Preparation method of graphene cloud wool

Abstract

The invention discloses a preparation method of graphene cloud wool, and relates to the technical field of cloud wool. The preparation method comprises the following steps: carrying out an addition reaction on p-aminostyrene and graphite scale to introduce double bonds, then mixing with gamma-methacryloxypropyltrimethoxysilane to prepare hydrogel and form a dual cross-linked network, and then preparing aerogel to improve the strength of cloud wool; titanium dioxide nanocrystals are attached to aerogel, then dehydration and crystal form transformation are carried out after a hydrothermal reaction, the porosity is enhanced, the photocatalytic activity is improved, the concentration of active oxygen is increased, and the antibacterial performance is further improved. Secondly, polyester hollow special-shaped spinning is adopted in the cloud velvet to form a penetrating porous structure, more still air can be enriched, and the warm keeping effect is improved; in the fiber forming process, an all-dimensional annular high-speed strong cold air blowing technology is adopted, a spinning melt is instantly and rapidly cooled with a very small error, and the bulk density of cloud wool is very small. The cloud velvet prepared by the invention has the effects of high strength, antibiosis and warm keeping.

Description

Technical Field

[0001] The invention relates to the technical field of cloud velvet, and in particular to a method for preparing graphene cloud velvet. Background Art

[0002] Cloud velvet is actually a kind of fiber made using a new technology. It has good warmth retention and high elasticity, and is comfortable and bouncy. Usually, cloud velvet can be processed and used in many fields such as clothing and household items.

[0003] Cloud velvet is a completely different fiber from the traditional one. It uses a brand-new polyester production process and a blending technology of multiple PET polymer materials. After being processed into ball velvet, it feels very comfortable to touch, as if it is condensed fat. When you hold it with both hands, you will feel full. Now cloud velvet can be used as a filling for many items, including pillows, quilts, cloth dolls, sofas, soft beds, etc.

[0004] However, there are still many defects in the preparation of cloud velvet. First, cloud velvet has low hollowness, and its walls are thin and easy to break due to high hollowness, which consumes a large amount of material, thereby increasing the use of raw materials. Second, the addition of graphene is easy to agglomerate due to the π-π conjugated bonds, and the produced fiber has poor performance, and the bactericidal effect of graphene is also greatly reduced. Therefore, the present invention proposes a method for preparing graphene cloud velvet to solve the above problems. Summary of the invention

[0005] The purpose of the present invention is to provide a method for preparing graphene cloud velvet to solve the problems existing in the prior art.

[0006] In order to solve the above technical problems, the present invention provides the following technical solutions: a method for preparing graphene cloud velvet, comprising the following preparation steps: (1) First, weigh 1 part of graphite flakes and 10 parts of sodium chloride for ball milling for 0.5-1.5 hours; then add 5-10 parts of p-aminostyrene, mix and ball mill for 0.5-1.5 hours; finally, add 16-20 parts of nitrite and mix and ball mill for 24 hours, then wash twice with deionized water, and then vacuum dry at 0.085 MPa and 50°C to obtain modified graphene; (2) Mixing 1-5 parts of modified graphene with 50 parts of deionized water, stirring at 350 rpm for 1-2 hours, and then subjecting the mixture to 30 kHz ultrasonic treatment for 30 minutes, and then continuing to stir for 1-2 hours to prepare a suspension; then adding 0.2-1.2 parts of siloxane and 0.02-0.04 parts of a catalyst to the suspension, and then mixing and stirring at 150 rpm for 10 minutes to prepare a hydrogel; UV curing the hydrogel, freezing the cured hydrogel at -40°C to prepare an ice product, and then crushing the ice product to prepare an ice product powder with a diameter of 50-100 nm; placing the ice product powder in a freeze dryer tray, drying it by gradient heating, and the whole drying time is 15-30 hours to prepare a modified graphene aerogel powder; (3) Mix 3 parts of modified graphene aerogel powder, 0.5-1.5 parts of titanium dioxide powder and 70 parts of sodium hydroxide solution, stir at 150 rpm for 20 minutes, ultrasonicate at 50 kHz for 30 minutes, and then keep warm at 160-180°C for 48 hours. Filter the solid, wash it with deionized water for 3 times, then wash it with hydrochloric acid solution for 3 times, and finally wash it with deionized water for 3 times, and dry it at room temperature and pressure for 2 hours. Then disperse the dried product into nitric acid aqueous solution with a solid-liquid ratio of 1:100, keep warm at 100-120°C for 40 hours, dry it at room temperature and pressure for 2 hours, and then place it in a Mabo furnace for high temperature treatment at 450°C for 1-3 hours to obtain a composite filler. (4) Terephthalic acid, ethylene glycol and composite filler are mixed in a mass ratio of 1:0.9-1.1:0.1-0.3 for esterification reaction and polycondensation reaction. The temperature of the esterification reaction is 180°C, the pressure is 0.01MPa and the time is 2h. After the esterification reaction is completed, the polycondensation reaction is carried out in stages: the first stage polycondensation temperature is 220°C, the pressure is 0.4-0.8kPa and the time is 0.5-1.5h; the second stage polycondensation temperature is 240°C, the pressure is 20-80Pa and the time is 1-3h. The polyester raw material after polycondensation is passed through a screw After extrusion and melting, the slurry is transformed into hollow shaped spinning at the spinneret to obtain hollow shaped fibers. The ejected fibers are quickly shaped by high-speed stretching and ring-blown air cooling, and flow into the reciprocating machine for barrel bundling. When the technology reaches a total denier of 600 deniers for composite production, it is quickly stretched through an oil bath, and then enters the steam box for micro-stretching. The steam box temperature is 120°C, and the micro-stretching time is 2s. Three-dimensional curling is performed inside to fully form the fibers, and then they enter the cutting machine for cutting. After cutting, they are placed in a three-layer oven for heat setting to make graphene cloud velvet.

[0007] Furthermore, the ball milling conditions in step (1) are: 1.2 cm steel balls, and a ball-to-material ratio of 6-10:1.

[0008] Furthermore, in step (2), the siloxane is γ-methacryloxypropyltrimethoxysilane.

[0009] Furthermore, in step (2), the catalyst is N,N,N',N'-tetramethylethylenediamine.

[0010] Furthermore, the UV curing conditions in step (2) are as follows: the power of the UV lamp is 2.4 kW, and the curing time is 2 h.

[0011] Furthermore, the vacuum freeze-drying conditions in step (2) are: drying at a vacuum degree of 10 Pa and a partition temperature of -5°C.

[0012] Furthermore, the concentration of the sodium hydroxide aqueous solution in step (3) is 10M.

[0013] Furthermore, the concentration of the aqueous hydrochloric acid solution in step (3) is 0.1-0.3M.

[0014] Furthermore, the concentration of the nitric acid aqueous solution in step (3) is 0.05-0.07M.

[0015] Furthermore, the heat setting temperature in step (4) is 180°C.

[0016] Compared with the prior art, the beneficial effects achieved by the present invention are: The present invention uses modified graphene to make aerogel, with silicon dioxide nanocrystals attached to the surface to form filler, which is blended with polyester and spun into cloud velvet to achieve high strength, antibacterial and warmth-keeping effects.

[0017] Firstly, p-aminostyrene is reacted with the carbon layer of the surface of graphite flakes by chemical bonding, and double bonds are introduced into the surface of graphene to modify it; the modified graphene is mixed with γ-methacryloxypropyltrimethoxysilane to prepare hydrogel, and under the action of catalyst, the double bonds on graphene and siloxane are polymerized by ultraviolet light to form a double cross-linked network, which is then prepared into aerogel, maintaining this double network structure, which not only improves the strength of cloud velvet, but also avoids the aggregation of graphene in polyester without affecting the properties of graphene. Aggregation phenomenon improves the dispersion of graphene and further enhances the performance of cloud velvet; titanium dioxide nanocrystals are attached to aerogel, and then the surface becomes rough and uneven after a hydrothermal reaction. The titanium dioxide octahedrons on the fiber surface are dehydrated during contact with acid, and rearranged to form a crystal transformation to enhance porosity. This transformed crystal form allows photogenerated electrons and holes to transfer through the interface, reducing the recombination rate of photogenerated carriers, increasing the photocatalytic activity of titanium dioxide nanocrystals, and increasing the concentration of active oxygen generated by catalysis, further improving its antibacterial properties; Secondly, cloud velvet uses polyester hollow shaped spinning to form a penetrating porous structure, which can enrich more still air to enhance the warmth-keeping effect; in the fiber forming process, all-round annular high-speed strong cold blowing technology is used to rapidly cool the spinning melt in an instant with minimal error, resulting in a unique crystalline state of cloud velvet that is different from other polyester fibers. Its stacking density is very small, and the weight of cloud velvet of the same volume is about one-third lighter than other chemical fibers of the same specification. DETAILED DESCRIPTION

[0018] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative work are within the scope of protection of the present invention.

[0019] In order to more clearly illustrate the method provided by the present invention, the following examples are used to describe in detail the various index testing methods of the graphene cloud velvet prepared in the following examples are as follows: Antibacterial property: The antibacterial property of the examples and comparative examples was tested according to the national standard GB / T20944.3-2008 "Evaluation of antibacterial properties of textiles Part 3: Oscillation method". The bacteria used for the test were: Escherichia coli ATCC25922 and Staphylococcus aureus ATCC6538.

[0020] Warmth retention: The antibacterial properties of the embodiments and comparative examples were tested for warmth retention according to GB / T11048-2008-T “Determination of thermal and moisture resistance of textiles under steady-state conditions for physiological comfort”.

[0021] Strength: The antibacterial properties of the embodiments and comparative examples were tested for breaking strength according to the national standard GB / T 3923.1-1997 "Textile fabric tensile properties - Determination of breaking strength and breaking elongation - Strip method".

[0022] Example 1; (1) First, weigh 1 part of graphite flakes and 10 parts of sodium chloride for ball milling, with a 1.2 cm steel ball, a ball-to-material ratio of 6:1, and a ball milling time of 0.5 h; then add 5 parts of p-aminostyrene, mix and continue ball milling for 0.5 h; finally, add 16 parts of nitrite and mix and ball mill for 24 h, then wash twice with deionized water, and then vacuum dry at 0.085 MPa and 50° C. to obtain modified graphene; (2) Mix 1 part of modified graphene with 50 parts of deionized water, stir at 350 rpm for 1 hour, and then subject to 30 kHz ultrasonic treatment for 30 minutes, and continue stirring for 1 hour to prepare a suspension; then add 0.2 parts of γ-methacryloxypropyltrimethoxysilane and 0.02 parts of N,N,N',N'-tetramethylethylenediamine to the suspension, and then mix and stir at 150 rpm for 10 minutes to prepare a hydrogel; UV-curing the hydrogel, the power of the UV lamp is 2.4 KW, and the curing time is 2 hours; the cured hydrogel is frozen at -40°C to prepare an ice product, and then the ice product is crushed to prepare an ice product powder with a diameter of 50 nm; the ice product powder is placed in a freeze dryer tray, and dried at a vacuum degree of 10 Pa and a partition temperature of -5°C for 15 hours to obtain a modified graphene aerogel powder; (3) 3 parts of modified graphene aerogel powder, 0.5 parts of titanium dioxide powder and 70 parts of 10M sodium hydroxide solution were mixed, stirred at 150 rpm for 20 minutes, ultrasonicated at 50 kHz for 30 minutes, and then kept at 160°C for 48 hours. The solid was filtered and washed with deionized water for 3 times, then washed with 0.1M hydrochloric acid solution for 3 times, and finally washed with deionized water for 3 times, and dried at room temperature and pressure for 2 hours; the dried product was then dispersed in a 0.05M nitric acid aqueous solution with a solid-liquid ratio of 1:100, kept at 100°C for 40 hours, dried at room temperature and pressure for 2 hours, and then placed in a Mabo furnace for high-temperature treatment at 450°C for 1 hour to obtain a composite filler; (4) Terephthalic acid, ethylene glycol and composite filler are mixed in a mass ratio of 1:0.9:0.1 for esterification reaction and polycondensation reaction. The temperature of the esterification reaction is 180°C, the pressure is 0.01MPa and the time is 2h. After the esterification reaction is completed, the polycondensation reaction is carried out in stages: the first stage is at a temperature of 220°C, the pressure is 0.4kPa and the time is 0.5h; the second stage is at a temperature of 240°C, the pressure is 20Pa and the time is 1h. The polyester raw material after polycondensation is melted by screw extrusion and the slurry is transformed into a spinneret through the spinneret. Hollow shaped spinning is carried out to obtain hollow shaped fibers. The ejected fibers are quickly shaped by high-speed stretching and ring-blown air cooling, and then flow into the reciprocating machine for barrel bundling. When the technology reaches a total denier of 600 deniers for composite production, they are quickly stretched by an oil bath, and then enter the steam box for micro-stretching. The steam box temperature is 120°C, and the micro-stretching time is 2s. Three-dimensional curling is performed inside to fully form them, and then they enter the cutting machine for cutting. After cutting, they are placed in a three-layer oven for heat setting at 180°C to make graphene cloud velvet.

[0023] Example 2; (1) First weigh 1 part of graphite flakes and 10 parts of sodium chloride for ball milling, with a 1.2 cm steel ball, a ball-to-material ratio of 8:1, and a ball milling time of 1 h; then add 7.5 parts of p-aminostyrene, mix and continue ball milling for 1 h; finally add 18 parts of nitrite and mix and ball mill for 24 h, then wash twice with deionized water, and then vacuum dry at 0.085 MPa and 50° C. to obtain modified graphene; (2) Mix 3 parts of modified graphene with 50 parts of deionized water, stir at 350 rpm for 1.5 hours, and then subject to 30 kHz ultrasonic treatment for 30 minutes, and continue to stir for 1.5 hours to prepare a suspension; then add 0.6 parts of γ-methacryloxypropyltrimethoxysilane and 0.03 parts of N,N,N',N'-tetramethylethylenediamine to the suspension, and then mix and stir at 150 rpm for 10 minutes to prepare a hydrogel; UV-curing the hydrogel, the power of the UV lamp is 2.4 KW, and the curing time is 2 hours; the cured hydrogel is frozen at -40°C to prepare an ice product, and then the ice product is crushed to prepare an ice product powder with a diameter of 75 nm; the ice product powder is placed in a freeze dryer tray, and dried at a vacuum degree of 10 Pa and a partition temperature of -5°C for 23 hours to obtain a modified graphene aerogel powder; (3) Mix 3 parts of modified graphene aerogel powder, 1 part of titanium dioxide powder and 70 parts of 10M sodium hydroxide solution, stir at 150 rpm for 20 minutes, ultrasonicate at 50 kHz for 30 minutes, and then keep it at 170°C for 48 hours. Filter the solid, wash it with deionized water for 3 times, then wash it with 0.2M hydrochloric acid solution for 3 times, and finally wash it with deionized water for 3 times, and dry it at room temperature and pressure for 2 hours; then disperse the dried product into a 0.06M nitric acid aqueous solution with a solid-liquid ratio of 1:100, keep it at 110°C for 40 hours, dry it at room temperature and pressure for 2 hours, and then place it in a Mabo furnace for high temperature treatment at 450°C for 2 hours to obtain a composite filler; (4) Terephthalic acid, ethylene glycol and composite filler are mixed in a mass ratio of 1:1:0.2 for esterification reaction and polycondensation reaction. The temperature of the esterification reaction is 180°C, the pressure is 0.01MPa and the time is 2h. After the esterification reaction is completed, the polycondensation reaction is carried out in stages: the first stage is at a temperature of 220°C, the pressure is 0.6kPa and the time is 1h; the second stage is at a temperature of 240°C, the pressure is 50Pa and the time is 2h. The polyester raw material after polycondensation is melted by screw extrusion and the slurry is transformed into a hollow isocyanate through a spinneret. Shaped spinning is performed to obtain hollow special-shaped fibers. The ejected fibers are quickly shaped by high-speed stretching and ring-blown air cooling, and then flow into the reciprocating machine for barrel bundling. When the technology reaches a total denier of 600 deniers for composite production, they are quickly stretched by an oil bath, and then enter the steam box for micro-stretching. The steam box temperature is 120°C, and the micro-stretching time is 2s. Three-dimensional curling is performed inside to fully form them, and then they enter the cutting machine for cutting. After cutting, they are placed in a three-layer oven for heat setting at 180°C to make graphene cloud velvet.

[0024] Example 3; (1) First weigh 1 part of graphite flakes and 10 parts of sodium chloride for ball milling, a 1.2 cm steel ball, a ball-to-material ratio of 10:1, and a ball milling time of 1.5 h; then add 10 parts of p-aminostyrene, mix and continue ball milling for 1.5 h; finally add 20 parts of nitrite and mix and ball mill for 24 h, then wash twice with deionized water, and then vacuum dry at 0.085 MPa and 50 ° C to obtain modified graphene; (2) Mix 5 parts of modified graphene with 50 parts of deionized water, stir at 350 rpm for 2 hours, and then subject to 30 kHz ultrasonic treatment for 30 minutes, and continue stirring for 2 hours to prepare a suspension; then add 1.2 parts of γ-methacryloxypropyltrimethoxysilane and 0.04 parts of N,N,N',N'-tetramethylethylenediamine to the suspension, and then mix and stir at 150 rpm for 10 minutes to prepare a hydrogel; UV-curing the hydrogel, the power of the UV lamp is 2.4 KW, and the curing time is 2 hours; the cured hydrogel is frozen at -40°C to prepare an ice product, and then the ice product is crushed to prepare an ice product powder with a diameter of 100 nm; the ice product powder is placed in a freeze dryer tray, and dried at a vacuum degree of 10 Pa and a partition temperature of -5°C for 30 hours to obtain a modified graphene aerogel powder; (3) 3 parts of modified graphene aerogel powder, 1.5 parts of titanium dioxide powder and 70 parts of 10M sodium hydroxide solution were mixed, stirred at 150 rpm for 20 minutes, ultrasonicated at 50 kHz for 30 minutes, and then kept at 180°C for 48 hours. The solid was filtered and washed with deionized water for 3 times, then washed with 0.3M hydrochloric acid solution for 3 times, and finally washed with deionized water for 3 times, and dried at room temperature and pressure for 2 hours; the dried product was then dispersed in a 0.07M nitric acid aqueous solution with a solid-liquid ratio of 1:100, kept at 120°C for 40 hours, dried at room temperature and pressure for 2 hours, and then placed in a Mabo furnace for high-temperature treatment at 450°C for 3 hours to obtain a composite filler; (4) Terephthalic acid, ethylene glycol and composite filler are mixed in a mass ratio of 11.1:0.3 for esterification reaction and polycondensation reaction. The temperature of the esterification reaction is 180°C, the pressure is 0.01MPa and the time is 2h. After the esterification reaction is completed, the polycondensation reaction is carried out in stages: the first stage is at a temperature of 220°C, the pressure is 0.8kPa and the time is 1.5h; the second stage is at a temperature of 240°C, the pressure is 80Pa and the time is 3h. The polyester raw material after polycondensation is melted by screw extrusion and the slurry is transformed into a spinneret through the spinneret. Hollow shaped spinning is carried out to obtain hollow shaped fibers. The ejected fibers are quickly shaped by high-speed stretching and ring-blown air cooling, and then flow into the reciprocating machine for barrel bundling. When the technology reaches a total denier of 600 deniers for composite production, they are quickly stretched by an oil bath, and then enter the steam box for micro-stretching. The steam box temperature is 120°C, and the micro-stretching time is 2s. Three-dimensional curling is performed inside to fully form them, and then they enter the cutting machine for cutting. After cutting, they are placed in a three-layer oven for heat setting at 180°C to make graphene cloud velvet.

[0025] Comparative Example 1: The difference between Comparative Example 1 and Example 2 is that step (1) is omitted, and step (2) is changed to: 3 parts of graphene are mixed with 50 parts of deionized water, stirred at 350 rpm for 1.5 h, and then subjected to 30 kHz ultrasonic treatment for 30 min, and then stirred for 1.5 h to prepare a suspension; 0.6 parts of γ-methacryloxypropyltrimethoxysilane and 0.03 parts of N,N,N',N'-tetramethylethylenediamine are added to the suspension, and then mixed and stirred at 150 rpm for 1 0min to prepare a hydrogel; the hydrogel is UV-cured, the power of the UV lamp is 2.4KW, and the curing time is 2h; the cured hydrogel is frozen at -40°C to prepare an ice product, and the ice product is crushed to prepare an ice product powder with a diameter of 75nm; the ice product powder is placed in a freeze dryer tray, and dried at a vacuum degree of 10Pa and a partition temperature of -5°C for a total drying time of 23h to obtain a modified graphene aerogel powder; the remaining steps are the same as those in Example 2.

[0026] Comparative Example 2: The difference between Comparative Example 2 and Example 2 is that step (2) is different, and step (3) is changed to: 3 parts of modified graphene are mixed with 50 parts of deionized water, stirred at 350 rpm for 1.5 hours, and then subjected to 30 kHz ultrasonic treatment for 30 minutes, and then stirred for 1.5 hours to prepare a suspension; 0.03 parts of N, N, N', N'-tetramethylethylenediamine are added to the suspension, and then mixed and stirred at 150 rpm for 10 minutes to prepare a hydrogel; the hydrogel is ultraviolet cured, the power of the ultraviolet lamp is 2.4 KW, and the curing time is 2 hours; the cured hydrogel is frozen at -40°C to prepare an ice product, and then the ice product is crushed to prepare an ice product powder with a diameter of 75 nm; the ice product powder is placed in a freeze dryer tray, and dried at a vacuum degree of 10 Pa and a partition temperature of -5°C for a total drying time of 23 hours to obtain a modified graphene aerogel powder; the remaining steps are the same as Example 2.

[0027] Comparative Example 3: The difference between Comparative Example 3 and Example 2 is that there is no step (3), and step (4) is changed to: terephthalic acid, ethylene glycol, and modified graphene aerogel powder are mixed in a mass ratio of 1:1:0.2 to carry out esterification reaction and polycondensation reaction, the temperature of the esterification reaction is 180°C, the pressure is 0.01MPa, and the time is 2h; after the esterification reaction is completed, the polycondensation reaction is carried out in stages: the first stage polycondensation temperature is 220°C, the pressure is 0.6kPa, and the time is 1h; the second stage polycondensation temperature is 240°C, the pressure is 50Pa, and the time is 2h; the polyester raw material after polycondensation is melted by screw extrusion The slurry is transformed into hollow shaped fibers on the spinneret to obtain hollow shaped fibers. The ejected fibers are quickly shaped by high-speed stretching and annular air cooling, and flow into the reciprocating machine for barrel bundling. When the total denier of the composite production reaches 600 denier, it is quickly stretched by an oil bath, and then enters the steam box for micro-stretching. The steam box temperature is 120°C, and the micro-stretching time is 2s. Three-dimensional curling is performed inside to fully form the fibers, and then the fibers enter the cutting machine for cutting. After cutting, they are placed in a three-layer oven for heat setting at 180°C to make graphene cloud velvet. The remaining steps are the same as those in Example 2.

[0028] Comparative Example 4: The difference between Comparative Example 4 and Example 2 is that step (3) is different. Step (3) is changed to: 3 parts of modified graphene aerogel powder, 1 part of titanium dioxide powder and 70 parts of 10M sodium hydroxide solution are mixed, stirred at 150 rpm for 20 min, ultrasonicated at a power of 50 kHz for 30 min, and then kept at 170°C for 48 h. The solid is filtered and washed with deionized water for 3 times, then washed with 0.2M hydrochloric acid solution for 3 times, and finally washed with deionized water for 3 times, and dried at room temperature and pressure for 2 h to obtain a composite filler. The remaining steps are the same as those in Example 2.

[0029] Comparative Example 5: The difference between Comparative Example 5 and Example 2 is that step (4) is different. Step (4) is changed to: terephthalic acid, ethylene glycol and composite filler are mixed in a mass ratio of 1:1:0.2 to carry out esterification reaction and polycondensation reaction. The temperature of the esterification reaction is 180°C, the pressure is 0.01MPa, and the time is 2h. After the esterification reaction is completed, the polycondensation reaction is carried out in stages: the first stage polycondensation temperature is 220°C, the pressure is 0.6kPa, and the time is 1h; the second stage polycondensation temperature is 240°C, the pressure is 50Pa, and the time is 2h; the polyester raw material after polycondensation is passed through a screw The rod is extruded and melted, and the slurry is changed into cloud velvet fibers at the spinneret. The ejected fibers are quickly shaped by high-speed stretching and cooling by annular air, and flow into the reciprocating machine for barrel bundling. When the technology reaches a total denier of 600 deniers for composite production, they are quickly stretched by an oil bath, and then enter the steam box for micro-stretching. The steam box temperature is 120°C, and the micro-stretching time is 2s. Three-dimensional curling is performed inside to fully shape them, and then they enter the cutting machine for cutting. After cutting, they are placed in a three-layer oven for heat setting at 180°C to make graphene cloud velvet. The remaining steps are the same as Example 2.

[0030] Effect example The following Table 1 shows the performance analysis results of the graphene cloud fleece using Examples 1 to 3 of the present invention and Comparative Examples 1 to 5.

[0031] Table 1

[0032] From the comparison of the experimental data of the breaking strength of the embodiment and the comparative example, it can be found that the present invention carries out an addition reaction between p-aminostyrene and the carbon layer of the surface layer of graphite flakes through chemical bonding, introduces double bonds in the surface layer of graphene to modify it; the modified graphene is mixed with γ-methacryloxypropyltrimethoxysilane to prepare a hydrogel, and under the action of a catalyst, the double bonds on the graphene and siloxane are polymerized by ultraviolet light to form a double cross-linked network, which is then prepared into an aerogel, maintaining this double network structure, which on the one hand improves the strength of the cloud velvet, and on the other hand, without affecting the properties of the graphene, can avoid the agglomeration of graphene in polyester, improve the dispersibility of graphene, and further enhance the performance of the cloud velvet; from the comparison of the experimental data of the antibacterial property of the embodiment and the comparative example, it can be found that the present invention attaches titanium dioxide nanocrystals to the aerogel, and then after a hydrothermal reaction, the surface becomes rough and not The titanium dioxide octahedron on the fiber surface is dehydrated and rearranged during the contact with the acid to form a crystal transformation, which enhances the porosity. The transformed crystal form allows photogenerated electrons and holes to transfer through the interface, reduces the recombination rate of photogenerated carriers, and improves the photocatalytic activity of titanium dioxide nanocrystals, thereby increasing the concentration of active oxygen produced by catalysis and further improving its antibacterial properties. From the comparison of the experimental data on the warmth retention of the embodiment and the comparative example, it can be found that the present invention adopts polyester hollow shaped spinning to form a penetrating porous structure, which can enrich more still air to enhance the warmth retention effect. In the fiber forming process, all-round annular high-speed strong cold blowing technology is adopted to instantly cool the spinning melt with extremely small error, resulting in a unique crystalline state of cloud velvet that is different from other polyester fibers. Its packing density is very small, and the weight of cloud velvet of the same volume is about one-third lighter than that of other chemical fibers of the same specification.

[0033] It will be apparent to those skilled in the art that the invention is not limited to the details of the exemplary embodiments described above and that the invention can be implemented in other specific forms without departing from the spirit or essential features of the invention. Therefore, the embodiments should be considered in all respects as exemplary and non-limiting, and the scope of the invention is defined by the appended claims rather than the foregoing description, and it is intended that all variations within the meaning and scope of the equivalent elements of the claims be included in the invention. Any marking in a claim should not be considered as limiting the claim to which it relates.

Claims

1. A method for preparing graphene cloud velvet, characterized in that: The method comprises the following preparation steps: (1) First, weigh 1 part of graphite flakes and 10 parts of sodium chloride for ball milling for 0.5-1.5 hours; then add 5-10 parts of p-aminostyrene, mix and ball mill for 0.5-1.5 hours; finally, add 16-20 parts of nitrite and mix and ball mill for 24 hours, then wash twice with deionized water, and then vacuum dry at 0.085 MPa and 50°C to obtain modified graphene; (2) Mixing 1-5 parts of modified graphene with 50 parts of deionized water, stirring at 350 rpm for 1-2 hours, and then subjecting the mixture to 30 kHz ultrasonic treatment for 30 minutes, and then continuing to stir for 1-2 hours to prepare a suspension; then adding 0.2-1.2 parts of siloxane and 0.02-0.04 parts of a catalyst to the suspension, and then mixing and stirring at 150 rpm for 10 minutes to prepare a hydrogel; UV curing the hydrogel, freezing the cured hydrogel at -40°C to prepare an ice product, and then crushing the ice product to prepare an ice product powder with a diameter of 50-100 nm; placing the ice product powder in a freeze dryer tray, drying it by gradient heating, and the whole drying time is 15-30 hours to prepare a modified graphene aerogel powder; (3) Mix 3 parts of modified graphene aerogel powder, 0.5-1.5 parts of titanium dioxide powder and 70 parts of sodium hydroxide solution, stir at 150 rpm for 20 minutes, ultrasonicate at 50 kHz for 30 minutes, and then keep warm at 160-180°C for 48 hours. Filter the solid, wash it with deionized water for 3 times, then wash it with hydrochloric acid solution for 3 times, and finally wash it with deionized water for 3 times, and dry it at room temperature and pressure for 2 hours. Then disperse the dried product into nitric acid aqueous solution with a solid-liquid ratio of 1:100, keep warm at 100-120°C for 40 hours, dry it at room temperature and pressure for 2 hours, and then place it in a Mabo furnace for high temperature treatment at 450°C for 1-3 hours to obtain a composite filler. (4) Terephthalic acid, ethylene glycol and composite filler are mixed in a mass ratio of 1:0.9-1.1:0.1-0.3 for esterification reaction and polycondensation reaction. The temperature of the esterification reaction is 180°C, the pressure is 0.01MPa and the time is 2h. After the esterification reaction is completed, the polycondensation reaction is carried out in stages: the first stage polycondensation temperature is 220°C, the pressure is 0.4-0.8kPa and the time is 0.5-1.5h; the second stage polycondensation temperature is 240°C, the pressure is 20-80Pa and the time is 1-3h. The polyester raw material after polycondensation is passed through a screw After extrusion and melting, the slurry is transformed into hollow shaped spinning at the spinneret to obtain hollow shaped fibers. The ejected fibers are quickly shaped by high-speed stretching and ring-blown air cooling, and flow into the reciprocating machine for barrel bundling. When the technology reaches a total denier of 600 deniers for composite production, it is quickly stretched through an oil bath, and then enters the steam box for micro-stretching. The steam box temperature is 120°C, and the micro-stretching time is 2s. Three-dimensional curling is performed inside to fully form the fibers, and then they enter the cutting machine for cutting. After cutting, they are placed in a three-layer oven for heat setting to make graphene cloud velvet.

2. The method for preparing graphene cloud velvet according to claim 1, characterized in that: The ball milling conditions in step (1) are: 1.2 cm steel balls, and a ball-to-material ratio of 6-10:

1.

3. The method for preparing graphene cloud velvet according to claim 1, characterized in that: The siloxane in step (2) is γ-methacryloxypropyltrimethoxysilane.

4. The method for preparing graphene cloud velvet according to claim 1, characterized in that: The catalyst in step (2) is N,N,N',N'-tetramethylethylenediamine.

5. The method for preparing graphene cloud velvet according to claim 1, characterized in that: The UV curing conditions in step (2) are: the power of the UV lamp is 2.4 kW, and the curing time is 2 h.

6. The method for preparing graphene cloud velvet according to claim 1, characterized in that: The vacuum freeze-drying conditions in step (2) are: drying at a vacuum degree of 10 Pa and a partition temperature of -5°C.

7. The method for preparing graphene cloud velvet according to claim 1, characterized in that: The concentration of the sodium hydroxide aqueous solution in step (3) is 10M.

8. The method for preparing graphene cloud velvet according to claim 1, characterized in that: The concentration of the hydrochloric acid aqueous solution in step (3) is 0.1-0.3M.

9. The method for preparing graphene cloud velvet according to claim 1, characterized in that: The concentration of the nitric acid aqueous solution in step (3) is 0.05-0.07M.

10. The method for preparing graphene cloud velvet according to claim 1, characterized in that: The heat setting temperature in step (4) is 180°C.

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