A graphene-based thermal clothing fabric and its preparation method

Abstract

This invention relates to the field of textile materials technology, specifically to a graphene-based heat-generating clothing fabric and its preparation method. It addresses the problems of existing graphene-based heat-generating clothing fabrics having limited heat-generating performance and antibacterial effects. This preparation method, by adding modified graphene and various metal elements, endows the clothing fabric with heat-generating and heat-retaining properties, actively providing extra heat to the human body, significantly improving warmth retention. Simultaneously, the addition of modified graphene also endows the fabric with excellent antibacterial properties, resulting in a clothing fabric that combines warmth, health benefits, and antibacterial functions, while also maintaining softness, moisture absorption, and comfort, providing a superior wearing experience. Furthermore, the preparation method is simple, easy to operate, suitable for large-scale industrial production, and has broad market application prospects.

Description

Technical Field

[0001] This invention relates to the field of textile materials technology, specifically to a graphene-based heat-generating clothing fabric and its preparation method. Background Technology

[0002] As living standards improve, people's demand for textiles and clothing is no longer limited to traditional covering, warmth, and aesthetic decoration; clothing fabrics with heat-generating functions are receiving increasing attention.

[0003] Graphene is a two-dimensional material with excellent thermal and electrical conductivity. Due to its thinness, lightness, flexibility, and medical antibacterial properties, it is widely considered an ideal material for preparing novel heat-generating clothing fabrics. However, due to its own chemical structure and properties, graphene suffers from poor dispersibility and weak interfacial bonding when combined with fibrous materials. This makes it difficult to fully realize its heating performance and stability, and its antibacterial effect is limited, thus restricting the widespread application of graphene in the field of heat-generating clothing fabrics.

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

[0005] To address the aforementioned technical shortcomings, a solution is proposed. Summary of the Invention

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

[0007] The objective of this invention can be achieved through the following technical solutions:

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

[0009] Step 1: Weigh out 100 parts of PET chips, 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 their weight, and set aside.

[0010] Step 2: Add PET chips, modified graphene, iron oxide, aluminum oxide, zinc oxide, titanium dioxide, calcium stearate and magnesium stearate to a mixer, mix evenly, melt and extrude through an extruder, then convey to a spinning assembly, and then extrude through a spinneret to obtain modified graphene fibers.

[0011] Step 3: Mix the modified graphene fiber and cotton fiber evenly at a mass ratio of 2:8 to obtain the mixed fiber;

[0012] Step 4: Spin the blended fibers into a shape to obtain a weight of 250±10g / m². 2 Graphene-based heating clothing fabric with a thickness of 0.65±0.05mm.

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

[0014] As a further aspect of the present invention, the modified graphene fiber has a linear density of 1.66 dtex.

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

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

[0017] Step s1: Add graphite powder, concentrated sulfuric acid, and sodium nitrate to a three-necked flask equipped with a stirrer and thermometer. Stir the reaction at -5 to 0°C for 30 to 40 minutes. Then add potassium permanganate and continue stirring for 20 to 30 minutes. Then raise the temperature to 15 to 20°C and continue stirring for 1 to 2 hours. Then raise the temperature to 35 to 40°C and continue stirring for 30 to 40 minutes. Then add deionized water and raise the temperature to 95 to 100°C and continue stirring for 20 to 30 minutes. Then add hydrogen peroxide solution and continue stirring for 20 to 30 minutes. After the reaction is complete, cool the reaction product to room temperature and centrifuge. Wash the precipitate 3 to 5 times with hydrochloric acid solution and distilled water. Then place it in a vacuum drying oven and dry it at 50 to 55°C for 3 to 5 hours to obtain graphene oxide.

[0018] Step s2: Imidazole, sodium hydroxide, and dimethyl sulfoxide are added to a three-necked flask equipped with a stirrer, thermometer, gas delivery tube, and constant pressure dropping funnel. Nitrogen gas is introduced for protection. The mixture is stirred for 20-30 min at a temperature of 25-30℃ and a stirring rate of 300-400 r / min. Then, the temperature is raised to 60-65℃ and the mixture is stirred for 1-2 h. Then, 1,4-dibromobutane is added dropwise while stirring, with the dropping rate controlled at 1-2 drops / s. After the addition is complete, the mixture is stirred for 3-4 h. After the reaction is complete, the reaction product is cooled to room temperature and then added to ice water. The mixture is then vacuum filtered, and the filter cake is placed in a vacuum drying oven and dried for 2-3 h at a temperature of 60-65℃ to obtain the diimidazole intermediate.

[0019] Step s3: Add the diimidazole intermediate, 3-chloropropyltrimethoxysilane, potassium iodide, and N,N-dimethylformamide to a three-necked flask equipped with a stirrer, thermometer, and gas delivery tube. Purge with nitrogen for protection and stir the reaction at 25-30℃ and a stirring rate of 300-400 r / min for 30-40 min. Then raise the temperature to 125-130℃ and continue stirring for 10-15 h. After the reaction is complete, cool the reaction product to room temperature, then remove the solvent by rotary evaporation. Wash the product 3-5 times with anhydrous diethyl ether and then place it in a vacuum drying oven at 50-55℃ for 3-5 h to obtain the 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 thermometer. Sonicate the mixture at a frequency of 45-55 kHz for 20-30 min. Then add a quaternary ammonium siloxane modifier and stir the mixture at a temperature of 25-30℃ and a stirring rate of 300-400 r / min for 10-15 min. Then raise the temperature to 80-85℃ and continue stirring for 4-5 h. After the reaction is complete, cool the reaction product to room temperature and then filter it under vacuum. Wash the filter cake with anhydrous methanol and distilled water 3-5 times in sequence. Then place it in a vacuum drying oven and dry it at a temperature of 50-55℃ for 5-6 h to obtain modified graphene.

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

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

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

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

[0025] As a further aspect of the present invention: the ratio of 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 aspect of the present invention: the graphene heating clothing fabric is prepared according to the preparation method of the graphene heating clothing fabric.

[0027] The beneficial effects of this invention are:

[0028] This invention discloses a graphene-based thermal clothing fabric and its preparation method. The method involves adding PET chips, modified graphene, iron oxide, aluminum oxide, zinc oxide, titanium dioxide, calcium stearate, and magnesium stearate to a mixer, mixing them evenly, and then melting and extruding the mixture through an extruder. The resulting material is then fed into a spinning assembly and extruded through a spinneret to obtain modified graphene fibers. These modified graphene fibers are then evenly mixed with cotton fibers to obtain a mixed fiber. Finally, the mixed fiber is spun into the final graphene-based thermal clothing fabric. This preparation method, by adding modified graphene and various metal elements, endows the clothing fabric with thermal heating and heat storage properties, actively providing extra heat to the human body and significantly improving its warmth retention. Simultaneously, the addition of modified graphene also endows the fabric with excellent antibacterial properties, resulting in a clothing fabric that combines warmth, health benefits, and antibacterial functions while maintaining softness, moisture absorption, and comfort, providing a superior wearing experience. Furthermore, the preparation method is simple, easy to operate, suitable for large-scale industrial production, and has broad market application prospects.

[0029] In the preparation of graphene-based heating clothing fabric, a modified graphene was first prepared. Firstly, graphene oxide was prepared using graphite powder as a raw material. Then, imidazole and 1,4-dibromobutane were reacted, with the NH atom on the imidazole reacting with the bromine atom on the 1,4-dibromobutane to obtain a bisimidazole intermediate. Next, the bisimidazole intermediate was reacted with 3-chloropropyltrimethoxysilane, with the imidazole ring on the bisimidazole intermediate reacting with the chlorine atom on the 3-chloropropyltrimethoxysilane to form an imidazole cation. Simultaneously, a large amount of siloxane was introduced to obtain a quaternary ammonium siloxane modifier. Finally, the quaternary ammonium siloxane modifier was used to modify the graphene oxide. The siloxane on the quaternary ammonium siloxane modifier hydrolyzed to form silanols, which then dehydrated and condensed, grafting onto the surface of the graphene oxide to obtain the modified graphene. Graphene can absorb external energy (such as solar energy). After the energy emitted by the human body and the far-infrared energy emitted by various metal elements is absorbed, the electrons inside the graphene fiber jump to a higher energy level. When these electrons return to a lower 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. Moreover, infrared radiation has a certain degree of penetrability and can penetrate deep into the human skin and subcutaneous tissue, resonating with human cells, promoting blood circulation, accelerating the body's metabolism, and enhancing the body's feeling of warmth. Furthermore, graphene itself has excellent antibacterial properties. After being modified by quaternary ammonium siloxane modifier, its dispersibility is greatly improved, allowing it to be evenly and stably distributed in the modified graphene fiber. In addition, the large number of imidazole cations introduced act as quaternary ammonium salt antibacterial agents, thereby significantly improving the fabric's heating and antibacterial properties. Detailed Implementation

[0030] To enable those skilled in the art to better understand the present invention, the technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0031] Example 1:

[0032] This embodiment describes a method for preparing graphene-based thermal clothing fabric, comprising the following steps:

[0033] Step S1: Add 2g of graphite powder, 45mL of 98% concentrated sulfuric acid and 1g of sodium nitrate to a three-necked flask equipped with a stirrer and thermometer. Stir the reaction at -5℃ and 300r / min for 30min. Then add 6g of potassium permanganate and continue stirring for 20min. Then raise the temperature to 15℃ and continue stirring for 1h. Then raise the temperature to 35℃ and continue stirring for 30min. Then add 50mL of deionized water and raise the temperature to 95℃ and continue stirring for 20min. Then add 40mL of 40% hydrogen peroxide solution and continue stirring for 20min. After the reaction is complete, cool the reaction product to room temperature and centrifuge. Wash the precipitate three times with 5% hydrochloric acid solution and distilled water. Then place it in a vacuum drying oven and dry it at 50℃ for 3h to obtain graphene oxide.

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

[0035] Step S3: 10 mmol of diimidazole 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, thermometer and gas delivery tube. Nitrogen gas was introduced for protection. The mixture was stirred at 25 °C and 300 r / min for 30 min. Then the temperature was raised to 125 °C and the mixture was stirred for 10 h. After the reaction was completed, the reaction product was cooled to room temperature. The solvent was then removed by rotary evaporation. The product was washed three times with anhydrous diethyl ether and then placed in a vacuum drying oven and dried at 50 °C for 3 h to obtain the quaternary ammonium siloxane modifier.

[0036] Step S4: Add 2g of graphene oxide, 20mL of anhydrous ethanol and 20mL of deionized water to a three-necked flask equipped with a stirrer and thermometer. Sonicate at 45kHz for 20min. Then add 0.3g of quaternary ammonium siloxane modifier and stir at 25℃ and 300r / min for 10min. Then raise the temperature to 80℃ and continue stirring for 4h. After the reaction is completed, cool the reaction product to room temperature and then filter under vacuum. Wash the filter cake three times with anhydrous methanol and distilled water. Then place it in a vacuum drying oven and dry at 50℃ for 5h to obtain modified graphene.

[0037] Step S5: Weigh out 100 parts by weight of PET chips, 0.5 parts by weight of modified graphene, 0.05 parts by weight of iron oxide, 0.05 parts by weight of aluminum oxide, 0.05 parts by weight of zinc oxide, 0.05 parts by weight of titanium dioxide, 1 part by weight of calcium stearate, and 1 part by weight of magnesium stearate, and set aside; the PET chips are Yizheng chemical fiber polyester chips with a melting point of 260℃ and a viscosity of 0.68dl / g.

[0038] Step S6: Add PET chips, modified graphene, iron oxide, aluminum oxide, zinc oxide, titanium dioxide, calcium stearate and magnesium stearate to a mixer, mix evenly, melt and extrude through an extruder, then convey to a spinning assembly, and then extrude through a spinneret to obtain modified graphene fibers.

[0039] Step S7: Mix the modified graphene fiber and cotton fiber evenly at 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: Spin the blended fibers into a shape to obtain a weight of 252 g / m². 2 Graphene-based heating clothing fabric with a thickness of 0.61mm.

[0041] Example 2:

[0042] This embodiment describes a method for preparing graphene-based thermal clothing fabric, comprising the following steps:

[0043] Step S1: Add 2g of graphite powder, 50mL of 98% concentrated sulfuric acid and 1.2g of sodium nitrate to a three-necked flask equipped with a stirrer and thermometer. Stir the reaction at -3℃ and 350r / min for 35min. Then add 7g of potassium permanganate and continue stirring for 25min. Then raise the temperature to 18℃ and continue stirring for 1.5h. Then raise the temperature to 38℃ and continue stirring for 35min. Then add 55mL of deionized water and raise the temperature to 98℃ and continue stirring for 25min. Then add 42mL of 40% hydrogen peroxide solution and continue stirring for 25min. After the reaction is complete, cool the reaction product to room temperature and centrifuge. Wash the precipitate four times with 5% hydrochloric acid solution and distilled water. Then place it in a vacuum drying oven and dry it at 52℃ for 4h to obtain graphene oxide.

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

[0045] Step S3: 10 mmol of diimidazole 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, thermometer and gas delivery tube. Nitrogen gas was introduced for protection. The mixture was stirred at 28 °C and 350 r / min for 35 min. Then the temperature was raised to 128 °C and the mixture was stirred for 12 h. After the reaction was completed, the reaction product was cooled to room temperature. The solvent was then removed by rotary evaporation. The product was washed four times with anhydrous diethyl ether and then placed in a vacuum drying oven and dried at 52 °C for 4 h to obtain the quaternary ammonium siloxane modifier.

[0046] Step S4: Add 2g of graphene oxide, 22mL of anhydrous ethanol and 22mL of deionized water to a three-necked flask equipped with a stirrer and thermometer. Sonicate at 50kHz for 25min. Then add 0.9g of quaternary ammonium siloxane modifier and stir at 28℃ and 350r / min for 12min. Then raise the temperature to 82℃ and continue stirring for 4.5h. After the reaction is completed, cool the reaction product to room temperature and then filter under vacuum. Wash the filter cake with anhydrous methanol and distilled water four times in sequence. Then place it in a vacuum drying oven and dry at 52℃ for 5.5h to obtain modified graphene.

[0047] Step S5: Weigh out 100 parts by weight of PET chips, 1.5 parts by weight of modified graphene, 0.1 parts by weight of iron oxide, 0.1 parts by weight of aluminum oxide, 0.1 parts by weight of zinc oxide, 0.1 parts by weight of titanium dioxide, 3 parts by weight of calcium stearate, and 3 parts by weight of magnesium stearate, and set aside; the PET chips are Yizheng chemical fiber polyester chips with a melting point of 260℃ and a viscosity of 0.68dl / g.

[0048] Step S6: Add PET chips, modified graphene, iron oxide, aluminum oxide, zinc oxide, titanium dioxide, calcium stearate and magnesium stearate to a mixer, mix evenly, melt and extrude through an extruder, then convey to a spinning assembly, and then extrude through a spinneret to obtain modified graphene fibers.

[0049] Step S7: Mix the modified graphene fiber and cotton fiber evenly at 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: The mixed fibers are spun into shape to obtain a basis weight of 257 g / m². 2 Graphene-based heating clothing fabric with a thickness of 0.65mm.

[0051] Example 3:

[0052] This embodiment describes a method for preparing graphene-based thermal clothing fabric, comprising the following steps:

[0053] Step S1: Add 2g of graphite powder, 55mL of 98% concentrated sulfuric acid and 1.5g of sodium nitrate to a three-necked flask equipped with a stirrer and thermometer. Stir the reaction at 0℃ and 400r / min for 40min. Then add 8g of potassium permanganate and continue stirring for 30min. Then raise the temperature to 20℃ and continue stirring for 2h. Then raise the temperature to 40℃ and continue stirring for 40min. Then add 60mL of deionized water and raise the temperature to 100℃ and continue stirring for 30min. Then add 45mL of 40% hydrogen peroxide solution and continue stirring for 30min. After the reaction is complete, cool the reaction product to room temperature and centrifuge. Wash the precipitate five times with 5% hydrochloric acid solution and distilled water. Then place it in a vacuum drying oven and dry it at 55℃ for 5h to obtain graphene oxide.

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

[0055] Step S3: 10 mmol of diimidazole 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, thermometer and gas delivery tube. Nitrogen gas was introduced for protection. The mixture was stirred at 30 °C and 400 r / min for 40 min. Then the temperature was raised to 130 °C and the mixture was stirred for 15 h. After the reaction was completed, the reaction product was cooled to room temperature. The solvent was then removed by rotary evaporation. The product was washed 5 times with anhydrous diethyl ether and then placed in a vacuum drying oven and dried at 55 °C for 5 h to obtain the quaternary ammonium siloxane modifier.

[0056] Step S4: Add 2g of graphene oxide, 25mL of anhydrous ethanol and 25mL of deionized water to a three-necked flask equipped with a stirrer and thermometer. Sonicate at 55kHz for 30min. Then add 1.5g of quaternary ammonium siloxane modifier and stir at 30℃ and 400r / min for 15min. Then raise the temperature to 85℃ and continue stirring for 5h. After the reaction is completed, cool the reaction product to room temperature and then filter under vacuum. Wash the filter cake five times with anhydrous methanol and distilled water. Then place it in a vacuum drying oven and dry at 55℃ for 6h to obtain modified graphene.

[0057] Step S5: Weigh out 100 parts by weight of PET chips, 2.5 parts by weight of modified graphene, 0.15 parts by weight of iron oxide, 0.15 parts by weight of aluminum oxide, 0.15 parts by weight of zinc oxide, 0.15 parts by weight of titanium dioxide, 5 parts by weight of calcium stearate, and 5 parts by weight of magnesium stearate, and set aside; the PET chips are Yizheng chemical fiber polyester chips with a melting point of 260℃ and a viscosity of 0.68dl / g.

[0058] Step S6: Add PET chips, modified graphene, iron oxide, aluminum oxide, zinc oxide, titanium dioxide, calcium stearate and magnesium stearate to a mixer, mix evenly, melt and extrude through an extruder, then convey to a spinning assembly, and then extrude through a spinneret to obtain modified graphene fibers.

[0059] Step S7: Mix the modified graphene fiber and cotton fiber evenly at 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: Spin the blended fibers into a shape to obtain a weight of 245 g / m². 2 Graphene-based heating clothing fabric with a thickness of 0.63mm.

[0061] Comparative Example 1:

[0062] This comparative example illustrates a method for preparing a graphene-based thermal clothing fabric, comprising the following steps:

[0063] Step S1: Weigh out 100 parts of PET chips, 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 the weight ratio, and set aside; the PET chips are Yizheng chemical fiber polyester chips with a melting point of 260℃ and a viscosity of 0.68dl / g.

[0064] Step S2: Add PET chips, iron oxide, aluminum oxide, zinc oxide, titanium dioxide, calcium stearate and magnesium stearate to a mixer, mix evenly, melt and extrude through an extruder, then convey to a spinning assembly, and then extrude through a spinneret to obtain modified fibers.

[0065] Step S3: Mix the modified fiber and cotton fiber evenly at a mass ratio of 2:8 to obtain the 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: The mixed fibers are spun into shape to obtain a basis weight of 253 g / m². 2 Graphene-based heating clothing fabric with a thickness of 0.68mm.

[0067] Comparative Example 2:

[0068] This comparative example illustrates a method for preparing a graphene-based thermal clothing fabric, comprising the following steps:

[0069] Step S1: Add 2g of graphite powder, 55mL of 98% concentrated sulfuric acid and 1.5g of sodium nitrate to a three-necked flask equipped with a stirrer and thermometer. Stir the reaction at 0℃ and 400r / min for 40min. Then add 8g of potassium permanganate and continue stirring for 30min. Then raise the temperature to 20℃ and continue stirring for 2h. Then raise the temperature to 40℃ and continue stirring for 40min. Then add 60mL of deionized water and raise the temperature to 100℃ and continue stirring for 30min. Then add 45mL of 40% hydrogen peroxide solution and continue stirring for 30min. After the reaction is complete, cool the reaction product to room temperature and centrifuge. Wash the precipitate five times with 5% hydrochloric acid solution and distilled water. Then place it in a vacuum drying oven and dry it at 55℃ for 5h to obtain graphene oxide.

[0070] Step S2: Weigh out 100 parts of PET chips, 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 the weight ratio, and set aside; the PET chips are Yizheng chemical fiber polyester chips with a melting point of 260℃ and a viscosity of 0.68dl / g.

[0071] Step S3: Add PET chips, graphene oxide, iron oxide, aluminum oxide, zinc oxide, titanium dioxide, calcium stearate and magnesium stearate to a mixer, mix evenly, melt and extrude through an extruder, then convey to a spinning assembly, and then extrude through a spinneret to obtain modified graphene fibers.

[0072] Step S4: Mix the modified graphene fiber and cotton fiber evenly at 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: Spin the blended fibers into a shape to obtain a weight of 255 g / m². 2 Graphene-based heating clothing fabric with a thickness of 0.66mm.

[0074] Comparative Example 3:

[0075] This comparative example illustrates a method for preparing a graphene-based thermal clothing fabric, comprising the following steps:

[0076] Step S1: Add 2g of graphite powder, 55mL of 98% concentrated sulfuric acid and 1.5g of sodium nitrate to a three-necked flask equipped with a stirrer and thermometer. Stir the reaction at 0℃ and 400r / min for 40min. Then add 8g of potassium permanganate and continue stirring for 30min. Then raise the temperature to 20℃ and continue stirring for 2h. Then raise the temperature to 40℃ and continue stirring for 40min. Then add 60mL of deionized water and raise the temperature to 100℃ and continue stirring for 30min. Then add 45mL of 40% hydrogen peroxide solution and continue stirring for 30min. After the reaction is complete, cool the reaction product to room temperature and centrifuge. Wash the precipitate five times with 5% hydrochloric acid solution and distilled water. Then place it in a vacuum drying oven and dry it at 55℃ for 5h to obtain graphene oxide.

[0077] Step S2: Add 2g of graphene oxide, 25mL of anhydrous ethanol and 25mL of deionized water to a three-necked flask equipped with a stirrer and thermometer. Sonicate at 55kHz for 30min. Then add 1.5g of 3-chloropropyltrimethoxysilane and stir at 30℃ and 400r / min for 15min. Then raise the temperature to 85℃ and continue stirring for 5h. After the reaction is completed, cool the reaction product to room temperature and then filter under vacuum. Wash the filter cake five times with anhydrous methanol and distilled water. Then place it in a vacuum drying oven and dry at 55℃ for 6h to obtain modified graphene.

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

[0079] Step S4: Add PET chips, modified graphene, iron oxide, aluminum oxide, zinc oxide, titanium dioxide, calcium stearate and magnesium stearate to a mixer, mix evenly, melt and extrude through an extruder, then convey to a spinning assembly, and then extrude through a spinneret to obtain modified graphene fibers.

[0080] Step S5: Mix the modified graphene fiber and cotton fiber evenly at 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: Spin the blended fibers into a shape to obtain a basis weight of 251 g / m². 2 Graphene-based heating clothing fabric with a thickness of 0.62mm.

[0082] Comparative Example 4:

[0083] This comparative example illustrates a method for preparing a graphene-based thermal clothing fabric, comprising the following steps:

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

[0085] Step S2: 10 mmol of diimidazole 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, thermometer and gas delivery tube. Nitrogen gas was introduced for protection. The mixture was stirred at 30 °C and 400 r / min for 40 min. Then the temperature was raised to 130 °C and the mixture was stirred for 15 h. After the reaction was completed, the reaction product was cooled to room temperature. The solvent was then removed by rotary evaporation. The product was washed 5 times with anhydrous diethyl ether and then placed in a vacuum drying oven and dried at 55 °C for 5 h to obtain the quaternary ammonium siloxane modifier.

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

[0087] Step S4: Add PET chips, quaternary ammonium siloxane modifier, iron oxide, aluminum oxide, zinc oxide, titanium dioxide, calcium stearate and magnesium stearate to a mixer, mix evenly, melt extrude through an extruder, then convey to a spinning assembly, and then extrude through a spinneret to obtain modified fibers.

[0088] Step S5: Mix the modified fiber and cotton fiber evenly at a mass ratio of 2:8 to obtain the 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: The blended fibers are spun into shape to obtain a basis weight of 249 g / m². 2 Graphene-based heating clothing fabric with a thickness of 0.65mm.

[0090] Blank example:

[0091] This blank example illustrates a method for preparing a graphene-based thermal clothing fabric, comprising the following steps:

[0092] Step S1: PET chips are melted and extruded through an extruder, then fed into a spinning assembly, and then extruded through a spinneret to obtain PET fibers; the PET chips are Yizheng Chemical Fiber polyester chips PET with a melting point of 260℃ and a viscosity of 0.68dl / g.

[0093] Step S2: Mix PET fiber and cotton fiber evenly at 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: Spin the blended fibers into a shape to obtain a weight of 254 g / m². 2 Graphene-based heating clothing fabric with a thickness of 0.67mm.

[0095] The graphene-based heating clothing fabrics from Examples 1-3, Comparative Examples 1-4, and the blank example were subjected to performance tests. The test results are shown in the table below:

[0096]

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

[0098] In the description of this specification, references to terms such as "an embodiment," "example," "specific example," etc., indicate that a specific feature, structure, material, or characteristic described in connection with that embodiment or example is included in at least one embodiment or example of the invention. In this specification, illustrative expressions of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in one or more embodiments or examples.

[0099] The above description is merely an example and illustration of the present invention. Those skilled in the art can make various modifications or additions to the specific embodiments described or use similar methods to replace them, as long as they do not deviate from the invention or exceed the scope defined in this application, they should all fall within the protection scope of the present invention.

Claims

1. A method for preparing a graphene-based heating clothing fabric, characterized in that, Includes the following steps: Step 1: Weigh out 100 parts of PET chips, 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 their weight, and set aside. Step 2: Add PET chips, modified graphene, iron oxide, aluminum oxide, zinc oxide, titanium dioxide, calcium stearate and magnesium stearate to a mixer, mix evenly, melt and extrude through an extruder, then convey to a spinning assembly, and then extrude through a spinneret to obtain modified graphene fibers. Step 3: Mix the modified graphene fiber and cotton fiber evenly at a mass ratio of 2:8 to obtain the mixed fiber; Step 4: Spin the blended fibers into a shape to obtain a weight of 250±10g / m². 2 Graphene-based heating clothing fabric with a thickness of 0.65±0.05mm; The modified graphene was prepared by the following steps: Step s1: Graphite powder, concentrated sulfuric acid and sodium nitrate are stirred and reacted. Then potassium permanganate, deionized water and hydrogen peroxide solution are added in sequence and the reaction is continued. After the reaction is completed, the reaction product is cooled, centrifuged, and the precipitate is washed and dried to obtain graphene oxide. Step s2: Imidazole, sodium hydroxide and dimethyl sulfoxide are stirred and reacted. Then, 1,4-dibromobutane is added dropwise while stirring. After the addition is complete, the reaction is stirred and reacted. After the reaction is completed, the reaction product is cooled and then added to ice water. After vacuum filtration, the filter cake is dried to obtain the diimidazole intermediate. Step s3: The diimidazole intermediate, 3-chloropropyltrimethoxysilane, potassium iodide and N,N-dimethylformamide were stirred and reacted. After the reaction was completed, the reaction product was cooled, then rotary evaporated, washed and dried to obtain the quaternary ammonium siloxane modifier. Step s4: Ultrasonic treatment is performed on graphene oxide, anhydrous ethanol and deionized water. Then, quaternary ammonium siloxane modifier is added and the mixture is stirred to react. After the reaction is completed, the reaction product is cooled and then vacuum filtered. The filter cake is washed and dried to obtain modified graphene.

2. The method for preparing a graphene-based thermal clothing fabric according to claim 1, characterized in that, The PET chips are Yizheng Chemical Fiber polyester chips with a melting point of 260℃ and a viscosity of 0.68dl / g. The modified graphene fiber has a linear density of 1.66 dtex; The linear density of the cotton fiber is 1.47 dtex.

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

4. The method for preparing a graphene-based thermal clothing fabric according to claim 1, characterized in that, The concentrated sulfuric acid in step s1 has a mass fraction of 98%; the hydrogen peroxide solution has a mass fraction of 40%.

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

6. The method for preparing a graphene-based thermal clothing fabric according to claim 1, characterized in that, The ratio of the amount of the diimidazole intermediate, 3-chloropropyltrimethoxysilane, potassium iodide, and N,N-dimethylformamide used in step s3 is 10 mmol: 20 mmol: 0.05-0.07 g: 40-50 mL.

7. The method for preparing a graphene-based thermal clothing fabric according to claim 1, characterized in that, The ratio of graphene oxide, anhydrous ethanol, deionized water and quaternary ammonium siloxane modifier used in step s4 is 2g: 20-25mL: 20-25mL: 0.3-1.5g.

8. A graphene-based heating clothing fabric, characterized in that, The graphene-heated clothing fabric is prepared by the method described in any one of claims 1-7.

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