087] Step S4: adding PET chips, quaternary ammonium siloxane modifier, iron oxide, aluminum oxide, zinc oxide, titanium dioxide, calcium stearate and magnesium stearate into a mixer, mixing them evenly, and then melting and extruding them through an extruder, and then conveying them to a spinning assembly, and then extruding them through a spinneret to obtain modified fibers;

[0088] Step S5: uniformly mixing the modified fiber and the cotton fiber in a mass ratio of 2:8 to obtain mixed fiber; the linear density of the modified fiber is 1.66 dtex; the linear density of the cotton fiber is 1.47 dtex;

[0089] Step S6: spinning the mixed fiber into a shape to obtain a weight of 249 g / m 2 , graphene heating clothing fabric with a thickness of 0.65mm.

[0090] Blank example:

[0091] This blank example is a method for preparing a graphene heating clothing fabric, comprising the following steps:

[0092] Step S1: melt-extrude PET chips through an extruder, then transport them to a spinning assembly, and then extrude them through a spinneret to obtain PET fibers; the PET chips are Yizheng chemical fiber polyester chips PET with a melting point of 260° C. and a viscosity of 0.68 dl / g;

[0093] Step S2: PET fiber and cotton fiber are mixed evenly in a mass ratio of 2:8 to obtain mixed fiber; the linear density of the PET fiber is 1.66 dtex; the linear density of the cotton fiber is 1.47 dtex;

[0094] Step S3: spinning the mixed fiber into a shape to obtain a fiber having a gram weight of 254 g / m 2 , graphene heating clothing fabric with a thickness of 0.67mm.

[0095] The performance of the graphene heating clothing fabrics of Examples 1-3, Comparative Examples 1-4 and the blank example was tested, and the test results are shown in the following table:

[0096]

[0097] Referring to the data in the above table, based on the comparison between Examples 1-3, Comparative Examples 1-4 and the blank example, it can be seen that the graphene heating clothing fabric of the present application has excellent heating performance and antibacterial performance.

[0098] In the description of this specification, the description with reference to the terms "one embodiment", "example", "specific example", etc. means that the specific features, structures, materials or characteristics described in conjunction with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic representation of the above terms does not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described can be combined in any one or more embodiments or examples in a suitable manner.

[0099] The above contents are merely examples and explanations of the present invention. Those skilled in the art may make various modifications or additions to the specific embodiments described or replace them in a similar manner. As long as they do not deviate from the invention or exceed the scope defined in this application, they shall all fall within the protection scope of the present invention.

Claims

1. A method for preparing graphene heating clothing fabric, characterized in that: The following steps are involved: Step 1: Weigh 100 parts of PET slices, 0.5-2.5 parts of modified graphene, 0.05-0.15 parts of iron oxide, 0.05-0.15 parts of aluminum oxide, 0.05-0.15 parts of zinc oxide, 0.05-0.15 parts of titanium dioxide, 1-5 parts of calcium stearate and 1-5 parts of magnesium stearate according to weight parts, and set aside; Step 2: adding PET slices, modified graphene, iron oxide, aluminum oxide, zinc oxide, titanium dioxide, calcium stearate and magnesium stearate into a mixer, mixing them evenly, and then melting and extruding them through an extruder, and then conveying them to a spinning assembly, and then extruding them through a spinneret to obtain modified graphene fibers; Step 3: uniformly mixing the modified graphene fiber and the cotton fiber in a mass ratio of 2:8 to obtain mixed fiber; Step 4: Weaving the mixed fiber into a shape to obtain a weight of 250±10g / m 2 , graphene heating clothing fabric with a thickness of 0.65±0.05mm.

2. The method for preparing a graphene heating clothing fabric according to claim 1, characterized in that: The PET chips are Yizheng chemical fiber polyester chips PET with a melting point of 260°C and a viscosity of 0.68 dl / g; The linear density of the modified graphene fiber is 1.66 dtex; The linear density of the cotton fiber is 1.47 dtex.

3. The method for preparing a graphene heating clothing fabric according to claim 1, characterized in that: The modified graphene is prepared by the following steps: Step s1: stirring graphite powder, concentrated sulfuric acid and sodium nitrate for reaction, then sequentially adding potassium permanganate, deionized water and hydrogen peroxide solution and continuing stirring for reaction, cooling the reaction product after the reaction is completed, then centrifuging, washing and drying the precipitate to obtain graphene oxide; Step s2: stirring imidazole, sodium hydroxide and dimethyl sulfoxide for reaction, then adding 1,4-dibromobutane dropwise while stirring, and continuing to stir the reaction after the addition is complete. After the reaction is complete, the reaction product is cooled, then added into ice water, and then vacuum filtered, and the filter cake is dried to obtain a bisimidazole intermediate; Step s3: stirring the bisimidazole intermediate, 3-chloropropyltrimethoxysilane, potassium iodide and N,N-dimethylformamide for reaction, cooling the reaction product after the reaction is completed, then rotary evaporating, then washing and drying to obtain a quaternary ammonium siloxane modifier; Step s4: subjecting graphene oxide, anhydrous ethanol and deionized water to ultrasonic treatment, and then adding a quaternary ammonium siloxane modifier for stirring reaction. After the reaction is completed, the reaction product is cooled, and then vacuum filtered, and the filter cake is washed and dried to obtain modified graphene.

4. The method for preparing a graphene heating clothing fabric according to claim 3, characterized in that: The usage ratio of the graphite powder, concentrated sulfuric acid, sodium nitrate, potassium permanganate, deionized water and hydrogen peroxide solution in step s1 is 2g:45-55mL:1-1.5g:6-8g:50-60mL:40-45mL.

5. The method for preparing a graphene heating clothing fabric according to claim 3, characterized in that: The mass fraction of the concentrated sulfuric acid in step s1 is 98%; the mass fraction of the hydrogen peroxide solution is 40%.

6. The method for preparing a graphene heating clothing fabric according to claim 3, characterized in that: The usage ratio of the imidazole, sodium hydroxide, dimethyl sulfoxide and 1,4-dibromobutane in step s2 is 22-25mmol:8-10g:40-50mL:10mmol.

7. The method for preparing a graphene heating clothing fabric according to claim 3, characterized in that: The usage ratio of the bisimidazole intermediate, 3-chloropropyltrimethoxysilane, potassium iodide and N,N-dimethylformamide in step s3 is 10 mmol: 20 mmol: 0.05-0.07 g: 40-50 mL.

8. The method for preparing a graphene heating clothing fabric according to claim 3, characterized in that: The usage ratio of the graphene oxide, anhydrous ethanol, deionized water and quaternary ammonium siloxane modifier in step s4 is 2g:20-25mL:20-25mL:0.3-1.5g.

9. A graphene heating clothing fabric, characterized in that: The graphene heating clothing fabric is prepared according to the preparation method of the graphene heating clothing fabric according to any one of claims 1-8.

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