Preparation method of antibacterial warm-keeping graphene quantum dot cloud velvet

Abstract

The invention discloses a preparation method of antibacterial warm-keeping graphene quantum dot cloud velvet, and relates to the technical field of cloud velvet. Single-layer graphene is prepared through a chemical method, then single-layer graphene quantum dots are prepared through an electrochemical reaction, the size reaches the nanometer level, the single-layer structure is sharper, and the sterilization effect can be improved; modification enables the surface to be rich in carboxyl and to be attached to cellulose to improve the agglomeration problem; secondly, breaking intermolecular hydrogen bonds of cellulose macromolecules by utilizing the strong action of ball milling and a polar solvent rich in hydroxyl and combining ultrasonic waves; then, the cellulose is combined with hydroxyl cardanol with a side chain containing a hydroxyl group, and cooperates with graphene quantum dots attached to the cellulose for efficient catalysis to generate active oxygen, so that the sterilization effect is achieved; then the modified nanocellulose is prepared into aerogel, and the aerogel is added into polyester as antibacterial master batch to prepare the cloud velvet, so that the warm keeping effect is improved. The cloud velvet prepared by the invention has antibacterial and warm-keeping effects.

Description

Technical Field

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

[0002] Cloud velvet is actually a fiber made using a new process. It has good warmth retention and high elasticity, and is comfortable and light. Usually, cloud velvet can be processed and applied in many fields such as clothing and household items. Cloud velvet is a new fiber that is completely different 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 with your hands, and it feels like condensed fat. When you hold it with both hands, you will feel full when you look at it. Now cloud velvet can be used as a filler for many items, including pillows, quilts, cloth dolls, sofas, soft beds, etc.

[0003] However, there are still many defects in the preparation of cloud velvet. First, the antibacterial cellulose is to prepare cellulose nanofibers first, and then physically combine them with antibacterial agents. The process is cumbersome, the operation is complicated, the separation of intermediate products is difficult, and the yield is low. Since the antibacterial agent is only dispersed on the surface of the nanofiber, it is easy to fall off, the antibacterial durability is poor, it is difficult to reuse, and the stability is poor. In addition, the addition of a single inorganic antibacterial agent makes the antibacterial effect insufficient. Second, the addition of graphene quantum dots is easy to agglomerate due to the π-π conjugated bonds. The cloud velvet produced has poor performance and the bactericidal effect of the graphene quantum dots is also greatly reduced. Therefore, the present invention proposes a preparation method to solve the above problems. Summary of the invention

[0004] The purpose of the present invention is to provide a method for preparing antibacterial and heat-retaining graphene quantum dot cloud velvet to solve the problems existing in the prior art.

[0005] In order to solve the above technical problems, the present invention provides the following technical solutions: a method for preparing antibacterial and heat-retaining graphene quantum dot cloud velvet, comprising the following preparation steps: (1) Take 3 parts of natural graphite powder, add 12 parts of concentrated sulfuric acid, 2-3 parts of potassium persulfate and 2-3 parts of phosphorus pentoxide, mix them evenly at 80°C, and react for 4-6 hours; after the reaction is completed, cool to room temperature, add 10 parts of deionized water to dilute, let stand for 24 hours, and then separate by membrane filtration, take the solid and wash it with deionized water for 3 times, and then let stand for 24 hours to obtain oxidized graphite; slowly add the pre-oxidized graphite to 120-140 parts of the cooled 0°C mixed solution while stirring, the stirring speed is 60rpm, stir at 35°C for 2 hours, dilute with 250 parts of deionized water, continue to stir for 2 hours, add 600 parts of deionized water, and then add 15-25 parts of hydrogen peroxide solution after stirring for 2 hours; filter, take the solid and dilute it with 8% concentration of hydrogen peroxide solution The obtained graphene oxide was washed twice with a hydrochloric acid aqueous solution and then washed three times with deionized water, and then the product was dialyzed for one week to obtain graphite oxide; the obtained graphite oxide was prepared into an aqueous solution with a concentration of 0.5 mg / ml, and ultrasonically treated in an ultrasonic machine for 30 minutes with an ultrasonic power of 35 kHz to obtain a single-layer graphite oxide sheet solution; the single-layer graphite oxide sheet solution was centrifuged in a high-speed centrifuge at a centrifugal speed of 15000 rpm for 20 minutes, and the obtained solid was vacuum dried at 0.085 MPa for 2 hours; the dried graphene oxide solid was dispersed in a dimethyl sulfoxide solution at a dosage ratio of 1:1, and the mixture was transferred to a reactor after stirring at 150 rpm for 20 minutes and then heated at 160-200 °C for 2 hours. ℃ for 10-14h, after filtering, wash with deionized water for 3 times, and dry under vacuum at 0.085MPa for 2h to obtain single-layer graphene; weigh 2 parts of single-layer graphene, put 1 part each in a centrifuge tube with holes, put a 1000Da dialysis bag on the outside of the centrifuge tube, use them as positive and negative electrode materials respectively, and the distance between the two electrode materials is 2cm; take 20 parts of 1-butyl-3-methyl tetrafluoroborate ionic liquid and 20 parts of deionized water as electrolyte, soak the electrodes for 1h, start to connect the DC power supply, and the DC voltage used is 10V; during the power-on process, exchange the positive and negative electrodes every 2h, and stop the power-on after 10h of reaction; put the electrolyzed electrolyte in a centrifuge tube, and centrifuge at a speed of 8000-10000rpm. Centrifuge for 30 minutes to obtain a bottom precipitate, dialyze, place the liquid in the bag in a hydrothermal autoclave and keep it at 180°C for 3 hours; then centrifuge the solution at 8000-10000rpm for 30 minutes, wash the solid with deionized water twice, and then dry it at room temperature and pressure for 5 hours to obtain a single-layer graphene quantum dot; mix 1 part of the single-layer graphene quantum dot with 100 parts of deionized water, then add 10-20 parts of bromoacetic acid, ultrasonicate at 30kHz power for 10-30 minutes, and then react at room temperature for 5 hours; after the reaction is completed, centrifuge at 8000-10000rpm for 30 minutes, wash the solid with deionized water 3 times, and then freeze-dry at -40°C for 2 hours to obtain a carboxyl-functionalized single-layer graphene quantum dot; (2) First, the mass ratio of the nanocellulose raw material and montmorillonite is 0.2-1:1, and the ball milling treatment is carried out at a ball milling speed of 300-600 rpm and a ball milling time of 3-8 h; prepare a pretreatment solution, adjust the pH to 7, raise the temperature to 40-50°C, and completely immerse the ball-milled nanocellulose in the pretreatment solution for 12-24 h, and the solid-liquid mass ratio is 1:10; then the pretreatment solution is heated to 50-60°C, the pH is adjusted to 8, and the nanocellulose is immersed for another 1-2 h, and ultrasonic low-frequency short-time oscillation is performed at the current temperature to obtain pretreated nanocellulose; the pretreated nanocellulose micro-particles, hydroxycardanol containing hydroxyl groups in the side chains, and ethanol are mixed at a mass ratio of 2-4:1:10, placed in a reactor, heated to 100-140°C for reaction for 2-4 h, and after the reaction, centrifuged and washed three times with deionized water at a centrifugal speed of 10000 rpm, and the upper suspension is collected. , the modified nanocellulose is obtained; the modified nanocellulose is mixed with deionized water in proportion to prepare a modified nanofiber dispersion with a mass fraction of 1.0%, and stirred at 150 rpm for 30 min; 10 portions of the modified nanofiber dispersion are taken, an appropriate amount of glacial acetic acid is added to adjust the pH value of the dispersion to 4, and then stirred at 150 rpm for 1 h, and then carboxyl functionalized single-layer graphene quantum dots are added to the dispersion and mixed and stirred at 150 rpm for 3 h to obtain a uniform solution; finally, the solution is poured into a polytetrafluoroethylene mold and frozen in liquid nitrogen for 3 min, and the frozen solid sample is further vacuum freeze-dried at -60 ° C and 1 Pa for 48 h to obtain a 0.1-1.5 mm composite aerogel masterbatch; (3) Terephthalic acid, ethylene glycol and composite aerogel masterbatch 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 melted by screw extrusion, and the ejected fiber is quickly shaped by high-speed stretching and ring-blown air cooling, and flows into the reciprocating machine for barrel bundling. When the technology reaches the total denier of composite production of 600 denier, 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 it, and then it enters the cutting machine for cutting. After cutting, it is placed in a three-layer oven for heat setting to make cloud velvet.

[0006] Furthermore, the concentration of concentrated sulfuric acid in step (1) is 92-98%.

[0007] Furthermore, the filter membrane in step (1) is a cellulose acetate membrane with a pore size of 0.2 micrometers.

[0008] Furthermore, the mixed solution in step (1) is composed of 95% concentrated sulfuric acid and potassium permanganate in a mass ratio of 8:1.

[0009] Furthermore, the concentration of the dilute hydrochloric acid aqueous solution in step (1) is 8%.

[0010] Furthermore, the dialysis process in step (1) is to place the bottom precipitate in a dialysis bag with a molecular weight cutoff of 1000Da, use water as the dialysis fluid, dialyze for 3 days, and change the water every 8 hours.

[0011] Furthermore, the pretreatment solution in step (2) is prepared by mixing a sodium hydroxide solution with a mass concentration of 2-10% and a n-butanol solution with a mass concentration of 45-75% in a volume ratio of 1:1-5.

[0012] Furthermore, the ultrasonic conditions used in step (2) are: frequency 20-50kHz, power 200-600W, and ultrasonic time 10-20min.

[0013] Furthermore, in step (2), the mass ratio of carboxyl functionalized single-layer graphene quantum dots to the dispersion is 0.01-0.05:1.

[0014] Furthermore, the heat setting temperature in step (3) is 180°C.

[0015] Compared with the prior art, the beneficial effects achieved by the present invention are: The present invention prepares aerogel antibacterial masterbatch by combining single-layer graphene quantum dots with modified cardanol nanocellulose, and adds the masterbatch into polyester to prepare cloud velvet, so as to achieve the antibacterial and warm-keeping effects.

[0016] Firstly, the present invention uses a chemical method to prepare graphene with a single-layer two-dimensional structure, namely, single-layer graphene; using the single-layer graphene as a raw material, graphene nano-quantum dots with a single-layer structure are prepared through an electrochemical reaction; compared with ordinary graphene quantum dots, the graphene quantum dots prepared by the present invention not only reach the nanometer level in size, but also can increase the contact area between the quantum dots and bacterial cells, so that they can interact with the phospholipid molecules on the bacterial cell membrane, thereby killing the bacteria; its single-layer two-dimensional structure also makes the edges of the quantum dots sharper, which can improve the effect and success rate of cutting the cell wall of damaged bacteria; on this basis, the single-layer graphene quantum dots are functionally modified, so that the surface of the single-layer graphene quantum dots is rich in carboxyl groups, and the carboxyl groups are connected to nanocellulose and attached to the cellulose surface, thereby greatly improving the agglomeration problem of the graphene quantum dots; Secondly, the mechanical chemical action generated during the ball milling process is used to destroy the physical structure of the nanocellulose, and then the strong effect of the hydroxyl-rich polar solvent is used in combination with ultrasound to destroy the intermolecular hydrogen bonds of the cellulose macromolecules, causing them to dissociate; then it is combined with hydroxycardanol containing hydroxyl groups on the side chain, and its photosensitivity to release active oxygen under the action of sunlight is utilized, and it cooperates with the graphene quantum dots attached to the cellulose to efficiently catalyze the production of active oxygen, thereby achieving the effect of sterilization; then the modified nanocellulose is prepared into aerogel and added into polyester as an antibacterial masterbatch to prepare cloud velvet, which solves the dispersion problem of cellulose and effectively improves the warmth retention effect of the cloud velvet. DETAILED DESCRIPTION

[0017] 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.

[0018] 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 an antibacterial and heat-retaining graphene quantum dot 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.

[0019] Warmth retention: The antibacterial properties of the examples and comparative examples were tested for warmth retention in accordance with GB / T11048-2008-T “Determination of thermal and moisture resistance of textiles under steady-state conditions for physiological comfort”.

[0020] Example 1; (1) Take 3 parts of natural graphite powder, add 12 parts of 92% concentrated sulfuric acid, 2 parts of potassium persulfate and 2 parts of phosphorus pentoxide, mix them evenly at 80°C, and react for 4 hours; after the reaction is completed, cool to room temperature, add 10 parts of deionized water to dilute, let stand for 24 hours, then filter and separate with a 0.2 micron pore cellulose acetate membrane, wash the solid with deionized water 3 times, and then let stand for 24 hours to obtain oxidized graphite; slowly add the pre-oxidized graphite to 120 parts of a cooled 0°C mixed solution with 95% concentrated sulfuric acid and potassium permanganate in a mass ratio of 8:1, stir at 60 rpm, stir at 35°C for 2 hours, dilute with 250 parts of deionized water, continue stirring for 2 hours, add 600 parts of deionized water, and then add 15 parts of hydrogen peroxide solution after stirring for 2 hours; filter, take the solid and The obtained graphene oxide was washed twice with 8% dilute hydrochloric acid aqueous solution, and then washed three times with deionized water, and then the product was dialyzed for one week to obtain graphite oxide; the obtained graphite oxide was prepared into a 0.5 mg / ml aqueous solution, and ultrasonically treated in an ultrasonic machine for 30 minutes, and the ultrasonic power was 35kHz to obtain a single-layer graphite oxide sheet solution; the single-layer graphite oxide sheet solution was centrifuged in a high-speed centrifuge, and the centrifugal speed was 15000rpm, and the time was 20min. The obtained solid was vacuum dried at 0.085MPa for 2h; the dried graphene oxide solid was dispersed in dimethyl sulfoxide solution, and the amount ratio of the two was 1:1. After stirring at 150rpm for 20min, it was transferred to a reactor and reacted at 160℃ for 10h. After filtering, it was washed three times with deionized water and 0.085MPa vacuum drying for 2h to obtain single-layer graphene; weigh 2 parts of single-layer graphene, put 1 part each in a centrifuge tube with holes, put a 1000Da dialysis bag on the outside of the centrifuge tube, as the positive and negative electrode materials, respectively, and the distance between the two electrode materials is 2cm; take 20 parts of 1-butyl-3-methyl tetrafluoroborate ionic liquid and 20 parts of deionized water as electrolyte, soak the electrodes for 1h, start to connect the DC power supply, the DC voltage used is 10V; during the power-on process, the positive and negative electrodes are exchanged every 2h, and the power is stopped after the reaction for 10h; the electrolyte after electrolysis is placed in a centrifuge tube, centrifuged at 8000rpm for 30min to obtain a bottom precipitate, and the bottom precipitate is placed in a centrifuge tube with a molecular weight cutoff of 10 00Da dialysis bag, water was used as the dialysis fluid, and the dialysis was performed for 3 days, and the water was changed every 8 hours. The liquid in the bag was placed in a hydrothermal autoclave and maintained at 180°C for 3 hours; then the solution was centrifuged at 8000rpm for 30 minutes, the solid was washed twice with deionized water, and then dried at room temperature and pressure for 5 hours to obtain single-layer graphene quantum dots; 1 part of single-layer graphene quantum dots was mixed with 100 parts of deionized water, and then 10 parts of bromoacetic acid were added, and ultrasound was performed at 30kHz power for 10 minutes, and then reacted at room temperature for 5 hours; after the reaction was completed, it was centrifuged at 8000rpm for 30 minutes, the solid was washed three times with deionized water, and then freeze-dried at -40°C for 2 hours to obtain carboxyl functionalized single-layer graphene quantum dots;. (2) First, the nanocellulose raw material and montmorillonite were mixed at a mass ratio of 0.2:1, and ball milling was performed at a ball milling speed of 300 rpm for 3 hours. A 2% sodium hydroxide solution and a 45% n-butanol solution were mixed at a volume ratio of 1:1 to prepare a pretreatment solution, the pH was adjusted to 7, the temperature was raised to 40°C, and the ball-milled nanocellulose was completely immersed in the pretreatment solution for 12 hours, with a solid-liquid mass ratio of 1:10. The pretreatment solution was then heated to 50°C, the pH was adjusted to 8, and the solution was immersed for another hour. Ultrasonic low-frequency short-time oscillation was performed at the current temperature. The ultrasonic conditions were: frequency 20 kHz, power 200 W, and ultrasonic time 10 min to obtain pretreated nanocellulose. The pretreated nanocellulose micro-, hydroxy cardanol containing hydroxyl groups on the side chains and ethanol were mixed at a mass ratio of 2:1:10, placed in a reactor, and heated to 100°C for reaction for 2 hours. After the reaction, the mixture was centrifuged and washed three times with deionized water at a speed of 10000 rpm, and the upper suspension was collected to obtain modified nanocellulose; the modified nanocellulose and deionized water were mixed in proportion to prepare a modified nanofiber dispersion with a mass fraction of 1.0%, and the mixture was stirred at 150 rpm for 30 min to make it uniform; 10 portions of the modified nanofiber dispersion were taken, and an appropriate amount of glacial acetic acid was added to adjust the pH value of the dispersion to 4, and then stirred at 150 rpm for 1 h, and then carboxyl functionalized single-layer graphene quantum dots were added to the dispersion and mixed and stirred at 150 rpm for 3 h to obtain a uniform solution, and the mass ratio of carboxyl functionalized single-layer graphene quantum dots to the dispersion was 0.01:1; finally, the solution was poured into a polytetrafluoroethylene mold and frozen in liquid nitrogen for 3 min, and the frozen solid sample was further vacuum freeze-dried at -60 ° C and 1 Pa for 48 h to obtain a 0.1 mm composite aerogel masterbatch; (3) Terephthalic acid, ethylene glycol and composite aerogel masterbatch were mixed in a mass ratio of 1:0.9:0.1 for esterification reaction and polycondensation reaction. The temperature of the esterification reaction was 180°C, the pressure was 0.01MPa and the time was 2h. After the esterification reaction, the polycondensation reaction was carried out in stages: the first stage was at a temperature of 220°C, the pressure was 0.4kPa and the time was 0.5h; the second stage was at a temperature of 240°C, the pressure was 20Pa and the time was 1h. The polyester raw material after polycondensation was passed through a screw After extrusion and melting, 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 denier 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 fiber, and then it enters the cutting machine for cutting. After cutting, it is placed in a three-layer oven for heat setting at 180°C to make cloud velvet.

[0021] Example 2; (1) Take 3 parts of natural graphite powder, add 12 parts of 95% concentrated sulfuric acid, 2.5 parts of potassium persulfate and 2.5 parts of phosphorus pentoxide, mix them evenly at 80°C, and react for 5 hours; after the reaction is completed, cool to room temperature, add 10 parts of deionized water to dilute, let stand for 24 hours, then filter and separate with a 0.2 micron pore cellulose acetate membrane, take the solid and wash it with deionized water 3 times, then let stand for 24 hours to obtain oxidized graphite; slowly add the pre-oxidized graphite to 130 parts of a cooled 0°C mixed solution with 95% concentrated sulfuric acid and potassium permanganate in a mass ratio of 8:1, stir at 60 rpm, stir at 35°C for 2 hours, dilute with 250 parts of deionized water, continue stirring for 2 hours, add 600 parts of deionized water, and then add 20 parts of hydrogen peroxide solution after stirring for 2 hours; filter, take the solid The solid was washed twice with a dilute hydrochloric acid solution of 8% concentration, and then washed three times with deionized water, and then the product was dialyzed for one week to obtain graphite oxide; the obtained graphite oxide was prepared into an aqueous solution with a concentration of 0.5 mg / ml, and ultrasonically treated in an ultrasonic machine for 30 minutes with an ultrasonic power of 35 kHz to obtain a single-layer graphite oxide sheet solution; the single-layer graphite oxide sheet solution was then centrifuged in a high-speed centrifuge at a centrifugal speed of 15000 rpm for 20 minutes, and the obtained solid was vacuum dried at 0.085 MPa for 2 hours; the dried graphene oxide solid was dispersed in a dimethyl sulfoxide solution at a dosage ratio of 1:1, and the mixture was transferred to a reactor after stirring at 150 rpm for 20 minutes and reacted at 180°C for 12 hours. After filtering, the mixture was washed three times with deionized water and 0.085MPa vacuum drying for 2h to obtain single-layer graphene; weigh 2 parts of single-layer graphene, put 1 part each in a centrifuge tube with holes, put a 1000Da dialysis bag on the outside of the centrifuge tube, use them as positive and negative electrode materials respectively, and the distance between the two electrode materials is 2cm; take 20 parts of 1-butyl-3-methyl tetrafluoroborate ionic liquid and 20 parts of deionized water as electrolyte, soak the electrodes for 1h, start to connect the DC power supply, and the DC voltage used is 10V; during the power-on process, the positive and negative electrodes are exchanged every 2h, and the power is stopped after the reaction for 10h; the electrolyte after electrolysis is placed in a centrifuge tube, centrifuged at 9000rpm for 30min to obtain a bottom precipitate, and the bottom precipitate is placed in a centrifuge tube with a molecular weight cutoff of 10 00Da dialysis bag, water was used as the dialysis fluid, and the dialysis was performed for 3 days, and the water was changed every 8 hours. The liquid in the bag was placed in a hydrothermal autoclave and kept at 180℃ for 3 hours; then the solution was centrifuged at 9000rpm for 30 minutes, the solid was washed twice with deionized water, and then dried at room temperature and pressure for 5 hours to obtain single-layer graphene quantum dots; 1 part of single-layer graphene quantum dots was mixed with 100 parts of deionized water, and then 15 parts of bromoacetic acid were added, and ultrasonicated at 30kHz power for 20 minutes, and then reacted at room temperature for 5 hours; after the reaction was completed, it was centrifuged at 9000rpm for 30 minutes, the solid was washed three times with deionized water, and then freeze-dried at -40℃ for 2 hours to obtain carboxyl functionalized single-layer graphene quantum dots;. (2) First, the mass ratio of nanocellulose raw material and montmorillonite was 0.6:1, and ball milling was performed. The ball milling speed was 450 rpm and the ball milling time was 5.5 h. A 6% sodium hydroxide solution and a 60% n-butanol solution were mixed in a volume ratio of 1:3 to prepare a pretreatment solution. The pH value was adjusted to 7 and the temperature was raised to 45°C. The ball-milled nanocellulose was completely immersed in the pretreatment solution for 18 h. The solid-liquid mass ratio was 1:10. The pretreatment solution was then heated to 55°C and the pH value was adjusted to 8. The solution was then immersed for another 1.5 h. Ultrasonic low-frequency short-time oscillation was performed at the current temperature. The ultrasonic conditions were: frequency 35 kHz, power 400 W, and ultrasonic time 15 min to obtain pretreated nanocellulose. The pretreated nanocellulose micro-cellulose, hydroxyl cardanol containing hydroxyl groups on the side chains, and ethanol were mixed in a mass ratio of 3:1:10, placed in a reactor, heated to 120°C for reaction for 3 h, and after the reaction, the nanocellulose was centrifuged and washed three times with deionized water. The centrifuge speed was 10000rpm, and the upper suspension was collected to obtain modified nanocellulose; the modified nanocellulose was mixed with deionized water in proportion to prepare a modified nanofiber dispersion with a mass fraction of 1.0%, and stirred at 150rpm for 30min; 10 portions of the modified nanofiber dispersion were taken, and an appropriate amount of glacial acetic acid was added to adjust the pH value of the dispersion to 4, and then stirred at 150rpm for 1h, and then carboxyl functionalized single-layer graphene quantum dots were added to the dispersion and mixed and stirred at 150rpm for 3h to obtain a uniform solution, and the mass ratio of carboxyl functionalized single-layer graphene quantum dots to the dispersion was 0.03:1; finally, the solution was poured into a polytetrafluoroethylene mold and frozen in liquid nitrogen for 3min, and the frozen solid sample was continued to be vacuum freeze-dried at -60℃ and 1Pa for 48h to obtain a 0.8mm composite aerogel masterbatch; (3) Terephthalic acid, ethylene glycol, and composite aerogel masterbatch 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 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 extruded by a screw After melting and ejecting, the fibers are quickly shaped through high-speed stretching and cooling by annular air, and then flow into the reciprocating machine for barrel bundling. When the technology reaches the total denier of 600 denier 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. After cutting, they are placed in a three-layer oven for heat setting at 180°C to make cloud velvet.

[0022] Example 3; (1) Take 3 parts of natural graphite powder, add 12 parts of 98% concentrated sulfuric acid, 3 parts of potassium persulfate and 3 parts of phosphorus pentoxide, mix evenly at 80°C, and react for 6 hours; after the reaction is completed, cool to room temperature, add 10 parts of deionized water to dilute, let stand for 24 hours, then filter and separate with a 0.2 micron pore cellulose acetate membrane, take the solid and wash it with deionized water 3 times, then let stand for 24 hours to obtain oxidized graphite; slowly add the pre-oxidized graphite to 140 parts of a cooled 0°C mixed solution with 95% concentrated sulfuric acid and potassium permanganate in a mass ratio of 8:1, stir at 60rpm, stir at 35°C for 2 hours, dilute with 250 parts of deionized water, continue stirring for 2 hours, add 600 parts of deionized water, and then add 25 parts of hydrogen peroxide solution after stirring for 2 hours; filter, take the solid and The obtained graphene oxide was washed twice with 8% dilute hydrochloric acid aqueous solution, and then washed three times with deionized water, and then the product was dialyzed for one week to obtain graphite oxide; the obtained graphite oxide was prepared into a 0.5 mg / ml aqueous solution, and ultrasonically treated in an ultrasonic machine for 30 minutes, and the ultrasonic power was 35kHz to obtain a single-layer graphite oxide sheet solution; the single-layer graphite oxide sheet solution was centrifuged in a high-speed centrifuge, and the centrifugal speed was 15000rpm, and the time was 20min. The obtained solid was vacuum dried at 0.085MPa for 2h; the dried graphene oxide solid was dispersed in dimethyl sulfoxide solution, and the amount ratio of the two was 1:1. After stirring at 150rpm for 20min, it was transferred to a reactor and reacted at 200℃ for 14h. After filtering, it was washed three times with deionized water and 0.085MPa vacuum drying for 2h to obtain single-layer graphene; weigh 2 parts of single-layer graphene, put 1 part each in a centrifuge tube with holes, put a 1000Da dialysis bag on the outside of the centrifuge tube, as the positive and negative electrode materials, respectively, and the distance between the two electrode materials is 2cm; take 20 parts of 1-butyl-3-methyl tetrafluoroborate ionic liquid and 20 parts of deionized water as electrolyte, soak the electrodes for 1h, start to connect the DC power supply, the DC voltage used is 10V; during the power-on process, the positive and negative electrodes are exchanged every 2h, and the power is stopped after the reaction for 10h; the electrolyte after electrolysis is placed in a centrifuge tube, centrifuged at a speed of 10000rpm for 30min to obtain a bottom precipitate, and the bottom precipitate is placed in a 100 molecular weight cutoff 0Da dialysis bag, water was used as the dialysis fluid, and the dialysis was performed for 3 days, and the water was changed every 8 hours. The liquid in the bag was placed in a hydrothermal autoclave and kept at 180°C for 3 hours; then the solution was centrifuged at 10000rpm for 30 minutes, the solid was washed twice with deionized water, and then dried at room temperature and pressure for 5 hours to obtain single-layer graphene quantum dots; 1 part of single-layer graphene quantum dots was mixed with 100 parts of deionized water, and then 20 parts of bromoacetic acid were added, and ultrasound was performed at 30kHz power for 30 minutes, and then reacted at room temperature for 5 hours; after the reaction was completed, it was centrifuged at 10000rpm for 30 minutes, the solid was washed three times with deionized water, and then freeze-dried at -40°C for 2 hours to obtain carboxyl functionalized single-layer graphene quantum dots;. (2) First, the nanocellulose raw material and montmorillonite were mixed in a mass ratio of 1:1 and ball-milled at a speed of 600 rpm for 8 h. A 10% sodium hydroxide solution and a 75% n-butanol solution were mixed in a volume ratio of 1:5 to prepare a pretreatment solution. The pH value was adjusted to 7 and the temperature was raised by 50°C. The ball-milled nanocellulose was completely immersed in the pretreatment solution for 24 h. The solid-liquid mass ratio was 1:10. The pretreatment solution was then heated to 60°C and the pH value was adjusted to 8. The solution was then immersed for another 2 h. Ultrasonic low-frequency short-time oscillation was performed at the current temperature. The ultrasonic conditions were: frequency 50 kHz, power 600 W, and ultrasonic time 20 min to obtain pretreated nanocellulose. The pretreated nanocellulose micro-cellulose, hydroxy cardanol containing hydroxyl groups on the side chains, and ethanol were mixed in a mass ratio of 4:1:10, placed in a reactor, heated to 140°C for reaction for 4 h, and after the reaction, the nanocellulose was centrifuged and washed three times with deionized water at a speed of 100 00rpm, collect the upper suspension to obtain modified nanocellulose; mix the modified nanocellulose and deionized water in proportion to prepare a modified nanofiber dispersion with a mass fraction of 1.0%, and stir at 150rpm for 30min; take 10 parts of the modified nanofiber dispersion, add an appropriate amount of glacial acetic acid to adjust the pH value of the dispersion to 4, and then stir at 150rpm for 1h, then add carboxyl functionalized single-layer graphene quantum dots to the dispersion and mix and stir at 150rpm for 3h to obtain a uniform solution, and the mass ratio of carboxyl functionalized single-layer graphene quantum dots to the dispersion is 0.05:1; finally, pour the solution into a polytetrafluoroethylene mold and freeze it in liquid nitrogen for 3min, and continue to vacuum freeze-dry the frozen solid sample at -60℃ and 1Pa for 48h to obtain a 1.5mm composite aerogel masterbatch; (3) Terephthalic acid, ethylene glycol and composite aerogel masterbatch are mixed in a mass ratio of 1:1.1:0.3 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 0.8kPa, and the time is 1.5h; the second stage polycondensation temperature is 240°C, the pressure is 80Pa, and the time is 3h. The polyester raw material after polycondensation is passed through a screw After extrusion and melting, 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 denier 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 fiber, and then it enters the cutting machine for cutting. After cutting, it is placed in a three-layer oven for heat setting at 180°C to make cloud velvet.

[0023] Comparative Example 1: The difference between Comparative Example 1 and Example 2 is that steps (1) and (2) are different. Steps (1) and (2) are changed to: (1) Weigh 2 parts of micron-sized graphene and put them in 1 part each in a centrifuge tube with holes. A 1000Da dialysis bag is put on the outside of the centrifuge tube to serve as the positive and negative electrode materials, respectively. The distance between the two electrode materials is 2 cm; 20 parts of 1-butyl-3-methyl tetrafluoroborate ionic liquid are mixed with 20 parts of deionized water as an electrolyte. After soaking the electrodes for 1 hour, a DC power supply is turned on. The DC voltage used is 10 V; during the power-on process, the positive and negative electrodes are exchanged every 2 hours. After the reaction lasts for 10 hours, the power is stopped; the electrolyte after electrolysis is placed in a centrifuge tube and centrifuged at 9000 rpm for 30 minutes to obtain a bottom precipitate. The bottom precipitate is placed in a dialysis bag with a molecular weight cutoff of 1000Da, and water is used as the dialysis fluid for 3 days. The water is changed every 8 hours, and the liquid in the bag is placed in a hydrothermal autoclave and maintained at 180°C for 3 hours; then the solution is centrifuged at 9000rpm for 30 minutes, the solid is washed twice with deionized water, and then dried at room temperature and pressure for 5 hours to obtain a single-layer graphene quantum dot; 1 part of the single-layer graphene quantum dot is mixed with 100 parts of deionized water, and then 15 parts of bromoacetic acid are added, and ultrasound is carried out at a power of 30kHz for 20 minutes, and then reacted at room temperature for 5 hours; after the reaction is completed, it is centrifuged at 9000rpm for 30 minutes, the solid is washed three times with deionized water, and then freeze-dried at -40°C for 2 hours to obtain a carboxyl-functionalized single-layer graphene quantum dot; (2) First, the nanocellulose raw material and montmorillonite were mixed in a mass ratio of 0.6:1, and ball milled at a speed of 450 rpm for 5.5 h. A 6% sodium hydroxide solution and a 60% n-butanol solution were mixed in a volume ratio of 1:3 to prepare a pretreatment solution, the pH was adjusted to 7, the temperature was raised to 45°C, and the ball-milled nanocellulose was completely immersed in the pretreatment solution for 18 h. The solid-liquid mass ratio was 1:10. The pretreatment solution was then heated to 55°C, the pH was adjusted to 8, and the solution was immersed for another 1.5 h. Ultrasonic low-frequency short-time oscillation was performed at the current temperature. The ultrasonic conditions were: frequency 35 kHz, power 400 W, and ultrasonic time 15 min to obtain pretreated nanocellulose. The pretreated nanocellulose micro-, hydroxycardanol containing hydroxyl groups on the side chains and ethanol were mixed in a mass ratio of 3:1:10, placed in a reactor, heated to 120°C for reaction for 3 h, and after the reaction, the nanocellulose was centrifuged and washed three times with deionized water at a centrifugal speed. The reaction mixture was stirred at 10000 rpm, and the upper suspension was collected to obtain modified nanocellulose; the modified nanocellulose was mixed with deionized water in proportion to prepare a modified nanofiber dispersion with a mass fraction of 1.0%, and the mixture was stirred at 150 rpm for 30 min to obtain a uniform solution; 10 parts of the modified nanofiber dispersion were taken, and an appropriate amount of glacial acetic acid was added to adjust the pH value of the dispersion to 4, and the mixture was stirred at 150 rpm for 1 h, and then the carboxyl functionalized graphene quantum dots were added to the dispersion and mixed at 150 rpm for 3 h to obtain a uniform solution, wherein the mass ratio of the carboxyl functionalized graphene quantum dots to the dispersion was 0.03:1; finally, the solution was poured into a polytetrafluoroethylene mold and frozen in liquid nitrogen for 3 min, and the frozen solid sample was further vacuum freeze-dried at -60°C and 1 Pa for 48 h to obtain a 0.8 mm composite aerogel masterbatch; the remaining steps were the same as those in Example 2.

[0024] Comparative Example 2: The difference between Comparative Example 2 and Example 2 is that steps (1) and (2) are different. Steps (1) and (2) are changed to: (1) 3 parts of natural graphite powder are taken, 12 parts of concentrated sulfuric acid with a concentration of 95%, 2.5 parts of potassium persulfate and 2.5 parts of phosphorus pentoxide are added, and the mixture is uniformly mixed at 80°C and reacted for 5 hours; after the reaction is completed, the mixture is cooled to room temperature, 10 parts of deionized water are added, and the mixture is allowed to stand for 24 hours, and then filtered and separated with a 0.2 micron pore cellulose acetate membrane, and the solid is washed with deionized water 3 times, and then allowed to stand for 24 hours to obtain a graphite oxide. ; The pre-oxidized graphite was slowly added to 130 parts of a cooled 0°C mixed solution while stirring, wherein the solution was composed of 95% concentrated sulfuric acid and potassium permanganate in a mass ratio of 8:1, and the stirring speed was 60 rpm. After stirring at 35°C for 2 hours, 250 parts of deionized water were added, and 600 parts of deionized water were added after continuing to stir for 2 hours. After stirring for another 2 hours, 20 parts of hydrogen peroxide solution were added; filtration was performed, and the solid was washed twice with 8% dilute hydrochloric acid aqueous solution, and then washed three times with deionized water. The product was then dialyzed for one week to obtain oxidized graphite; the obtained graphite was The graphite was prepared into a 0.5 mg / ml aqueous solution, and ultrasonically treated for 30 minutes in an ultrasonic machine with an ultrasonic power of 35 kHz to obtain a monolayer graphite oxide sheet solution; the monolayer graphite oxide sheet solution was then centrifuged in a high-speed centrifuge at a centrifugal speed of 15000 rpm for 20 minutes, and the obtained solid was vacuum dried at 0.085 MPa for 2 hours; the dried graphene oxide solid was dispersed in a dimethyl sulfoxide solution at a dosage ratio of 1:1, and stirred at 150 rpm for 20 minutes. After being uniformly mixed, it was transferred to a reactor and reacted at 180°C for 12 hours. After filtering, it was washed with deionized water for 3 times and dried under vacuum at 0.085MPa for 2 hours to obtain a single-layer graphene; 1 part of the single-layer graphene was mixed with 100 parts of deionized water, and then 15 parts of bromoacetic acid were added, and ultrasonicated at 30kHz power for 20 minutes, and then reacted at room temperature for 5 hours; after the reaction was completed, it was centrifuged at 9000rpm for 30 minutes, and the solid was washed with deionized water for 3 times, and then freeze-dried at -40°C for 2 hours to obtain a carboxyl-functionalized single-layer graphene; (2) First, the nanocellulose raw material and montmorillonite were mixed in a mass ratio of 0.6:1, and ball milled at a speed of 450 rpm for 5.5 h. A 6% sodium hydroxide solution and a 60% n-butanol solution were mixed in a volume ratio of 1:3 to prepare a pretreatment solution. The pH was adjusted to 7 and the temperature was raised to 45°C. The ball-milled nanocellulose was completely immersed in the pretreatment solution for 18 h. The solid-liquid mass ratio was 1:10. The pretreatment solution was then heated to 55°C and the pH was adjusted to 8. The solution was then immersed for another 1.5 h. Ultrasonic low-frequency short-time oscillation was performed at the current temperature. The ultrasonic conditions were: frequency 35 kHz, power 400 W, and ultrasonic time 15 min to obtain pretreated nanocellulose. The pretreated nanocellulose micro-cellulose, hydroxyl cardanol containing hydroxyl groups on the side chains, and ethanol were mixed in a mass ratio of 3:1:10, placed in a reactor, heated to 120°C for reaction for 3 h, and after the reaction, the nanocellulose was washed by centrifugation 3 times with deionized water. The speed is 10000rpm, and the upper suspension is collected to obtain modified nanocellulose; the modified nanocellulose and deionized water are mixed in proportion to prepare a modified nanofiber dispersion with a mass fraction of 1.0%, and the mixture is stirred at 150rpm for 30min; 10 parts of the modified nanofiber dispersion are taken, and an appropriate amount of glacial acetic acid is added to adjust the pH value of the dispersion to 4, and then stirred at 150rpm for 1h, and then the carboxyl functionalized single-layer graphene is added to the dispersion and mixed and stirred at 150rpm for 3h to obtain a uniform solution, and the mass ratio of the carboxyl functionalized single-layer graphene to the dispersion is 0.03:1; finally, the solution is poured into a polytetrafluoroethylene mold and frozen in liquid nitrogen for 3min, and the frozen solid sample is further vacuum freeze-dried at -60°C and 1Pa for 48h to obtain a 0.8mm composite aerogel masterbatch; the remaining steps are the same as those in Example 2.

[0025] Comparative Example 3: The difference between Comparative Example 3 and Example 2 is that steps (1) (2) are different. Steps (1) (2) are changed to: (1) Take 3 parts of natural graphite powder, add 12 parts of 95% concentrated sulfuric acid, 2.5 parts of potassium persulfate and 2.5 parts of phosphorus pentoxide, mix them evenly at 80°C, and react for 5 hours; after the reaction is completed, cool to room temperature, add 10 parts of deionized water and let stand for 24 hours, then filter and separate with a 0.2 micron pore cellulose acetate membrane, take the solid and wash it with deionized water 3 times, then let stand for 24 hours to obtain oxidized graphite; slowly add the pre-oxidized graphite to 130 parts of the cooled 0°C mixed solution while stirring, and add 95% concentrated sulfuric acid and potassium permanganate in a mass ratio of 8:1 The composition is as follows: the stirring speed is 60 rpm, after stirring at 35°C for 2 hours, 250 parts of deionized water are used for dilution, 600 parts of deionized water are added after continuing to stir for 2 hours, and 20 parts of hydrogen peroxide solution are added after stirring for another 2 hours; filtering, washing the solid with a dilute hydrochloric acid aqueous solution with a concentration of 8% twice, and then washing it with deionized water for 3 times, and then dialyzing the product for one week to obtain graphite oxide; the obtained graphite oxide is prepared into an aqueous solution with a concentration of 0.5 mg / ml, and ultrasonically treated in an ultrasonic machine for 30 minutes with an ultrasonic power of 35 kHz to obtain a single-layer graphite oxide sheet solution; and then the single-layer graphite oxide sheet solution is centrifuged in a high-speed centrifuge at a centrifugal speed of 15000 rpm for 20 minutes. , and the obtained solid was vacuum dried at 0.085MPa for 2h; the dried graphene oxide solid was dispersed in dimethyl sulfoxide solution, the dosage ratio of the two was 1:1, and the mixture was transferred to a reactor after stirring at 150rpm for 20min, and reacted at 180℃ for 12h. After filtering, it was washed with deionized water for 3 times, and vacuum dried at 0.085MPa for 2h to obtain single-layer graphene; 2 portions of single-layer graphene were weighed and placed in each of the centrifuge tubes with holes, and a 1000Da dialysis bag was put on the outside of the centrifuge tube as the positive and negative electrode materials, respectively, and the distance between the two electrode materials was 2cm; 20 portions of 1-butyl-3-methyltetrafluoroborate ionic liquid and 20 portions of deionized water were taken. The mixture is used as an electrolyte, and after the electrode is soaked for 1 hour, a direct current power supply is turned on, and a direct current voltage of 10V is used; during the power-on process, the positive and negative electrodes are exchanged every 2 hours, and the power is stopped after the reaction for 10 hours; the electrolyzed electrolyte is placed in a centrifuge tube, and centrifuged at 9000rpm for 30 minutes to obtain a bottom precipitate, and the bottom precipitate is placed in a dialysis bag with a molecular weight cutoff of 1000Da, and water is used as a dialysis fluid, and the dialysis is performed for 3 days, and the water is changed every 8 hours, and the liquid in the bag is placed in a hydrothermal autoclave and maintained at 180°C for 3 hours; then the solution is centrifuged at 9000rpm for 30 minutes, and the solid is washed twice with deionized water, and then dried at room temperature and pressure for 5 hours to obtain a single-layer graphene quantum dot; (2) First, the mass ratio of nanocellulose raw material and montmorillonite was 0.6:1, and ball milling was performed. The ball milling speed was 450 rpm and the ball milling time was 5.5 h. A 6% sodium hydroxide solution and a 60% n-butanol solution were mixed in a volume ratio of 1:3 to prepare a pretreatment solution. The pH value was adjusted to 7 and the temperature was raised to 45°C. The ball-milled nanocellulose was completely immersed in the pretreatment solution for 18 h. The solid-liquid mass ratio was 1:10. The pretreatment solution was then heated to 55°C and the pH value was adjusted to 8. The solution was then immersed for another 1.5 h. Ultrasonic low-frequency short-time oscillation was performed at the current temperature. The ultrasonic conditions were: frequency 35 kHz, power 400 W, and ultrasonic time 15 min to obtain pretreated nanocellulose. The pretreated nanocellulose micro-cellulose, hydroxyl cardanol containing hydroxyl groups on the side chains, and ethanol were mixed in a mass ratio of 3:1:10, placed in a reactor, heated to 120°C for reaction for 3 h, and after the reaction, the nanocellulose was centrifuged and washed three times with deionized water. The centrifuge speed is 10000rpm, and the upper suspension is collected to obtain modified nanocellulose; the modified nanocellulose and deionized water are mixed in proportion to prepare a modified nanofiber dispersion with a mass fraction of 1.0%, and stirred at 150rpm for 30min; 10 parts of the modified nanofiber dispersion are taken, and an appropriate amount of glacial acetic acid is added to adjust the pH value of the dispersion to 4, and then stirred at 150rpm for 1h, and then the single-layer graphene quantum dots are added to the dispersion and mixed and stirred at 150rpm for 3h to obtain a uniform solution, and the mass ratio of the single-layer graphene quantum dots to the dispersion is 0.03:1; finally, the solution is poured into a polytetrafluoroethylene mold and frozen in liquid nitrogen for 3min, and the frozen solid sample is continued to be vacuum freeze-dried at -60°C and 1Pa for 48h to obtain a 0.8mm composite aerogel masterbatch; the remaining steps are the same as Example 2.

[0026] Comparative Example 4: The difference between Comparative Example 4 and Example 2 is that step (2) is different, and step (2) is changed to: nanocellulose micro-particles, hydroxycardanol containing hydroxyl groups in the side chain and ethanol are mixed in a mass ratio of 3:1:10, placed in a reactor, heated to 120°C for reaction for 3 hours, and after the reaction is completed, centrifuged and washed three times with deionized water at a centrifugal speed of 10000 rpm, and the upper suspension is collected to obtain modified nanocellulose; the modified nanocellulose is mixed with deionized water in proportion to prepare a modified nanofiber dispersion with a mass fraction of 1.0%, and stirred at a speed of 150 rpm for 30 minutes. uniform; taking 10 parts of the modified nanofiber dispersion, adding an appropriate amount of glacial acetic acid to adjust the pH value of the dispersion to 4, and then stirring at 150rpm for 1h, and then adding the carboxyl functionalized single-layer graphene quantum dots to the dispersion and mixing and stirring at 150rpm for 3h to obtain a uniform solution, the mass ratio of the carboxyl functionalized single-layer graphene quantum dots to the dispersion is 0.03:1; finally, pouring the solution into a polytetrafluoroethylene mold and freezing it in liquid nitrogen for 3min, and continuing the vacuum freeze-drying of the frozen solid sample at -60°C and 1Pa for 48h to obtain a 0.8mm composite aerogel masterbatch; the remaining steps are the same as in Example 2.

[0027] Comparative Example 5; The difference between Comparative Example 5 and Example 2 is that step (2) is different. Step (2) is changed to: first, the mass ratio of nanocellulose raw material and montmorillonite is 0.6:1, and ball milling is performed. The ball milling speed is 450 rpm and the ball milling time is 5.5 hours; a sodium hydroxide solution with a mass concentration of 6% and a n-butanol solution with a mass concentration of 60% are mixed in a volume ratio of 1:3 to prepare a pretreatment solution, the pH is adjusted to 7, the temperature is raised to 45°C, and the ball-milled nanocellulose is completely immersed in the pretreatment solution for 18 hours, the solid-liquid mass ratio is 1:10, and then the pretreatment solution is heated to 55°C, the pH is adjusted to 8, and the solution is immersed for another 1.5 hours. At the current temperature, ultrasonic low-frequency short-time oscillation is performed, and the ultrasonic conditions are: frequency 35kHz, power 400W, and ultrasonic time 15min to obtain modified nanocellulose; the modified nanocellulose is mixed with deionized water in proportion to prepare a nanocellulose having a mass fraction of 1.0%. The modified nanofiber dispersion was stirred at 150 rpm for 30 min to make it uniform; 10 parts of the modified nanofiber dispersion were taken, an appropriate amount of glacial acetic acid was added to adjust the pH value of the dispersion to 4, and then stirred at 150 rpm for 1 h, and then the carboxyl functionalized single-layer graphene quantum dots were added to the dispersion and mixed at 150 rpm for 3 h to obtain a uniform solution, and the mass ratio of the carboxyl functionalized single-layer graphene quantum dots to the dispersion was 0.03:1; finally, the solution was poured into a polytetrafluoroethylene mold and frozen in liquid nitrogen for 3 min, and the frozen solid sample was continued to be vacuum freeze-dried at -60°C and 1 Pa for 48 h to obtain a 0.8 mm composite aerogel masterbatch; the remaining steps were the same as in Example 2.

[0028] Comparative Example 6; The difference between Comparative Example 6 and Example 2 is that step (2) is different, and step (2) is changed to: first, the mass ratio of the nanocellulose raw material and the montmorillonite is 0.6:1 and mixed, and the ball milling is performed at a ball milling speed of 450 rpm, ball milling time is 5.5h; a 6% sodium hydroxide solution and a 60% n-butanol solution are mixed in a volume ratio of 1:3 to prepare a pretreatment solution, the pH is adjusted to 7, the temperature is raised to 45°C, the ball-milled nanocellulose is completely immersed in the pretreatment solution for 18h, the solid-liquid mass ratio is 1:10, and then the pretreatment solution is heated to 55°C, the pH is adjusted to 8, and then immersed for another 1.5h, and ultrasonic low-frequency short-time oscillation is performed at the current temperature. The ultrasonic conditions are: frequency 35kHz, power 400W, ultrasonic time 15min, and pretreated nanocellulose is obtained; the pretreated nanocellulose micro, hydroxy cardanol containing hydroxyl groups in the side chain and ethanol are mixed in a mass ratio of 3:1:10, placed in a reactor, heated to 120°C for reaction for 3h, and after the reaction is completed, deionized water is used to The mixture was centrifuged and washed for 3 times at a centrifugal speed of 10000 rpm, and the upper suspension was collected to obtain modified nanocellulose; the modified nanocellulose was mixed with deionized water in proportion to prepare a modified nanofiber dispersion with a mass fraction of 1.0%, and stirred at 150 rpm for 30 min; 10 parts of the modified nanofiber dispersion were taken, and an appropriate amount of glacial acetic acid was added to adjust the pH value of the dispersion to 4, and then stirred at 150 rpm for 1 h, and then carboxyl functionalized single-layer graphene quantum dots were added to the dispersion and mixed and stirred at 150 rpm for 3 h to obtain a uniform solution, and the mass ratio of carboxyl functionalized single-layer graphene quantum dots to the dispersion was 0.03:1; finally, the solution was centrifuged at 10000 rpm for 20 min, and the solid was dried at room temperature and pressure for 5 h to obtain a composite aerogel masterbatch; the remaining steps were the same as in Example 2.

[0029] Effect example Table 1 below shows the performance analysis results of an antibacterial and thermal insulation graphene quantum dot cloud fleece using Examples 1 to 3 of the present invention and Comparative Examples 1 to 6.

[0030] Table 1 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 uses a chemical method to prepare graphene with a single-layer two-dimensional structure, that is, a single-layer graphene; using this single-layer graphene as a raw material, a graphene nano-quantum dot with a single-layer structure is prepared by an electrochemical reaction; compared with ordinary graphene quantum dots, the graphene quantum dots prepared by the present invention not only reach the nanometer level in size, but also can increase the contact surface between the quantum dots and the bacterial cells, so that it interacts with the phospholipid molecules on the bacterial cell membrane, thereby killing bacteria; its single-layer two-dimensional structure also makes the edges of the quantum dots sharper, which can improve the effect and success rate of cutting the cell wall of damaged bacteria; on this basis, the single-layer graphene quantum dots are functionally modified to make their surface rich in carboxyl groups, and they are connected to nanocellulose through carboxyl groups and attached to the cellulose surface, which greatly improves the agglomeration problem of graphene quantum dots. Secondly, the present invention uses the mechanical force chemical action generated during the ball milling process to destroy the physical structure of nanocellulose, and then uses the strong action of a polar solvent rich in hydroxyl groups, combined with ultrasound to destroy the intermolecular hydrogen bonds of cellulose macromolecules, so that it dissociates. Then, it is combined with hydroxycardanol containing a hydroxyl group in the side chain, and its photosensitive property of releasing active oxygen under the action of sunlight is utilized to cooperate with the graphene quantum dots attached to cellulose to efficiently catalyze the generation of active oxygen, thereby achieving the sterilization effect. From the comparison of the experimental data of the antibacterial properties of the embodiment and the comparative example, it can be found that the present invention prepares the modified nanocellulose into aerogel, and adds it into the polyester as an antibacterial masterbatch to prepare the cloud velvet, which solves the dispersibility problem of cellulose and effectively improves the warmth retention effect of the cloud velvet.

[0031] 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 antibacterial and heat-retaining graphene quantum dot cloud velvet, characterized in that: The method comprises the following preparation steps: (1) Take 3 parts of natural graphite powder, add 12 parts of concentrated sulfuric acid, 2-3 parts of potassium persulfate and 2-3 parts of phosphorus pentoxide, mix them evenly at 80°C, and react for 4-6 hours; after the reaction is completed, cool to room temperature, add 10 parts of deionized water to dilute, let stand for 24 hours, and then separate by membrane filtration, take the solid and wash it with deionized water for 3 times, and then let stand for 24 hours to obtain oxidized graphite; slowly add the pre-oxidized graphite to 120-140 parts of the cooled 0°C mixed solution while stirring, the stirring speed is 60rpm, stir at 35°C for 2 hours, dilute with 250 parts of deionized water, continue to stir for 2 hours, add 600 parts of deionized water, and then add 15-25 parts of hydrogen peroxide solution after stirring for 2 hours; filter, take the solid and dilute it with 8% concentration of hydrogen peroxide solution The obtained graphene oxide was washed twice with a hydrochloric acid aqueous solution and then washed three times with deionized water, and then the product was dialyzed for one week to obtain graphite oxide; the obtained graphite oxide was prepared into an aqueous solution with a concentration of 0.5 mg / ml, and ultrasonically treated in an ultrasonic machine for 30 minutes with an ultrasonic power of 35 kHz to obtain a single-layer graphite oxide sheet solution; the single-layer graphite oxide sheet solution was centrifuged in a high-speed centrifuge at a centrifugal speed of 15000 rpm for 20 minutes, and the obtained solid was vacuum dried at 0.085 MPa for 2 hours; the dried graphene oxide solid was dispersed in a dimethyl sulfoxide solution at a dosage ratio of 1:1, and the mixture was transferred to a reactor after stirring at 150 rpm for 20 minutes and then heated at 160-200 °C for 2 hours. ℃ for 10-14h, after filtering, wash with deionized water for 3 times, and dry under vacuum at 0.085MPa for 2h to obtain single-layer graphene; weigh 2 parts of single-layer graphene, put 1 part each in a centrifuge tube with holes, put a 1000Da dialysis bag on the outside of the centrifuge tube, use them as positive and negative electrode materials respectively, and the distance between the two electrode materials is 2cm; take 20 parts of 1-butyl-3-methyl tetrafluoroborate ionic liquid and 20 parts of deionized water as electrolyte, soak the electrodes for 1h, start to connect the DC power supply, and the DC voltage used is 10V; during the power-on process, exchange the positive and negative electrodes every 2h, and stop the power-on after 10h of reaction; put the electrolyzed electrolyte in a centrifuge tube, and centrifuge at a speed of 8000-10000rpm. Centrifuge for 30 minutes to obtain a bottom precipitate, dialyze, place the liquid in the bag in a hydrothermal autoclave and keep it at 180°C for 3 hours; then centrifuge the solution at 8000-10000rpm for 30 minutes, wash the solid with deionized water twice, and then dry it at room temperature and pressure for 5 hours to obtain a single-layer graphene quantum dot; mix 1 part of the single-layer graphene quantum dot with 100 parts of deionized water, then add 10-20 parts of bromoacetic acid, ultrasonicate at 30kHz power for 10-30 minutes, and then react at room temperature for 5 hours; after the reaction is completed, centrifuge at 8000-10000rpm for 30 minutes, wash the solid with deionized water 3 times, and then freeze-dry at -40°C for 2 hours to obtain a carboxyl-functionalized single-layer graphene quantum dot; (2) First, the mass ratio of the nanocellulose raw material and montmorillonite is 0.2-1:1, and the ball milling treatment is carried out at a ball milling speed of 300-600 rpm and a ball milling time of 3-8 h; prepare a pretreatment solution, adjust the pH to 7, raise the temperature to 40-50°C, and completely immerse the ball-milled nanocellulose in the pretreatment solution for 12-24 h, and the solid-liquid mass ratio is 1:10; then the pretreatment solution is heated to 50-60°C, the pH is adjusted to 8, and the nanocellulose is immersed for another 1-2 h, and ultrasonic low-frequency short-time oscillation is performed at the current temperature to obtain pretreated nanocellulose; the pretreated nanocellulose micro-particles, hydroxycardanol containing hydroxyl groups in the side chains, and ethanol are mixed at a mass ratio of 2-4:1:10, placed in a reactor, heated to 100-140°C for reaction for 2-4 h, and after the reaction, centrifuged and washed three times with deionized water at a centrifugal speed of 10000 rpm, and the upper suspension is collected. , the modified nanocellulose is obtained; the modified nanocellulose is mixed with deionized water in proportion to prepare a modified nanofiber dispersion with a mass fraction of 1.0%, and stirred at 150 rpm for 30 min; 10 portions of the modified nanofiber dispersion are taken, an appropriate amount of glacial acetic acid is added to adjust the pH value of the dispersion to 4, and then stirred at 150 rpm for 1 h, and then carboxyl functionalized single-layer graphene quantum dots are added to the dispersion and mixed and stirred at 150 rpm for 3 h to obtain a uniform solution; finally, the solution is poured into a polytetrafluoroethylene mold and frozen in liquid nitrogen for 3 min, and the frozen solid sample is further vacuum freeze-dried at -60 ° C and 1 Pa for 48 h to obtain a 0.1-1.5 mm composite aerogel masterbatch; (3) Terephthalic acid, ethylene glycol and composite aerogel masterbatch 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 melted by screw extrusion, and the ejected fiber is quickly shaped by high-speed stretching and ring-blown air cooling, and flows into the reciprocating machine for barrel bundling. When the technology reaches the total denier of composite production of 600 denier, 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 it, and then it enters the cutting machine for cutting. After cutting, it is placed in a three-layer oven for heat setting to make cloud velvet.

2. The method for preparing the antibacterial and heat-retaining graphene quantum dot cloud velvet according to claim 1, characterized in that: The concentration of concentrated sulfuric acid in step (1) is 92-98%.

3. The method for preparing the antibacterial and heat-retaining graphene quantum dot cloud velvet according to claim 1, characterized in that: The filter membrane in step (1) is a cellulose acetate membrane with a pore size of 0.2 micrometers.

4. The method for preparing the antibacterial and heat-retaining graphene quantum dot cloud velvet according to claim 1, characterized in that: The mixed solution in step (1) is composed of 95% concentrated sulfuric acid and potassium permanganate in a mass ratio of 8:

1.

5. The method for preparing the antibacterial and heat-retaining graphene quantum dot cloud velvet according to claim 1, characterized in that: The concentration of the dilute hydrochloric acid aqueous solution in step (1) is 8%.

6. The method for preparing the antibacterial and heat-retaining graphene quantum dot cloud velvet according to claim 1, characterized in that: The dialysis process in step (1) is to place the bottom precipitate in a dialysis bag with a molecular weight cutoff of 1000Da, use water as the dialysis fluid, and dialyze for 3 days, changing the water every 8 hours.

7. The method for preparing the antibacterial and heat-retaining graphene quantum dot cloud velvet according to claim 1, characterized in that: The pretreatment solution in step (2) is prepared by mixing a sodium hydroxide solution with a mass concentration of 2-10% and a n-butanol solution with a mass concentration of 45-75% in a volume ratio of 1:1-5.

8. The method for preparing the antibacterial and heat-retaining graphene quantum dot cloud velvet according to claim 1, characterized in that: The ultrasonic conditions used in step (2) are: frequency 20-50 kHz, power 200-600 W, and ultrasonic time 10-20 min.

9. The method for preparing the antibacterial and heat-retaining graphene quantum dot cloud velvet according to claim 1, characterized in that: In the step (2), the mass ratio of carboxyl functionalized single-layer graphene quantum dots to the dispersion is 0.01-0.05:

1.

10. The method for preparing the antibacterial and heat-retaining graphene quantum dot cloud velvet according to claim 1, characterized in that: The heat setting temperature in step (3) is 180°C.

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